200161by PDF

SW8463C
TEST METHODS FOR EVALUATING

SOLID WASTE, .PHYSICAL/CHEMICAL
METHODS, SW-846, 3RD EDITION,
PROPOSED UPDATE II
W Recycled/Recyctable
rX :\\ Printed on paper t~t contains
'0(7 at least 50% <ec;yd41<! fiber
PROPOSED UPDATE II
THIS PACKET CONTAINS THE OFFICIAL PROPOSED UPDATE II FOR

TEST METHODS FOR EVALUATING SOLID WASTE, PHYSICAL/CHEMICAL
METHODS, SW-846, 3RD EDITION
• Table of Contents
• Proposed Methods for Update II, dated November 1992
• Proposed Chapters Two, Three, Four, and Seven
;.·:_, i,_i _.,:w._;,_: _~'- · J'·d ,· · :· _•.:_P'_,'. :. •.· •., ~ ~lr ~strib~
·:-.·:·::::'.""·:·.··-.·:···:·::"'.'.': .. :...... :· ., ....:"
.;
colbred sheets ot
If you have any problems, telephone the Methods Information

Communication Exchange at 703-821-4789. If you have any questions
concerning your SW-846 subscription, telephone the U.S. Government
Printing Office at 202-783-3238.
ME'IHOOO INCLUDED IN PRO:Fa>ED UPDA.TE PACKAGE I
* Cllapter 1 Definitions
* Chapter 2 Tables
* Chapter 4 Table 4-1
* Chapter 7 Reactive Cyanide and Sulfide
* Method 1310 - Extraction Procedure (EP) Toxicity Test Method and Structural
Integrity Test
* Method 1330 - Extraction Procedure for Oily Wastes
* Method 3005 - Acid Digestion of Waters for Total Recoverable or Dissolved
Metals for Analysis by Flame Atomic Absorption Spectroscopy
or Inductively Coupled Plasma Spectroscopy
* Method 3010 - Acid Digestion of Aqueous Samples of Extracts for Total Metals
for Analysis by Flame Atanic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
* Method 3020 - Acid Digestion of Aqueous Samples and Extracts for Total Metals
for Analysis by Furnace Atomic Absorption Spectroscopy
* Method 3050 - Acid Digestion of Sediments, Sludges, and Soils
* Method 3510 - Separatory Funnel Liquid - Liquid Extraction
* Method 3520 - Continuous Liquid-Liquid Extraction
* Method 3540 - Soxhlet Extraction
* Method 3600 - Cleanup
T Method 3650 - Acid-Base Partition Cleanup
* Method 5030 - Purge-and-Trap
T Method 6010 - Inductively Coupled Plasma Atanic Emission Spectroscopy
* Method 7000 - Atomic Absorption Methods
* Method 7061 - Arsenic (AA, Gaseous Hydride)
N Method 7081 - Barium (AA, Furnace Technique)
* Method 7196 - Chraniun, Hexavalent (Colorimetric)
N Method 7211 - Copper (AA, Furnace Technique)
N Method 7381 - Iron (AA; Furnace Technique)
N Method 7430 - Lithitm (AA, Direct Aspiration)
N Method 7461 - Manganese (AA, Furnace Technique)
T Method 7760 - Silver (AA, Direct Aspiration)
N Method 7761 - Silver (AA, Furnace Technique)
N Method 7780 - Strontitm (AA, Direct Aspiration)
N Method 7951 - Zinc (AA, Furnace Technique)
* Method 8000 - Gas Chromatography
* Method 8010 - Halogenated Volatile Organics
N Method 8011 - 1,2-Dibroroc>ethane and 1,2-Dibrano-3-chloropropane in Water by
Microextraction and Gas Chranatography
* Method 8015 - Nonhalogenated Volatile Organics
N Method 8021 - Volatile Organic Corrpounds in Water by Purge-and-Trap capillary
Column Gas Chromatography with PID and Electroconductivity
Detector in Series
* Method 8030 - Acrolein, Acrylonitrile, Acetonitrile
* Method 8040 - Phenols
N Method 8070 - Nitrosamines
N Method 8110 - Haloethers
* Method 8120 - Chlorfnated Hydrocarbons
N Method 8141 - Organophosphorus Pesticides capillary Column
* Method 8150 - Chlorinated Herbicides
* Method 8240 - OC/MS for Volatile Organics
* Method 8250 - OC/MS for Semivolatile Organics: Packed Column Technique
N Method 8260 - OC/MS for Volatile Organics: capillary Column
METHOI:S INCLUDED IN PROPOSED UPfll\TE PACKAGE I (cont'd)
* Method 8270 - GC/MS for Semivolatile Organics: Capillary Column Technique

T Method 9010 and 9010A - Total and Amenable Cyanides
N Method 9021 - Purgeable Organic Halides (POX)
T Method 9030 - Acid-Soluble and Acid-Insoluble Sulfides
N Method 9031 - Extractable Sulfides
* Method 9090 - Compatibility Test for Wastes and Membrane Liners
* Indicates partial rev1s1on

N Indicates a new method
T Indicates a total revision
ABSTRACT
Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-
846) provides test procedures and guidance which are recommended for use in
conducting the evaluations and measurements needed to comply with the Resource
Conservation and Recovery Act (RCRA), Public Law 94-580. These methods are
approved by the U.S. Environmental Protection Agency for obtaining data to
satisfy the requirements of 40 CFR Parts 122 through 270. This manual
presents the state-of-the-art in routine analytical testing adapted for the
RCRA program. It contains procedures for field and laboratory quality
control, sampling, determining hazardous constituents in wastes, determining
the hazardous characteristics of wastes (toxicity, ignitibility, reactivity,
and corrosivity), and for determining physical properties of wastes. It also
contains guidance on how to select appropriate methods.
The hazardous waste regulations under Subtitle C of the Resource
Conservation and Recovery Act (RCRA) require that specific testing methods
described in this manual be employed for certain applications. The following
sections of 40 CFR require the use of SW-846 methods:
260.22(d)(l)(i) - Submission of data in support of petitions to
exclude a waste produced at a particular facility (delisting petitions).
261.22(a) - Eva1uation of wastes against the Corrosivity
Characteristic (corrosivity).
261.24(a) - Evaluation of wastes against the Extraction Procedure
Toxicity Characteristic (mobility of toxic species).
264.314(c) and 265.314(d) - Evaluation of wastes to determine if free
liquid is a component of the waste (free liquid).
270.62(b)(2)(i)(C) - Analysis of wastes prior to conducting a trial
burn in support of an application for a hazardous waste incineration permit
(incinerator permit).
ABSTRACT - I Revision I
December 1987
Disclaimer
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use by the U.S. En vi ronmenta l Protection
Agency.
DISCLAIMER - I Revision 0
December 1987
T A B L E 0 F C 0 NT E NT S
VOLUME ONE
SECTION A
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
PART I METHODS FOR ANALYTES AND PROPERTIES

CHAPTER ONE -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
CHAPTER TWO -- CHOOSING THE CORRECT PROCEDURE
2.1 Purpose
2.2 Required Information
2.3 Implementing the Guidance
2.4 Characteristics
2.5 Ground Water
2.6 References
CHAPTER THREE -- METALLIC ANALYTES
3.1 Sampling Considerations
3.2 Sample Preparation Methods
Method 3005A: Acid Digestion of Waters for Total Recoverable or
Dissolved Metals for Analysis by Flame Atomic Absorption
(FAA) or Inductively Coupled Plasma {ICP) Spectroscopy
Method 3010A: Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Flame Atomic Absorption {FAA) or
Inductively Coupled Plasma (ICP) Spectroscopy
Method 3015: Microwave Assisted Acid Digestion of Aqueous Samples and
Extracts
CONTENTS - 1 Revision 2
November 1992
Method 3020A: Acid Digestion of Aqueous Samples and Extracts for Total
Meta 1s for Ana 1ys is by Graphite Furnace Atomic
Absorption (GFAA) Spectroscopy
Method 3040: Dissolution Procedure for Oils, Greases, or Waxes
Method 3050A: Acid Digestion of Sediments, Sludges, and Soils
Method 3051: Microwave Assisted Acid Digestion of Sediments, Sludges,
Soils, and Oils
3.3 Methods for Determination of Metals
Method 6010A: Inductively Coupled Plasma-Atomic Emission Spectroscopy
Method 6020: Inductively Coupled Plasma - Mass Spectrometry
Method 7000A: Atomic Absorption Methods
Method 7020: Aluminum (AA, Direct Aspiration)
Method 7040: Antimony (AA, Direct Aspiration)
Method 7041: Antimony (AA, Furnace Technique)
Method 7060A: Arsenic (AA, Furnace Technique)
Method 7061A: Arsenic (AA, Gaseous Hydride)
Method 7062: Antimony and Arsenic (AA, Gaseous Borohydride)
Method 7080A: Barium (AA, Direct Aspiration)
Method 7081: Barium (AA, Furnace Technique)
Method 7090: Berylliu~ (AA, Direct Aspiration)
Method 7091: Beryllium (AA, Furnace Technique)
Method 7130: Cadmium (AA, Direct Aspiration)
Method 7131A: Cadmium (AA, Furnace Technique)
Method 7140: Calcium (AA, Direct Aspiration)
Method 7190: Chromium (AA, Direct Aspiration)
Method 7191 : Chromium (AA, Furnace Technique)
Method 7195: Chromium, Hexavalent (Coprecipitation)
Method 7196A: Chromium, Hexavalent (Colorimetric)
Method 7197: Chromium, Hexavalent (Chelation/Extraction)
Method 7198: Chromium, Hexavalent (Differential Pulse Polarography)
Method 7200: Cobalt (AA, Direct Aspiration)
Method 7201: Cobalt (AA, Furnace Technique)
Method 7210: Copper (AA, Direct Aspiration)
Method 7211: Copper (AA, Furnace Technique)
Method 7380: Iron (AA, Direct Aspiration)
Method 7381: Iron (AA, Furnace Technique)
Method 7420: Lead (AA, Direct Aspiration)
Method 7421: Lead (AA, Furnace Technique)
Method 7430: Lithium (AA, Direct Aspiration)
Method 7450: Magnesium (AA, Direct Aspiration)
Method 7460: Manganese (AA, Direct Aspiration)
Method 7461: Manganese (AA, Furnace Technique)
Method 7470A: Mercury in Liquid Waste (Manual Cold-Vapor Technique)
Method 7471A: Mercury in Solid or Semisolid Waste (Manual Cold-Vapor
Technique)
Method 7480: Molybdenum (AA, Direct Aspiration)
Method 7481: Molybdenum (AA, Furnace Technique)
Method 7520: Nickel (AA, Direct Aspiration)
Method 75.50: Osmium (AA, Direct Aspiration)
Method 7610: Potassium (AA, Direct Aspiration)
Method 7740: Selenium (AA, Furnace Technique)
November 1992
Method 7741A: Selenium (AA, Gaseous Hydride)
Method 7742: Selenium (AA, Gaseous Borohydride)
Method 7760A: Silver (AA, Direct Aspiration)
Method 7761: Silver (AA, Furnace Technique)
Method 7770: Sodium (AA, Direct Aspiration)
Method 7780: Strontium (AA, Direct Aspiration)
Method 7840: Thallium (AA, Direct Aspiration)
Method 7841: Thallium (AA, Furnace Technique)
Method 7870: Tin (AA, Direct Aspiration)
Method 7910: Vanadium (AA, Direct Aspiration)
Method 7911: Vanadium (AA, Furnace Technique)
Method 7950: Zinc (AA, Direct Aspiration)
Method 7951: Zinc (AA, Furnace Technique)
APPENDIX -- COMPANY REFERENCES
November 1992
VOLUME ONE
SECTION B
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
PREFACE
ACKNOWLEDGEMENTS
CHAPTER ONE. REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
5.0 Definitions
6.0 References
CHAPTER FOUR -- ORGANIC ANALYTES
4.1 General Considerations
4.2 Sample Preparation Methods
4.2.l Extractions and Preparations
Method 3500A: Organic Extraction and Sample Preparation
Method 35108: Separatory Funnel Liquid-Liquid Extraction
Method 35208: Continuous Liquid-Liquid Extraction
Method 35408: Soxhlet Extraction
Method 3541: Automated Soxhlet Extraction
Method 3550A: Ultrasonic Extraction
Method 3580A: Waste Dilution
Method 5030A: Purge-and-Trap
Method 5040A: Analysis of Sorbent Cartridges from Volatile Organic
Sampling Train {VOST): Gas Chromatography/Mass
Spectrometry Technique
Method 5041: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train: Wide-bore Capillary
Column Technique
Method 5100: Determination of the Volatile Organic Concentration of
Waste Samples
Method 5l10: Determination of Organic Phase Vapor Pressure in Waste
Samples
4.2.2 Cleanup
Method 36008: Cleanup
Method 3610A: Alumina Column Cleanup
November 1992
Method 3611A: Alumina Column Cleanup and Separation of
Petroleum Wastes
Method 3620A: Florisil Column Cleanup
Method 36308: Silica Gel Cleanup
Method 3640A: Gel-Permeation Cleanup
Method 3650A: Acid-Base Partition Cleanup
Method 3660A: Sulfur Cleanup
Method 3665: Sulfuric Acid/Permanganate Cleanup
4.3 Determination of Organic Analytes
4.3.1 Gas Chromatographic Methods
Method 8000A: Gas Chromatography
Method 80108: Halogenated Volatile Organics by Gas Chromatography
Method 8011: 1,2-Dibromoethane and 1,2-Dibromo-3-chloropropane by
Microextraction and Gas Chromatography
Method 8015A: Nonhalogenated Volatile Organics by Gas Chromatography
Method 8020A: Aromatic Volatile Organics by Gas Chromatography
Method 8021A: Halogenated Volatiles by Gas Chromatography Using
Photoionization and Electrolytic Conductivity Detectors
in Series: Capillary Column Technique
Method 8030A: Acrolein and Acrylonitrile by Gas Chromatography
Method 8031: Acrylonitrile by Gas Chromatography
Method 8032: Acrylamide by Gas Chromatography
Method 8040A: Phenols by Gas Chromatography
Method 8060: Phthalate Esters
Method 8061: Phthalate Esters by Capillary Gas Chromatography with
Electron Capture Detection {GC/ECD)
Method 8070: Nitrosamines by Gas Chromatography
Method 8080A: Organochlorine Pesticides and Polychlorinated Biphenyls
by Gas Chromatography
Method 8081: Organochlorine Pesticides, Halowaxes and PCBs as
Aroclors by Gas Chromatography: Capillary Column
Technique
Method 8090: Nitroaromatics and Cyclic Ketones
Method 8100: Polynuclear Aromatic Hydrocarbons
Method 8110: Haloethers by Gas Chromatography
Method 8120A: Chlorinated Hydrocarbons by Gas Chromatography
Method 8121: Chlorinated Hydrocarbons by Gas Chromatography:
Capillary Column Technique
Method 8140: Organophosphorus Pesticides
Method 8141A: Organophosphorus Compounds by Gas Chromatography:
Capillary Column Technique
Method 81508: Chlorinated Herbicides by Gas Chromatography
Method 8151: Chlorinated Herbicides by GC Using Methylation or
Pentafluorobenzylation Derivatization: Capillary Column
Technique
4.3.2 Gas Chromatographic/Mass Spectroscopic Methods
Method 82408: Volatile Organics by Gas Chromatography/Mass
Spectrometry {GC/MS)
November 1992
Method 8250A: Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS)
Method 8260A: Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS): Capillary Column Technique
Method 82708: Semi vol at i1 e Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS): Capillary
Column Technique
Method 8280: The Analysis of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans
Appendix A: Signal-to-Noise Determination Methods
Appendix B: Recommended Safety and Handling Procedures for
PCDDs/PCDFs
Method 8290: Polychlorinated Dibenzodioxins (PCDDs) and
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas Chromatography/High-Resolution Mass Spectrometry
(HRGC/HRMS)
4.3.3 High Performance Liquid Chromatographic Methods
Method 8310: Polynuclear Aromatic Hydrocarbons
Method 8315: Determination of Carbonyl Compounds by High Performance
Liquid C~romatography (HPLC)
Appendix A: Recrystallization of 2,4-Dinitrophenylhydrazine
(DNPH)
Method 8316: Acrylamide, Acrylonitrile and Acrolein by High
Performance Liquid Chromatography (HPLC)
Method 8318: N-Methylcarbamates by High Performance Liquid
Chromatography (HPLC)
Method 8321: Solvent Extractable Non-Volatile Compounds by High
Performance Liquid Chromatography/Thermospray/Mass
Spectrometry (HPLC/TSP/MS) or Ultraviolet (UV) Detection
Method 8330: Nitroaromatics and Nitramines by High Performance Liquid
Method 8331: Tetrazene by Reverse Phase High Performance Liquid
4.3.4 Fourier Transform Infrared Methods
Method 8410: Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
Spectrometry for Semivolatile Organics: Capillary
Column
4.4 Miscellaneous Screening Methods
Method 3810: Head space
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
Method 8275: Thermal Chromatography/Mass Spectrometry (TC/MS) for
Screening Semivolatile Organic C~mpounds
November 1992
VOLUME ONE
SECTION C
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
PREFACE
CHAPTER ONE, REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
5.0 Definitions
6.0 References
CHAPTER FIVE -- MISCELLANEOUS TEST METHODS
Method 5050: Bomb Combustion Method for Solid Waste
Method 9010A: Total and Amenable Cyanide (Colorimetric, Manual)
Method 9012: Total and Amenable Cyanide (Colorimetric, Automated UV)
Method 9013: Cyanide Extraction Procedure for Solids and Oils
Method 90208: Total Organic Halides (TOX)
Method 9021: Purgeable Organic Halides (POX)
Method 9022: Total Organic Halides (TOX) by Neutron Activation
Analysis
Method 9030A: Sulfides
Method 9031: Extractable Sulfides
Method 9035: Sulfate (Colorimetric, Automated, Chloranilate)
Method 9036: Sulfate (Colorimetric, Automated, Methylthymol Blue, AA
II)
Method 9038: Sulfate (Turbidimetric)
Method 9056: Anion Chromatography Method
Method 9060: Total Organic Carbon
Method 9065: Phenol ics (Spectrophotometric, Manual 4-AAP with
Distillation)
Method 9066: Phenolics (Colorimetric, Automated 4-AAP with
Distillation)
Method 9067: Phenolics (Spectrophotometric, MBTH with Distillation)
Method 9070: Total Recoverable Oil &Grease (Gravimetric, Separatory
Funnel Extraction)
Method 9071A: Oil and Grease Extraction Method for Sludge and Sediment
Samples
Method 9075: Test Method for Total Chlorine in New and Used Petroleum
Products by X-Ray Fluorescence Spectrometry (XRF)
Method 9076: Test Method for Total Chlorine in New and Used Petroleum
Products by Oxidative Combustion and Microcoulometry
November 1992
Method 9077: Test Methods for Total Chlorine in New and Used
Petroleum Products (Field Test Kit Methods)
Method 9131: Total Coliform: Multiple Tube Fermentation Technique
Method 9132: Total Coliform: Membrane Filter Technique
Method 9200A: Nitrate
Method 9250: Chloride (Colorimetric, Automated Ferricyanide AAI)
Method 9251: Chloride (Colorimetric, Automated Ferricyanide AAll)
Method 9252A: Chloride (Titrimetric, Mercuric Nitrate)
Method 9253: Chloride (Titrimetric, Silver Nitrate)
Method 9320: Radium-228
CHAPTER SIX -- PROPERTIES
Method 1312: Synthetic Precipitation Leaching Procedure
Method 1320: Multiple Extraction Procedure
Method 1330A: Extraction Procedure for Oily Wastes
Method 9040A: pH Electrometric Measurement
Method 9041A: pH Paper Method
Method 90458: Soil and Waste pH
Method 9050: Specific Conductance
Method 9080: Cation-Exchange Capacity of Soils (Ammonium Acetate)
Method 9081: Cation-E~change Capacity of Soils (Sodium Acetate)
Method 9090A: Compatibility Test for Wastes and Membrane Liners
Method 9095: Paint Filter Liquids Test
Method 9096: Liquid Release Test (LRT) Procedure
Method 9100: Saturated Hydraulic Conductivity, Saturated Leachate
Conductivity, and Intrinsic Permeability
Method 9310: Gross Alpha and Gross Beta
Method 9315: Alpha-Emitting Radium Isotopes
PART II CHARACTERISTICS
CHAPTER SEVEN -- INTRODUCTION AND REGULATORY DEFINITIONS
7.1 Ignitability
7.2 Corrosivity
7.3 Reactivity
Test Method to Determine Hydrogen Cyanide Released from Wastes
Test Method to Determine Hydrogen Sulfide Released from Wastes
7.4 Toxicity Characteristic Leaching Procedure
CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS

8.1 Ignitability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Method 1020A: Setaflash Closed-Cup Method for Determining Ignitability
November 1992
8.2 Corrosivity
Method 1110: Corrosivity Toward Steel
8.3 Reactivity
8.4 Toxicity
Method 1310A: Extraction Procedure (EP) Toxicity Test Method and
Structural Integrity Test
Method 1311: Toxicity Characteristic Leaching Procedure
November 1992
VOLUME TWO
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
PREFACE
CHAPTER ONE, REPRINTED -- QUALITY CONTROL

1.0 Introduction
2.0 QA Project Plan
5.0 Definitions
6.0 References
PART III SAMPLING

CHAPTER NINE -- SAMPLING PLAN
9.1 Design and Development
9.2 Implementation
CHAPTER TEN -- SAMPLING METHODS
Method 0010: Modified Method 5 Sampling Train
Appendix A: Preparation of XAD-2 Sorbent Resin
Appendix B: Total Chromatographable Organic Material Analysis
Method 0020: Source Assessment Sampling System (SASS)
Method 0030: Volatile Organic Sampling Train
PART IV MONITORING
CHAPTER ELEVEN -- GROUND WATER MONITORING
11.1 Background and Objectives
11.2 Relationship to the Regulations and to Other Documents
11.3 Revisions and Additions
11.4 Acceptable Designs and Practices
11.5 Unacceptable Designs and Practices
CHAPTER TWELVE -- LAND TREATMENT MONITORING

12.1 Background
12.2 Treatment Zone
12.3 Regulatory Definition
November 1992
12.4 Monitoring and Sampling Strategy
12.5 Analysis
12.6 References and Bibliography
CHAPTER THIRTEEN - INCINERATION
13.1 Introduction
13.2 Regulatory Definition
13.3 Waste Characterization Strategy
13.4 Stack-Gas Effluent Characterization Strategy
13.5 Additional Effluent Characterization Strategy
13.6 Selection of Specific Sampling and Analysis Methods
13.7 References
Revision 2 methods (methods which have been revised in the proposed

Update II package) are designated by the letter "B" in the method
number. Likewise, Revision 1 methods (methods which were previously
revised in the promulgated Update I package or are being revised for
the first time in the proposed Update II package) are designated by
the letter "A" in the method number. In order to properly document
the method revision used, the entire method number, inc 1ud i ng the
letter designation, must be identified by the method user. A method
reference found within the text of SW-846 methods and chapters refers
to the 1atest promulgated revision of the method, even though the
referenced method number is without an appropriate letter designation.
November 1992
Method Number Chapter Number Method Number Current Revision

Third Edition Third Edition Second Edition Number
0010 Ten None {new method) 0

1010 Eight (8.1) 1010 0
1020 Eight (8 .1) 1020 0
1110 Eight (8.2) 1110 0
1310 Eight (8.4) 1310 1 (PR)
1320 Six None {new method) 0
1330 Six None (new method) 1 (PR)
3005 Three None (new method) 1 (PR)
3010 Three 3010 1 (PR)
3020 Three 3020 1 (PR)
3040 Three 3040 0
3050 Three 3050 1 (PR)
3500 Four (4.2.1) None (new method) 1 (PR)
3510 Four (4.2.1) 3510 1 (PR)
3520 Four (4.2.1) 3520 1 (PR)
3540 Four (4.2.1) 3540 1 (PR)
3550 Four (4.2.1) 3550 0
3580 Four (4.2.1) None (new method) 0
3611 Four (4.2.2) 3570 0

3650 Four (4.2.2) 3530 1
3810 Four (4.4) 5020 0
3820 Four (4.4) None (new method) 0
5030 Four (4.2.1) 5030 1 (PR)
5040 Four (4.2.1) None {new method) 0
6010 Three None (new method) 1
7000 Three None (new method) 1 (PR)
METHOD INDEX - 1 Revision 1

December 1987
METHOD INDEX ANO CONVERSION TABLE
(Continued)

Third Edition Thi rd Edition Second Edition Number
7040 Three 7040 0

7041 Three 7041 0
7060 Three 7060 0
7061 Three 7061 1 (PR)
7080 Three 7080 0
7081 Three 7081 0
7090 Three 7090 0
7091 Three 7091 0
7130 Three 7130 0
7131 Three 7131 0
7190 Three 7190 0
7191 Three 7191 0
7195 Three 7195 0
7196 Three 7196 1 (PR)
7197 Three 7197 0
7211 Three 7211 0
7381 Three 7381 0
7420 Three 7420 0
7421 Three 7421 0
7461 Three 7461 0
7470 Three 7470 0
7471 Three 7471 0
7520 Three 7520 0

December 1987
(Continued)

Thi rd Edition Third Edition Second Edition Number

7740 Three 7740 0
7741 Three 7741 0
7760 Three 7760 1
7761 Three 7761 0
7951 Three 7951 0
8010 Four (4.3.1) 8010 1 (PR)
8015 Four (4.3.1) 8015 1 (PR)
8020 Four (4.3.1) 8020 0
8030 Four (4.3.1) 8030 1 (PR)
8040 Four (4.3.1) 8040 1 (PR)
8060 Four (4.3.1) 8060 0
8080 Four (4.3.1) 8080 0
8090 Four (4.3.1) 8090 0
8100 Four (4.3.1) 8100 0
8120 Four (4.3.1) 8120 1 (PR)
8140 Four (4.3.1) 8140 0
8150 Four (4.3.1) 8150 1 (PR)
8240 Four (4.3.2) 8240 1 (PR)
8250 Four (4.3.2) 8250 1 (PR)

December 1987
(Continued)

Thi rd Edition Thi rd Edition Second Edition Number
8270 Four (4.3.2) 8270 1 (PR)

8310 Four (4.3.3) 8310 0
9010 Five 9010 1
9020 Five 9020 0
9021 Five None (new method) 0
9030 Five 9030 1

9040 Six 9040 0
9041 Six None (new method) 0
9090 Six None (new method) 1 (PR)
9100 Six None (new method) a
9131 Five None (new method) a

9310 Six None (new method) a

December 1987
(Continued)

Third Edition Third Edition Second Edition Number
HCN Test Method Seven None (new method) I (PR)

H2S Test Method Seven None (new method) 0
(PR) Indicates a Partial Revision
METHOD INDEX - 5 Revision I

December 1987
CHAPTER ONE
QUALITY CONTROL
1.1 INTRODUCTION
Appropriate use of data generated under the great range of analytical
conditions encountered in RCRA analyses requires reliance on the quality
control practices incorporated into the methods and procedures. The
Environmental Protection Agency generally requires using approved methods for
sampling and analysis operations fulfilling regulatory requirements, but the
mere approval of these methods does not guarantee adequate results.
Inaccuracies can result from many causes, including unanticipated matrix
effects, equipment ma l functions, and operator error. Therefore, the qua 1i ty
control component of each method is indispensable.
The data acquired from quality control procedures are used to estimate and
evaluate the information content of analytical data and to determine the
necessity or the effect of corrective action procedures. The means used to
estimate information content include precision, accuracy, detection limit, and
other quantifiable and qualitative indicators.
I.I.I Purpose of this Chapter
This chapter defines the quality control procedures and components that
are mandatory in the performance of analyses, and indicates the quality
control information which must be generated with the analytical data.
Certain activities in an integrated program to generate quality data can
be classified as management (QA) and other as functional (QC). The
presentation given here is an overview of such a program.
The following sections discuss some minimum standards for QA/QC programs.
The chapter is not a guide to constructing quality assurance project
plans, quality control programs, or a quality assurance organization.
Generators who are choosing contractors to perform sampling or analytical
work, however, should make their choice only after evaluating the
contractor's QA/QC program against the procedures presented in these
sections. Likewise, laboratories that sample and/or analyze solid wastes
should similarily evaluate their QA/QC programs.
Most of the laboratories who will use this manual also carry out testing
other than that called for in SW-846. Indeed, many user laboratories have
multiple mandates, including analyses of drinking water, wastewater, air
and industrial hygiene samples, and process samples. These 1aboratori es
will, in most cases, already operate under an organizational structure
that includes QA/QC. Regardless of the extent and hi story of their
programs, the users of this manual should consider the development,
status, and effectiveness of their QA/QC program in carrying out the
testing described here.
I.1.2 Program Design
The initial step for any sampling or analytical work should be strictly to
define the program goa 1s. Once the goals have been defined, a program
ONE - 1 Revision 1
December 1987
must be designed to meet them. QA and QC measures will be used to monitor
the program and to ensure that all data generated are suitable for their
intended use. The responsibility of ensuring that the QA/QC measures are
properly employed must be assigned to a knowledgeable person who is not
directly involved in the sampling or analysis.
One approach that has been found to provide a useful structure for a QA/QC
program is the preparation of both general program plans and project-
specific QA/QC plans.
The program plan for a laboratory sets up basic laboratory policies,
including QA/QC, and may include standard operating procedures for
specific tests. The program plan serves as an operational charter for the
laboratory, defining its purposes, its organization and its operating
principles. Thus, it is an orderly assemblage of management policies,
objectives, principles, and general procedures describing how an agency or
laboratory intends to produce data of known and accepted qua 1 ity. The
elements of a program plan and its preparation are described in QAMS-
004/80 (see References, Step 1.6).
Project-specific QA/QC plans differ from program plans in that specific
details of a particular sampling/analysis program are addressed. For
example, a program plan might state that all analyzers will be calibrated
according to a specific protocol given in written standard operating
procedures for the laboratory (SOP), while a project plan would state that
a particular protocol will be used to calibrate the analyzer for a
specific set of analyses that have been defined in the plan. The project
plan draws on the program plan or its basic structure and applies this
management approach to specific determinations. A given agency or
laboratory would have only one quality assurance program plan, but would
have a quality assurance project plan for each of its projects. The
elements of a project plan and its preparation are described in
QAMS/005/80 (see References, Step 1.6) and are listed in Figure 1-1.
Some organizations may find it inconvenient or even unnecessary to prepare
a new project plan for each new set of analyses, especially analytical
laboratories which receive numerous batches of samples from various
customers within and outside their organizations. For these
organizations, it is especially important that adequate QA management
structures exist and that any procedures used exist as standard operating
procedures (SOP), written documents which detail an operation, analysis or
action whose mechanisms are thoroughly prescribed and which is commonly
accepted as the method for performing certain routine or repetitive tasks.
Having copies of SW-846 and all its referenced documents in one's
laboratory is not a substitute for having in-house versions of the methods
written to conform to specific instrumentation, data needs, and data
quality requirements.
ONE - 2 Revision I
December 1987
FIGURE I-I
ESSENTIAL ELEMENTS OF A QA PROJECT PLAN
I. Title Page
2. Table of Contents
3. Project Description
4. Project Organization and Responsibility
5. QA Objectives
6. Sampling Procedures
7. Sample Custody
8. Calibration Procedures and Frequency
9. Analytical Procedures
IO. Data Reduction, Validation, and Reporting
II. Internal Quality Control Checks
I2. Performance and System Audits
I3. Preventive Maintenance
I4. Specific Routine Procedures Used to Assess Data
Precision, Accuracy, and Completeness
I5. Corrective Action
I6. Quality Assurance Reports to Management
ONE - 3 Revision 1
December 1987
1.1.3 Organization and Responsibility
As part of any measurement program, activities for the data generators,
data reviewers/approvers, and data users/requestors must be clearly defined.
While the specific titles of these individuals will vary among agencies and
laboratories, the most basic structure will include at least one
representative of each of these three types. The data generator is typically
the individual who carries out the analyses at the direction of the data
user/requestor or a designate within or outside the laboratory. The data
reviewer/approver is responsible for ensuring that the data produced by the
data generator meet agreed-upon specifications.
Responsibility for data review is sometimes assigned to a "Quality
Assurance Officer" or "QA Manager." This individual has broad authority to
approve or disapprove project plans, specific analyses and final reports. The
QA Officer is independent from the data generation activities. In general,
the QA Officer is responsible for reviewing and advising on all aspects of
QA/QC, including:
Assisting the data requestor in specifying the QA/QC procedure to be used
during the program;
Making on-site evaluations and submitting audit samples to assist in
reviewing QA/QC procedures; and,
If problems are detected, making recommendations to the data requestor
and upper corporate/institutional management to ensure that appropriate
corrective actions are taken.
In programs where large and complex amounts of data are generated from
both field and laboratory activities, it is helpful to designate sampling
monitors, analysis monitors, and quality control/data monitors to assist in
carrying out the program or project.
The sampling monitor is responsible for field activities. These include:
Determining (with the analysis monitor) appropriate sampling equipment
. and sample containers to minimize contamination;
Ensuring that samples are co 11 ected, preserved, and transported as
specified in the workplan; and
Checking that all sample documentation (labels, field notebooks, chain-
of-custody records, packing 1 ists) is correct and transmitting that
information, along with the samples, to the analytical laboratory.
The analysis monitor is responsible for laboratory activities. These
include:
Training and qualifying personnel in specified laboratory QC and
analytical procedures, prior to receiving samples;
ONE - 4 Revision 1
December 1987
Receiving samples from the field and verifying that incoming samples
correspond to the packing list or chain-of-custody sheet; and
Verifying that laboratory QC and analytical procedures are being followed
as specified in the workplan, reviewing sample and QC data during the
course of analyses, and, if questionable data exist, determining which
repeat samples or analyses are needed.
The quality control and data monitor is responsible for QC activities and
data management. These include:
Maintaining records of all incoming samples, tracking those samples
through subsequent processing and analysis, and, ultimately,
appropriately disposing of those samples at the conclusion of the
program;
Preparing quality contra 1 samples for analysis prior to and during the
program;
Preparing QC and sample data for review by the analysis coordinator and
the program manager; and
Preparing QC and sample data for transmission and entry into a computer
data base, if appropriate.
1.1.4 Performance and Systems Audits
The QA Officer may carry out performance and/or systems audits to ensure
that data of known and defensible quality are produced during a program.
Systems audits are qualitative evaluations of all components of field and
laboratory quality control measurement systems. They determine if the
measurement systems are being used appropriately. The audits may be carried
out before all systems are operational, during the program, or after the
completion of the program. Such audits typically involve a comparison of the
activities given in the QA/QC plan with those actually scheduled or performed.
A special type of systems audit is the data management audit. This audit
addresses only data collection and management activities.
The performance audit is a quantitative evaluation of the measurement
systems of a program. It requires testing the measurement systems with
samples of known composition or behavior to evaluate precision and accuracy.
The performance audit is carried out by or under the auspices of the QA
Officer without the knowledge of the analysts. Since this is seldom
achievable, many variations are used that increase the awareness of the
analyst as to the nature of the audit material.
1.1.5 Corrective Action
Corrective action procedures should be addressed in the program plan,
project, or SOP. These should include the following elements:
ONE - 5 Revision 1
December 1987
The EPA predetermined limits for data acceptability beyond which
corrective action is required;
Procedures for corrective action; and,
For each measurement system, identification of the individual responsible
for initiating the corrective action and the individual responsible for
approving the corrective action, if necessary.
The need for corrective action may be identified by system or performance
audits or by standard QC procedures. The essential steps in the corrective
action system are:
Identification and definition of the problem;
Assignment of responsibility for investigating the problem;
Investigation and determination of the cause of the problem;
Determination of a corrective action to eliminate the problem;
Assigning and accepting responsibility for implementing the corrective
action;
Implementing the corrective action and evaluating its effectiveness; and
Verifying that the corrective action has eliminated the problem.
The QA Officer should ensure that these steps are taken and that the
problem which led to the corrective action has been resolved.
1.1.6 QA/QC Reporting to Management
QA Project Program or Plans should provide a mechanism for periodic
reporting to management (or to the data user) on the performance of the
measurement system and the data quality. Minimally, these reports should
include:
Periodic assessment of measurement quality indicators, i.e., data
accuracy, precision and completeness;
Results of performance audits;
Results of system audits; and
Significant QA problems and recommended solutions.
The individual responsible within the organization structure for preparing
the periodic reports should be identified in the organizational or management
plan. The final report for each project should also include a separate QA
section which summarizes data quality information contained in the periodic
reports.
ONE - 6 Revision 1
December 1987
Other guidance on quality assurance management and organizations is
available from the Agency and professional organizations such as ASTM, AOAC,
APHA and FDA.
1.1.7 Quality Control Program for the Analysis of RCRA Samples
An analytical quality control program develops information which can be
used to:
· Evaluate the accuracy and precision of analytical data in order to
establish the quality of the data;
Provide an indication of the need for corrections to the analytical
system, when comparison with existing regulatory or program criteria or
data trends shows that activities must be changed or monitored to a
different degree; and
To determine the effect of corrections to the analytical system.
1.1.8 Definitions
ACCURACY: Accuracy is the nearness of a measurement or the mean (x)
of a set of measurements to the true value. Accuracy is
assessed by means of reference samp 1es and percent
recoveries.
ANALYTICAL BATCH: The basic unit for analytical quality control is the
analytical batch. The analytical batch is defined as
samples which are analyzed together with the same method
sequence and the same 1ots of reagents and with the
manipulations common to each sample within the same time
period or in continuous sequential time periods. Samples
in each batch should be of similar composition (e.g. ground
water, sludge, ash, etc.}.
BLANKS:
CALIBRATION BLANK: Usually an organic or aqueous solution that is as free of
analyte as possible and prepared with the same volume of
chemical reagents used in the preparation of the
calibration standards and diluted to the appropriate volume
with the same solvent (water or organic) used in the
preparation of the ca 1 i brat ion standard. The ca 1 i brat ion
blank is used to give the null reading for the instrument
response versus concentration calibration curve. One
calibration blank should be analyzed with each analytical
batch or every 20 samples, whichever is greater.
EQUIPMENT BLANK: Usually an organic or aqueous solution that is as free of
analyte as possible and is transported to the site, opened
in the fie 1d, and poured over or through the samp 1e
collection device, collected in a sample container, and
returned to the 1aboratory. This serves as a check on
ONE - 7 Revision 1
December 1987
sampling device cleanliness. One equipment blank should be
analyzed with each analytical batch or every 20 samples,
whichever is greater.
FIELD BLANK: Usually an organic or aqueous solution that is as free of
analyte as possible and is transferred from one vessel to
another at the sampling site and preserved with the
appropriate reagents. This serves as a check on reagent
and environmental contamination. One field blank should be
analyzed with each analytical batch or every 20 samples,
whichever is greater.
REAGENT BLANK: Usually an organic or aqueous solution that is as free of
analyte as possible and contains all the reagents in the
same volume as used in the processing of the samples. The
reagent blank must be carried through the complete sample
preparation procedure and contains the same reagent
concentrations in the final solution as in the sample
solution used for analysis. The reagent blank is used to
correct for possible contamination resulting from the
preparation or processing of the sample. One reagent blank
should be prepared for every analytical batch or for every
20 samples, whichever is greater.
TRIP BLANK: Usually an organic or aqueous solution that is as free of

analyte as possible and is transported to the sampling site
and returned to the laboratory without being opened. This
serves as a check on sample contamination originating from
sample transport, shipping, and from the site conditions.
One trip blank should be analyzed with each analytical
batch or every 20 samples, whichever is greater.
CHECK STANDARD: A material of known composition that is analyzed
concurrently with test samples to evaluate a measurement
process. An analytical standard that is analyzed to verify
the calibration of the analytical system. One check
standard should be analyzed with each analytical batch or
every 20 samples, whichever is greater.
MATRIX SPIKE: A Matrix Spike is employed to provide a measure of accuracy
for the method used in a given matrix. A matrix spike
analysis is performed by adding a predetermined quantity of
stock solutions of certain analytes to a sample matrix
prior to sample extraction/digestion and analysis. The
concentration of the spike should be at the regulatory
standard level or the PQL for the method. When the
concentration of the analyte in the sample is greater than
0.1%, no spike of the analyte is necessary.
MOL: The method detection limit (MOL) is defined as the minimum
concentration of a substance that can be measured and
reported with 99% confidence that the analyte concentration
ONE - 8 Revision 1
December 1987
is greater than zero and is determined from analysis of a
sample in a given matrix containing the analyte.
PRECISION: Pree is ion is the agreement between a set of replicate
measurements without assumption or kn owl edge of the true
value. Precision is assessed by means of
duplicate/replicate sample analysis.
PQL: The pr act i cal quant itat ion l i mfr (POL) is the lowest level
that can be reliably achieved within specified limits of
precision and accuracy during routine laboratory operating
conditions.
RCRA: The Resource ~onservation and Recovery Act.
REAGENT GRADE: Anal yt i cal reagent .LAfll grade, ACS reagent grade, and
reagent grade are synonymous terms for reagents which
conform to the current specifications of the Committee on
Analytical Reagents of the American Chemical Society.
SAMPLES:
DUPLICATE SAMPLES: Duplicate samples are two separate samples taken from the
same source (i.e. in separate containers and analyzed
independently).
Sampling Point
or
Source in the Field
Field Duplicate I Field Duplicate II
Replicate IA Replicate 18 Replicate IIA Replicate IIB
ENVIRONMENTAL An environmental sample or field sample is a repre-

SAMPLES: sentative sample of any material (aqueous, nonaqueous, or
multimedia) collected from any source for which
determination of composition or contamination is requested
or required. For the purposes of this manual,
environmental samples shall be classified as follows:
Surface Water and Ground Water;
Drinking Water -- delivered water (treated or untreated)
designated as potable water;
ONE - 9 Revision I
December 1987
Water/Wastewater -- raw source waters for public drinking
water supplies, ground waters, municipal
influents/effluents, and industrial influents/effluents;
Sludge -- municipal sludges and industrial sludges;
Waste -- aqueous and nonaqueous 1 iquid wastes, chemical
solids, contaminated soils, and industrial liquid and solid
wastes.
QUALITY CONTROL A sample prepared from an independent standard at a
REFERENCE SAMPLE: concentration other than that used for calibration, but
within the ca 1 i brat ion range. An independent standard is
defined as a standard composed of the anal yte ( s) of
interest from a different source than that used in the
preparation of standards for use in the standard curve. A
qua 1 ity control reference sample is intended as an
independent check of technique, methodology, and standards
and should be run with every analytical batch or every 20
samples, whichever is greater. This is applicable to all
organic and inorganic analyses.
REPLICATE SAMPLES: Replicate samples are two aliquots taken from the same
samp 1e container and ana 1yzed independent 1y. In cases
where al iquoting is impossible, as in the case of
volatiles, duplicate samples must be taken for the
replicate analysis.
STANDARD CURVE: A standard curve is a curve which plots concentrations of
known analyte standards versus the instrument response to
the anal yte. Ca 1 i brat ion standards are prepared by
diluting the stock analyte solution in graduated amounts
which cover the expected range of the samples being
analyzed. Standards should be prepared at the frequency
specified in the appropriate section. The ca 1 i brat ion
standards must be prepared using the same type of acid or
solvent and at the same concentration as will result in the
samples following sample preparation. This is applicable
to organic and inorganic chemical analyses.
SURROGATE: Surrogates are organic compounds which are similar to
analytes of interest in chemical composition, extraction,
and chromatography, but which are not normally found in
environmental samples. These compounds are spiked into all
blanks, calibration and check standards, samples (including
duplicates and QC reference samples) and spiked samples
prior to analysis. Percent recoveries are calculated for
each surrogate.
WATER: Any reference to water in a Chapter or Method refers to
ASTM Type II reagent water (unless otherwise specified)
which is free of contaminants that may interfere with the
analytical test in question.
ONE - 10 Revision 1
December 1987
1.2 QUALITY CONTROL
The procedures indicated below are to be performed for all analyses.
Specific instructions relevant to particular analyses are given in the
pertinent analytical procedures.
1.2.l Field Quality Control
The sampling component of the Quality Assurance Project Plan (QAPP) shall
include as appropriate:
Reference to or incorporation of accepted sampling techniques in the
sampling plan;
Procedures for documenting and justifying any field actions contrary to
the accepted techniques;
Documentation of all pre-field activities such as equipment check-out,
calibrations, and container storage and preparation;
Documentation of field measurement quality control data (quality control
procedures for such measurements sha 11 be equivalent to corresponding
laboratory QC procedures);
Documentation of field activities;
Documentation of post-field activities including sample shipment and
receipt, field team de-briefing and equipment check-in;
Generation of quality control samples including field duplicate samples,
field blanks, equipment blanks, and trip blanks; and
The use of these samples in the context of data evaluation, with details
of the methods employed (including statistical methods) and of the
criteria upon which the information generated will be judged.
1.2.2 Analytical Quality Control
A quality contra l operation or component is only useful if it can be
measured or documented. The following components of analytical quality
contra l are re 1ated to the ana lyt i cal batch. The procedures described are
intended to be applied to chemical analytical procedures; although the
principles are applicable to radio-chemical or biological analysis, the
procedures may not be directly applicable to such techniques.
All quality control data and records required by these sections shall be
retained by the 1aboratory for three years from the time the results were
reported. The data must be made available to the client or enforcement
official upon request.
ONE - 11 Revision 1
December 1987
1.2.2.1 Spikes, Blanks and Duplicates
General Requirements
These procedures sha 11 be performed at least once with each
analytical batch with a minimum of once per twenty samples.
1.2.2.1.1 Matrix Spiked Samples
A matrix spiked sample shall be analyzed with every analytical
batch or every 20 samples, whichever is more frequent. The sample
shall be spiked with the analyte(s) of interest (see the appropriate
method). The sample to be spiked should be typical or representative
of the batch. Ideally, it should be an intermediate between the
cleanest and the most contaminated samples based on the best
information available. It is recommended that the spike be made in a
replicate of one of the field duplicate samples. This procedure is
applicable to all organic or inorganic chemical analytes.
1.2.2.1.2 Field Duplicate Samples
Field duplicate samples shall be analyzd with every analytical
batch or every 20 samples, whichever is greater. This procedure is
applicable to all organic or inorganic chemical analytes.
1.2.2.1.3 Blanks
Each batch shall be accompanied by a reagent blank. The reagent
blank shall be carried through the entire analytical procedure.
1.2.2.1.4 Surrogate Compounds
Every blank, standard, and environmental sample (including
duplicates, QC reference samples, and check standards) shall be
spiked with surrogate compounds prior to purging or extraction.
Surrogates shall be spiked into samples according to the appropriate
analytical methods. Surrogate spike recoveries shall fall within the
control limits set by the laboratory (in accordance with procedures
specified in the method or within ± 20%) for samples falling within
the quantification limits without dilution. Dilution of samples to
bring the analyte concentration into the linear range of calibration
may dilute the surrogates below the quantification limit; evaluation
of analytical quality then will rely on the quality control embodied
in the check, spiked and duplicate spiked samples. This is
applicable to organic analyses only.
1.2.2.1.5 Quality of Control Reference Sample
A quality control reference sample is a sample prepared from an
independent standard at a concentration other than that used for
calibration, but within the calibration range. An independent
standard is defined as a standard composed of the analytes of
interest from a different source than that used in the preparation of
ONE - 12 Revision 1
December 1987
standards for use in the standard curve. A quality control reference
sample is intended as an independent check of technique, methodology,
and standards and should be run with every analytical batch or every
20 samples, whichever is greater. This is applicable to all organic
and inorganic analyses.
1.2.2.1.6 Check Standard
A standard of known concentration prepared by the analyst to
monitor and verify instrument performance on a daily basis.
1.2.2.2 Clean-Ups
Quality control procedures described here are intended for adsorbent
chromatography and back extractions applied to organic extracts. All
batches of adsorbents (Florisil, alumina, silica gel, etc.) prepared for
use shall be checked for analyte recovery by running the elution pattern
with standards as a column check. The elution pattern shall be optimized
for maximum recovery of analytes and maximum rejection of contaminants.
This is applicable to organic analyses only.
1.2.2.2.1 Column Check Sample
The elution pattern shall be reconfirmed with a column check of
standard compounds after activating or deactivating a batch of
adsorbent. These compounds sha 11 be representative of each e1ut ion
fraction. Recovery as specified in the methods is considered an
acceptable column check. A result lower than specified indicates
that the procedure is not acceptable or has been misapplied. This is
applicable to organic analyses only.
1.2.2.2.2 Column Check Blank
The column check blank shall be run after activating or
deactivating a batch of adsorbent. This is applicable to organic
analyses only.
1.2.2.3 Determinations
1.2.2.3.1 Instrument Adjustment, Tuning, and Alignment
Requirements and procedures are instrument- and method-specific.
Analytical instrumentation shall be tuned and aligned in accordance
with requirements which are specific to the instrumentation
procedures employed. Individual determinative procedures shall be
consulted. Criteria for initial conditions and for continuing
confirmation conditions for methods within this manual are found in
the appropriate procedures. This is applicable to all organic and
inorganic analyses.
ONE - 13 Revision 1
December 1987
1.2.2.3.2 Calibration
Analytical instrumentation shall be calibrated in accordance

with requirements which are specific to the instrumentation and
procedures employed. Methods 6010, 7000, and 8000 as well as the
appropriate analytical procedures shall be consulted for criteria for
initial and continuing calibration.
1.2.2.3.3 Additional QC Requirements for Inorganic Analysis
Standard curves used in the determination of inorganic analytes

shall be prepared as follows:
Standard curves derived from data consisting of one calibration
blank and three concentrations shall be prepared for each analyte.
The response for each prepared standard sha 11 be based upon the
average of three replicate readings of each standard. The standard
curve shall be used with each subsequent analysis provided that the
standard curve is verified by using at least one reagent blank and
one standard at a level normally encountered or expected in such
samples. The response for each standard sha 11 be based upon the
average of three replicate readings of the standard. If the results
of the verification are not within ± 10% of the original curve, a new
standard shall be prepared and analyzed. If the results of the
second verification are not within ± 10% of the original standard
curve, a reference standard should be employed to determine if the
discrepancy is with the standard or with the instrument. New
standards should also be prepared on a quarterly basis at a minimum.
All data used in drawing or describing the curve shall be so
indicated on the curve or its description. A record shall be made of
the verification.
Standard deviations and relative standard deviations shall be

calculated for the percent recovery of analytes from the spiked
sample duplicates and from the check samples. These values shall be
established for the twenty most recent determinations in each
category.
1.2.2.3.4 Additional Quality Control Requirements for Organic

Analysis
The following requirements shall be applied to the analysis of

samples by gas chromatography, liquid chromatography and gas
chromatography/mass spectrometry.
The calibration of each instrument sha 11 be verified at

frequencies specified in the methods. A new standard curve must be
prepared as specified in the methods.
The tune of each GC/MS system used for the determination of

organic analytes shall be checked with 4-bromofluorobenzene (BFB) for
determinations of volatiles and with decafluorotriphenylphosphine
(DFTPP) for determinations of semi-volatiles. The required ion
ONE - 14 Revision 1
December 1987
abundance criteria shall be met before determination of any analytes.
If the system does not meet the required specification for one or
more of the required ions, the instrument must be retuned and
rechecked before proceeding with sample analysis. The tune
performance check criteria must be achieved daily or for each 12 hour
operating period, whichever is more frequent.
Background subtraction should be straightforward and designed
only to eliminate column bleed or instrument background ions.
Background subtraction actions resulting in spectral distortions for
the sole purpose of meeting special requirements are contrary to the
objectives of Quality Assurance and are unacceptable.
For determinations by HPLC or GC, the instrument calibration
shall be verified as specified in the methods.
1.2.2.3.5 Identification
Identification of all analytes must be accomplished with an
authentic standard of the analyte. When authentic standards are not
available, identification is tentative.
For gas chromatographic determinations of specific analytes, the
relative retention time of the unknown must be compared with that of
an authentic standard. For compound confirmation, a sample and
standard shall be re-analyzed on a column of different selectivity to
obtain a second characteristic relative retention time. Peaks must
elute within daily retention time windows to be declared a tentative
or confirmed identification.
For gas chromatographic/mass spectrometric determinations of
specific analytes, the spectrum of the analyte should conform to a
1 i terature representation of the spectrum or to a spectrum of the
authentic standard obtained after satisfactory tuning of the mass
spectrometer and within the same twelve-hour working shift as the
analytical spectrum. The appropriate analytical methods should be
consulted for specific criteria for matching the mass spectra,
relative response factors, and relative retention times to those of
authentic standards.
1.2.2.3.6 Quantification
The procedures for quantification of analytes are discussed in
the appropriate general procedures (7000, 8000) and the specific
analytical methods.
In some situations in the course of determining metal analytes,
matrix-matched calibration standards may be required. These
standards shall be composed of the pure reagent, approximation of the
matrix, and reagent addition of major interferents in the samples.
This will be stipulated in the procedures.
ONE - 15 Revision 1
December 1987
Estimation of the concentration of an organic comoound not
contained within the calibration standard may be accomplished by
comparing mass spectral response of the compound with that of an
internal standard. The procedure is specified in the methods.
1.3 METHOD DETECTION LIMIT
For ope rat i ona 1 purposes, when it is necessary to determine the method
detection limit in the sample matrix, the MDL defined in One-10 shall be
determined by multiplying by 7 the standard deviation obtained from the
triplicate analyses of a matrix spike containing the analyte of interest at a
concentration three to five times the estimated MDL.
Determine the estimated MDL as follows:
Obtain the concentration value that corresponds to:
a) an instrument signal/noise ratio within the range of 2.5 to
5.0, or
b) the region of the standard curve where there is a significant

change in sensitivity, i.e., a break in the slope of the
standard curve.
· Determine the variance (S2) for each analyte as follows:
n n
s2 = l/(n - 1) [:E Xi2 - l/n (:E X1)2]
i•l i·l
Determine the standard deviation (S) for each analyte as follows:
S = (S2)1/2
Determine the MDL for each analyte as follows:
MDL = t ( n-1 , 1- a .. O. 99) ( S)
where t(n-1 1- am 0.99) = 6.965 for three replicates as determined

from the table of sludent's t values at the 99 percent level.
1.4 DATA REPORTING
The requirement of reporting analytical results on a wet-weight or a dry-
weight basis is dictated by factors such as: sample matrix; program or
regulatory requirement; and objectives of the analysis.
Analytical results shall be reported with the percent moisture or percent
solid content of the sample.
1.5 QUALITY CONTROL DOCUMENTATION
The following sections list the QC documentation which comprises the
complete analytical package. This package can be obtained from the data
generator upon request. These forms, or adaptations of these forms, shall be
ONE - 16 Revision 1
December 1987
used by the data generator/reporter for inorganics (I), or for organics (0) or
both (1/0) types of determinations.
1.5.1 Analytical Results (1/0: Form I)
Analyte concentration.
Sample weight.
Percent water (for non-aqueous samples when specified).
Final volume of extract or diluted sample.
Holding times (I: Form X).
1.5.2 Calibration (I: Form 2A; 0: Form V, VI, VII, IX)
Calibration curve or coefficients of the linear equation which describes
the calibration curve.
Correlation coefficient of the linear calibration.
Concentration/response data (or relative response data) of the calibration
check standards, along with dates on which they were analytically determined.
1.5.3 Column Check (0: Form X)
Results of column chromatography check, with the chromatogram.
1.5.4 Extraction/Digestion (1/0: Form I)
Date of the extraction for each sample.
1.5.5 Surrogates {O: Form II)
Amount of surrogate spiked, and percent recovery of each surrogate.
1.5.6 Matrix Spiked Samples (I: Form 5, SA, 6; 0: Form Ill)
Amount spiked, percent recovery, and relative percent difference for each
compound in the spiked samples for the analytical batch.
1.5.7 Check Standard (I: Form 7; 0: Form VIII)
Amount spiked, and percent recovery of each compound spiked.
1.5.8 Blank (I: Form 3; 0: Form IV)
Identity and amount of each constituent.
1.5.9 Chromatograms (for organic analysis)
All chromatograms for reported results, properly labeled with:
Sample identification
Method identification
Identification of retention time of analyte on the chromatograms.
ONE - 17 Revision 1
December 1987
1.5.10 Quantitative Chromatogram Report (0: Forms VIII, IX, X)
Retention time of analyte.
Amount injected.
Area of appropriate calculation of detection response.
Amount of analyte found.
Date and time of injection.
1.5.11 Mass Spectrum
Spectra of standards generated from authentic standards (one for each
report for each compound detected).
Spectra of analytes from actual analyses.
Spectrometer identifier.
1.5.12 Metal Interference Check Sample Results (I: Form 4)
1.5.13 Detection Limit (I: Form 7; O: Form I)
Analyte detection limits with methods of estimation.
1.5.14 Results of Standard Additions (I: Form 8)
1.5.15 Results of Serial Dilutions (I: Form 9)
1.5.16 Instrument Detection Limits (I: Form 11)
1.5.17 ICP Interelement Correction Factors and ICP Linear Ranges (when
applicable) (I: Form 12a, 12b, Form 13).
1.6 REFERENCES
1. Guidelines and Specifications for Preparing Quality Assurance Program
Plans, September 20, 1980, Office of Monitoring Systems and Quality
Assurance, ORD, U.S. EPA, QAMS-004/80, Washington, DC 20460.
2. Interim Guidelines and Specifications for Preparing Quality Assurance
Project Plans, December 29, 1980, Office of Monitoring Systems and
Quality Assurance, ORD, U.S. EPA, QAMS-005/80, Washington, DC 20460.
ONE - 18 Revision 1
December 1987
COVER PAGE - INORGANIC ANALYSES DATA PACKAGE
Lab Name: Contract:
Lab Code: Case No.: SAS No.: SDG No.:
SOW No.:
EPA Sample No. Lab Sample ID.
Were ICP interelement corrections applied? Yes/No
Were ICP background corrections applied? Yes/N·o

If yes-were raw data generated before
application of background corrections? Yes/No
Comments:
Release of the data contained in this hardcopy data package and in the
computer-readable data submitted on floppy diskette has been authorized by
the Laboratory Manager or the Manager's designee, as verified by the
following signature.
Lab Manager:
Date:
ONE - 19 Revision I
December 1987
1 EPA SAMPLE NO.
INORGANIC ANALYSIS DATA SHEET
Lab Name: Contract:

Matrix (soil/water): Lab Sample ID:

Level (low/med): Date Received:
% Solids:
Concentration Units (ug/L or mg/kg dry weight):
I I I I I I I
I CAS No. I Analyte I Concentration I c I M I Q I
l _____=--1 l _ _ _ _ _ l_l _ _ l_I
17429-90-5 !Aluminum I l_I l_I
17440-36-0 !Antimony-I l_I l_I
17440-38-2 !Arsenic -I l_I l_I
I 7440-39-3 I Barium - I l_I l_I
17440-41-7 I Beryllium I l_I l_I
17440-43-9 !Cadmium I l_I l_I
I 7440-70-2 \Calcium-\ l_I \_I
17440-47-3 !Chromium- l_I l_I
17440-48-4 !Cobalt - l_I l_I
17440-50-8 !Copper===: l_I l_I
17439-89-6 IIron l_I l_I
17439-92-1 !Lead l_I l_I
17439-95-4 \Magnesium l_I l_I
17439-96-5 !Manganese l_I l_I
17439-97-6 !Mercury l_I l_I
17440-02-0 !Nickel - l_I l_I
17440-09-7 !Potassium l_I l_I
17782-49-2 !Selenium l_I l_I
17440-22-4 !Silver - l_I l_I
17440-23-5 !Sodium- l_I l_I
17440-28-0 IThalliUiil l_I l_I
17440-62-2 !Vanadium- l_I l_I
17440-66-6 IZinc -.I l_I l_I
I !Cyanide I l_I l_I
I I -, l_I l_I
Color Before: Clarity Before: Texture:
Color After: Clarity After: Artifacts:
Comments:
ONE - 20 Revision 1
December 1987
2A
INITIAL AND CONTINUING CALIBRATION VERIFICATION
Lab Name: Contract:
Initial Calibration Source:
Continuing Calibration Source:
Concentration Units: ug/L
I I I 11
I I Initial Calibration I II I
Continuing Calibration
IAnalyte I True Found %R(l) I True Found %R(l) 11 M I
%R(l) Found
I I___ I _ _ _ ____ ___ ____ II I
!Aluminum I I 11 I
!Antimony- I l_I
I Arsenic - I l_I
!Barium -- ll_I
I Beryllium II I
I Cadmium 11_1
jCalcium-- I l_I
IChromiuitl I l_I
ICobalt - I l_I
I Copper- 11_1
!Iron - 11_1
I Lead 11_1
IMagnesium II I
I Manganese II
I Mercury II
I Nickel -- II
I Potassium II
I Selenium II
!Silver - 11
JSodium-1 11
I Thalliwnl 11
I Vanadium-, II
I Zinc -I 11
!Cyanide I 11_1
I --1 11_1
(1) Control Limits: Mercury 80-120; Other Metals 90-110; Cyanide 85-115
ONE - 21 Revision 1
December 1987
2B
CRDL STANDARD FOR AA AND ICP
Lab Name: Contract:

AA CRDL Standard Source:
ICP CRDL Standard Source:
I I 11
I I CRDL Standard for AA 11 CRDL Standard for ICP
I I 11 Initial Final
IAnalyte I True Found %R I I True Found %R Found %R
I I II
I Aluminum_ I I I 11 I
!Antimony I I I I I
!Arsenic -I I I I I
I Barium-= I I I I I
I Beryllium I I I I I
!Cadmium I I I I I
!Calcium-I I I I I
I Chromium_ I I I I I
!Cobalt_! I I I I
I Copper_ I I I I I
!Iron I I I I I
!Lead I I I I I
I Magnesium! I I I I
IManganese I I I I I
IMercury_ I I I I I
]Nickel I I I I I
!Potassium! I I I I
!Selenium_! I I II I
!Silver_! I I II I
I Sodium_ I I I II I
!Thallium I I I 11 I
jVanadium-1 I I II I
!Zinc -, I I II I
I I I I II I
ONE - 22 Revision 1
December 1987
3
BLANKS
Lab Name: Contract:

Preparation Blank Matrix (soil/water):
Preparation Blank Concentration Units (ug/L or mg/kg):
I I I 11 11
I I Initial I II 11
I I Calib. I Continuing Calibration 11 Prepa- 11
I I Blank I Blank (ug/L) 11 ration I 11
IAnalyte I (ug/L) Cl l c 2 c 3 Cl I Blank c 11 MI
I I _I _I I _ll_I
!Aluminum I _I 1=1 1=1 l_l I l_ll_I
IAntimony-I _I l_I l_I l_l I l_ll_I
!Arsenic -I _I l_I l_I l_l I l_ll_I
IBarium-=:1 _I l_I l_I l_I l_ll_I
IBeryllium I _I l_I l_I l_I l_ll_I
!Cadmium I _I l_I l_I l_I l_ll_I
ICalcium-I _I l_I l_I l_ll_I
IChromium_ I
ICobalt_I
ICopper_ I
-'_I_I '-'l_Il_I l_I
l_I
l_I
l_ll_I
l_ll_ I
l_ll_I
I Iron
!Lead
f Magnesiuml
I
I I
I l_I
l_I
l_I
l_I
l_ll_I ,_,,_,
Manganese I
Mercury_!
_I
_I
I l_I
I_
I
I_!
'-'I_!
I
'-"-
'-"-'
l"_ll_I
1=
Nickel _ I I_ _I I_ l_ll_I
Potassium I
Selenium_!
I_
I_ -'_I_I I_
I_
'-'
l_I
I_!
l_ll_I
l_ll_I
Silver I I_ I_ l_I I- 11 - I
Sodium-I I_ _I I_ l_I I - II - I
Thallium_ I
Vanadium_ I
I_ ,_,
_I I_ l_I I- 11 - I
Zinc
cyanide_ I
I
I_
I_ l_I
l_I
'-I_
I
'-"
l_l I
I_! I
I - II - I
I- II - I
I - 11 - I
I '-I_ l_I I l_l I l_ll_ I
ONE - 23 Revision 1
December 1987
4
ICP INTERFERENCE CHECK SAMPLE
Lab Name: Contract:

Lab Code: Case No: SAS No.: SDG No.:
ICP ID Number: ICS Source:
I
I True Initial Found Final Found
I Sol. Sol. Sol. Sol. Sol. Sol.
Analyte I A AB A AB %R AB A %R
I I _ _ _ _ _ _ _ _ _ - - - - _ _ _ _ _ _ _ _ _ __
!Aluminum I
IAntimony_ I_ __
IArsenic - I ---
I Bari um - I ---
IBerylliuml ----
!Cadmium I --
I Calcium_ I _ __
I Chromium I ---
I Cobalt -I ---
1 Copper-I ----
I Iron - I --
I Lead ---
I _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
I Magnesium I - - -
IManganesel
---
!Mercury I_ _ _ _ _ _ _ _ _ - - - - - - - - - - - - - - -
I Nickel - I
I Potassium 1 - - -
!Selenium I ---
!Silver _I _ __
!Sodium-I ---
I Thallium I ---
1vanadium-1 ----
I Zinc -I --
1 I - - - - - _ _ _ _ ___
ONE - 24 Revision 1
December 1987
SA EPA SAMPLE NO.
SPIKE SAMPLE RECOVERY
Lab Name: Contract:
Matrix (soil/water): Level (low/med) :
Concentration Units (ug/L or mg/kg dry weight):
I I I I I I I
I control I I I I I I
I Limit Spiked Sample I Sample I Spike I I I I
'--=--=--- ___ ------- _I _______ I

IAnalyte
I Aluminum_
%R Result (SSR) Cl
l_I
Result (SR) Cl Added (SA)I
l_I I
%R IQI MI
l _ _ _ l_l _I
l_l_I
I Antimony l_I l_I I l_l_I
I Arsenic_- l_I l_I I l_l_I
I Barium_ l_I l_I I l_l_I
Beryllium l_I l_I I l_l_I
Cadmium_ l_I l_I I l_l_I
Calcium_ l_I l_I I l_l_I
Chromium_ l_I l_I I l_l_I
Cobalt_ I l_I _l_I
Copper_ I l_I _l_I
Iron I l_I _l_I
Lead I l_I _l_I
Magnesium I l_I _l_I
Manganese I l_I _l_I
Mercury_ I l_I _l_I
Nickel_ I l_I _l_I
Potassium I l_I _l_I
Selenium_! l_I _l_I
Silver I l_I _l_I
Sodium-I l_I _l_I
Thallium! l_I .I I I
Vanadium-I l_I l=l==I
Zinc -, l_I l_l_I
Cyanide I l_I l_l_I
_ _ _-_I l_I l_l_I
Comments:
ONE - 25 Revision 1
December 1987
SB EPA SAMPLE NO.
POST DIGEST SPIKE SAMPLE RECOVERY
Lab Name: Contract:
Matrix (soil/water): Level (low/med):
I I I I I I
I I control I I I I
I I Limit Spiked Sample I Sample I Spike I I I
I Analyte I %R Result ( SSR) CI Result (SR) CI Added ( SA)I %R QI M I
I I _ _ _ - - - - - - - _l _______ I l ____ l_I
I Aluminum_ I l_I l_I I _l_I
I Antimony_\ l_I l_I I _l_I
I Arsenic l_I I_ I _l_I
!Barium_- l_I I_ I _l_I
I Beryllium l_I I_ I _l_I
!Cadmium_ l_I I_ I _l_I
!Calcium_ l_I I_ I _l_I
I Chromium_ l_I I I _l_I
!Cobalt_ l_I I_ I !_!_!
I Copper l_I I_ I l_l_I
tiron - l_I I_ I I_!_!
!Lead l_I I_ I l_l_I
!Magnesium l_I I_ I l_l_I
!Manganese I_! I_ I l_l_I
!Mercury_ l_I I_ I l_l_I
I Nickel l_I l_I I l_l_l
I Potassium l_I l_I I l_l_I
I Selenium I l_I l_I I l_l_I
!Silver -, l_I 1_1 I l_l_I
!Sodium-I !_I l_I I l_l_I
!Thallium I l_I l_I I .l_l_I
!Vanadium=! l_I l_I I l_l_I
I Zinc I l_I I I I l_l_I
I cyanide I l_I 1-1 I l_l_I
I -, l_I l=I I l_l_I
Comments:
ONE - 26 Revision 1
December 1987
6 EPA SAMPLE NO.
DUPLICATES
Lab Name: Contract:

Matrix {soil/water): Level {low/med):
% Solids for Sample: % Solids for Duplicate:
Concentration Units {uq/L or mg/kg dry weight):
I I 11 11 I
I I Control 11 11 I I
IAnalyte I Limit 11 Sample (S) Cl I Duplicate (0) c .RPO QI MI
I I 11 _I I _l_I
I Aluminum_!
!Antimony I
II
I '-"
l_l I
1:I_ _l_I
_l_I
!Arsenic -I I l_l I I_ _l_I
IBarium-=I I l_l I I_ _l_I
I Beryllium I I l_l I I_ _l_I
!Cadmium I I l_l I I_ _l_I
f Calcium-1
Chromium_!
Cobalt_ I
I
I
I
'-"
_II
_I I
'-
I_
I_
_l_I
_l_I
_l_I
Copper_! I _I I l_ll _l_I
Iron
Lead
I
I
Magnesium I
I
I
_I I
_,,
_II
l_ll
l_ll
l_l I
-'-'
-'-'
Manganese!
Mercury_ I
I
I
I -"
_I I
I
I
'-'-'
l_l_I
l_l_I
Nickel
-'
Potassium I
Selenium_!
I
I
I
_I I
_II
11
I
I
I
l_l_I
l_l_I
l_l_I
Silver_ I I 11 I l_l_I
Sodium
-'
Thallium_!
Vanadium_ I
II
II
II
-"
_II
_I I
I
I
I
l_.l_I
"-'-'
ll_l_I
Zinc I II _II I ll_l_I
Cyanide_ I
I
II
II
_II
_II
I
I "-'-'
ll_l_I
ONE - 27 Revision I
December 1987
7
LABORATORY CONTROL SAMPLE
Lab Name: Contract:

Solid LCS Source:
Aqueous LCS Source:
I I I
I I Aqueous (ug/L) I Solid (mg/kg)
\Analyte I True Found %R I True Found c Limits %R
I I
Aluminum_ I I I I I 1=:1 I I
Antimony_ I I I I l_I I I
Arsenic
Barium
Beryllium
I
I
I
I
I
I
I
I
I
I
I
I
'-'
l_I
l_I
I
I
I
I
I
I
Cadmium- I I I I l_I I I
Calcium
Chromium
I
I
I
I
I
I
I
I '-'
l_I
I
I
I
I
Cobalt
Copper_
Iron
I
I
I
I
I
I
I
I
I
I
I
I
'-'
l_I
l_I
I
l
I
I
I
I
!Lead I I I I l_I I I
!Magnesium
!Manganese\
I Mercury_ I
I
I
I
I
I
I
I
I
I
I
I
I
'-'
I_ I
I_ I
I
I
I
I
I
I
!Nickel I I I I I l_I I I
I Potassium I I I I I l_I I I
I Selenium_ I I I I I l_l I I.
!Silver_! I I I I l_I I I
ISodium_ I I I I I I_ I I I
IThallium_I I I I I l_I I I
IVanadium_ I I I I I l_I I I
\Zinc I I l l l l_I I l
I Cyanide_ I I I I I I_ I I I
I I l l l I l_I I I
ONE - 28 Revision 1
December 1987
8
STANDARD ADDITION RESULTS
Lab Name: Contract:


I I I I I
I EPA
I Sample
I
I 0 ADD
I
I l ADD 2 ADD
'II 3 ADD Final
I
I
No. An Oil ABS ICON ABS CON ABS ICON ABS Cone. r QI
---
---
---
I_
I_
I_ =1
_I
I_
l_I
,_,
l_I
_I
_I
I
---
---
I_
I_
I_
-'
_I
_I
l_I
l_I
_l
_I
_I
--- I_ _I l_I _I
--- I_ _I l_I _I
--- I_ _I l_I _I
--- I_ _I l_I I_ I
--- I_ _I l_I l_I
---
=1=
_I_
_ I_
I_
I_
I_
I_
l_I
_I
l_I
l_I
l_I
l_I
_ I_ I_ l_I
_ I_ I_ l_I
_I_ I_ l_I
_I_ l_J l_ I
l_I_ l_I l_I
l_I_ l_I I_ I
l_I_ l_I I_ I
l_I_
l_I_
l_I_
l_I_
l_I
l_I
l_I
l_I
=1
_I
_I
I I
I_ I
l_I
l_I
ONE - 29 Revision 1
December 1987
9 EPA SAMPLE NO.
ICP SERIAL DILUTIONS
Lab Name: Contract:

Matrix (soil/water): Level (low/med) :

II II serial II % II I
I Initial Sample I I Dilution Differ- I I I
Analyte I Result (I) Cl I Result (S) C ence IQI MI
I_ _ _ _ _ _ I I l_l_I
Aluminum_ I l_ll l_l_l
Antimony I l_I I l_l_l
Arsenic_- I l_I I l_l_I
Barium_ ____________ l_I I l_l_I
Beryllium _______ l_I l_l_l
Cadmium__ _ ____________ !_! l~l_I
Calcium__ ____________ !_ l_l_I
Chromium ____________ !_ l_l_I
Cobalt ____________ !_ l_l_I
Copper_ ____________ I_ I_ I_ I
Iron I I I ·1 I
(Lead I ------.1 l _ _ _ l l=l=I
(Magnesium! _ _ _ _ _ _ I_ - - - - - - _ I I l_l_I
(Manganese I ___________ I _ _ _ _ _ _ _ I_ I I l_l_I
!Mercury__ ( ____________ ! _ _ _ _ _ _ _ !_I ll_l_I
INickel_I _ _ _ _ _ _ I_ _ _ _ _ _ _ I_ I I l_l_I
IPotassiuml ___________ I_ _ _ _ _ _ _ I_ I I l_l_I
f Selenium I _________ I _ _ _ _ _ _ I_ I I l_l_I
)Silver -, ________ I _ _ _ _ _ _ I_ I 11_1_1
ISodium___ I __________ I_ _ _ _ _ _ _ I_ I I l_l_I
\Thallium 11 I_! I l_l I l l_l_I
I Vanadium-I I l_l I l_l I I l_l_I
I Zinc -, , l_l I l_l I 11_1_1
I II l_ll l_ll 11_1_1
ONE - 30 Revision I
December 1987
10
HOLDING TIMES
Lab Name: Contract:

Lab Code: Case No.: SAS No.: - - - SDG No.:
I I 11 I I I I
I I I I Mercury I Mercury I Cyanide I Cyanide I
I EPA I I Date 11 Prep I Holding I Prep I Holding I
I Sample No. I Matrix I Received 11 Date I Time I Date I Time I
I I 11 I I I I
I I 11 I I I
I I 11 I I
I I 11 I I
I I 11 I I
I I 11 I I
I 11 I I
I 11 I I
I 11 I I
I 11 I I
11 11 I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I I
11 I .I
11 I I
11 I I
II I I
II I I
ONE - 31 Revision 1
December 1987
11
INSTRUMENT DETECTION LIMITS {QUARTERLY)
Lab Name: Contract:

ICP ID Number: Date:
Flame AA ID Number:
Furnace AA ID Number:
I I
I Wave- I I
I length ) Back- CRDL IDL I I
Analyte I (nm) ground {ug/L) {ug/L) I M I
--....----I--~- -~~ ~~~ _____ l_I
Aluminum_ I 200 l_I
Antimony I 60 l_I
Arsenic_- I 10 l_I
Barium I 200 l_I
Beryllium! 5 l_I
Cadmium__ 5 I_
Calcium__ 5000 I_
Chromium_ 10 I __
Cobalt 50 I
Copper_ 25 I_
Iron 100 I_
Lead s I_
Magnesium sooo I
Manganese 15 I
Mercury o. 2 I
!Nickel -- 40 I
I Potassium 5000 I_
I Selenium 5 I_
I Silver_-_ 10 I_
!Sodium 5000 I
IThalliun\ 10 I
!Vanadium- 50 I
I Zinc - 20 I
I I_
Comments:
ONE - 32 Revision 1
December 1987
12A
ICP INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name: Contract:

I
I Wave- Interelement Correction Factors for:
1 length
Analyte I (nm) Al Ca Fe Mg
-::----,-----'------
Aluminum I_______ ------- --------- --------- _________ ! _________
Antimony-I _______ ------- --------- --------- _________ ! _________
Arsenic -II_______
Barium __ ---------- --------- --------- _________ ! _________
---------- --------- --------- _________ ! _________
Beryllium I_______ ---------- --------- --------- _________ ! _________
Cadmium I______ --------- --------- --------- _________ ! _________
Calcium-- I
Chromiuiill _______ -------- --------- ---------
--------- --------- ---------
---------'---------
---------'---------
Cobalt -
Copper ------ ---------- --------- ---------
---------- --------- ---------
---------'---------
_________11 _________
Iron --- ---------- --------- --------- _________ ! _________
Lead ------
Magnesium ---------- ---------
-------- --------- ---------'---------
--------- --------- _________ ! _________
Manganese ------
______
---------- --------- --------- ---------'---------
Mercury
Nickel -- ---------- --------- --------- ---------'---------
Potassium - - - - - --------- --------- --------- ---------'---------
--------- --------- --------- ---------'---------
--------- --------- --------- ---------'---------
Selenium
--------- --------- -------- ---------'---------
Silver
ISodium- -------- --------- --------- _________ ! _______
IThalliUiil - - - - -
!Vanadium- -------- --------- --------- ---------'-------
!Zinc - ----- --------- --------- --------- ---------'-------
--------- --------- --------- ---------'-------
I~----- ------- -------- -------- --------- ---------'---------
Comments:
ONE - 33 Revision 1
December 1987
12B
ICP INTERELEMENT CORRECTION FACTORS (QUARTERLY)
Lab Name: Contract:

I I
I I wave- Interelement Correction Factors for:
I I length
IAnalyte I (nm)
I I _ __
!Aluminum I _ __
I Antimony-I
Arsenic _I _ __
Barium - I
Beryllium I _ __
Cadmium I
Calcium_ I _ __
Chromium I
Cobalt - , - - -
Copper-I _ __
Iron - I
Lead ---
I _ __
Magnesium I _ __
Manganese I _ __
Mercury I
Nickel-,---
Potassium!
Selenium I ---
!Silver - , - - -
!Sodium-I
I Thal 1 i\.iii\, - - -
t Vanadium-1
!Zinc -,---
1 '---
Comments:
ONE - 34 Revision 1
December 1987
13
ICP LINEAR RANGES (QUARTERLY)
Lab Name: Contract:

I I
I Integ. I
I Time Concentration I I
f Analyte (Sec.} (ug/L} IM I
'~~....-~- -~~~- -~~~~~~'-'
f Aluminum_ l_I
f Antimony_ l_I
f Arsenic_ l_I
f Barium_ l_I
f Beryllium l_I
f Cadmium_ _I
f Calcium_ _I
!Chromium_ _I
I Cobalt_ _I
!Copper_ _I
f Iron _I
Lead _I
Magnesium _I
Manganese _I
Mercury _I
Nickel_- _I
Potassium _I
Selenium _I
Silver _I
Sodium___ _I
Thallium_ _I
Vanadium l_I
Zinc l_I
~~-~- -~~~ ~~~----'-'
Comments:
ONE - 35 Revision 1
December 1987
lA EPA SAMPLE NO.
VOLATILE ORGANICS ANALYSIS DATA SHEET
Lab Name: Contract: ________
Matrix: (soil/water) Lab Sample ID:

---
Sample wt/vol: _ _ _ (g/mL) _ _ Lab File ID:
Level: (low/med) Date Received:
% Moisture: not dee. Date Analyzed:

---
Column: (pack/cap) Dilution Factor:
CONCENTRATION UNITS:
CAS NO. COMPOUND {ug/L or ug/Kg) _ _ __ Q
I I I
I 74-87-3---------Chloromethane I- - - - - - - I
' 74-83-9---------Bromomethane I -------- I
1 75-01-4---------Vinyl Chloride I_______ I
I 75-00-3---------Chloroethane I --------- I
1 75-09-2---------Methylene Chloride l _________ I I
I 67-64-1---------Acetone I l ___ I
I 75-15-0---------carbon Disulfide I I I
I 75-35-4---------1,1-Dichloroethene I I I
I 75-34-3---------1,1-Dichloroethane I I I
I 540-59-0--------1,2-Dichloroethene (total) I I I
I 67-66-3---------Chloroform -I I I
I 107-06-2--------1,2-Dichloroethane I I I
I 78-93-3---------2-Butanone I I I
I 71-55-6---------1,1,1-Trichloroethane I I I
I 56-23-5---------Carbon Tetrachloride I I I
I 108-05-4--------Vinyl Acetate I I I
I 75-27-4---------Bromodichloromethane I I I
I 78-87-5----··----1, 2-Dichloropropane I I I
I 10061·01-5------cis-l,3-Dichloropropene I I I
I 79-01-6---------Trichloroethene I I I
I 124-48-1--------Dibromochloromethane I I I
I 79-00-5---------1,l,2-Trichloroethane I I ---
1 71-43-2---------Benzene I I- - -
1 10061-02-6------trans-l,3-Dichloropropene___ I I _ __
I 75-25-2---------Bromoform I I ----
1 108-10-1--------4-Methyl-2-Pentanone I I- - -
1 591-78-6--------2-Hexanone I I
1 127-18-4--------Tetrachloroethene I I
---
1 79-34-5---------1,1,2,2-Tetrachloroethane__ I I ---
1 108-88-3--------Toluene I I- - -
----
1 108-90-7--------Chlorobenzene I I ___
I 100-41-4--··-----Ethylbenzene I I ---
' 100-42-5--------Styrene I I- - -
1 1330-20-7-------Xylene (total) I I ---
1 I '~-
ONE - 36 Revision 1
December 1987
lB EPA SAMPLE NO.
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
Contract: _ _ _ _ __
Matrix: (soil/water) _ __ Lab Sample ID:
% Moisture: not dee. dee. Date Extracted:

--- --- -----
Extraction: (SepF/Cont/Sonc) Date Analyzed:
GPC Cleanup: (Y/N) pH: _ _ Dilution Factor:
CAS NO. COMPOUND (ug/L or ug/Kg) _ _ __ Q
I
I 108-95-2--------Phenol ----...,--=-"'-~----
I lll-44-4--------bis(2-Chloroethyl)ether- - -
1 95-57-8---------2-Chlorophenol
-------
1 541-73-1--------1,3-Dichlorobenzene
1 106-46-7--------1,4-Dichlorobenzene
-----
-----
1 100-51-6--------Benzyl alcohol _ _ _ _ _ __
I 95-50-1---------1,2-Dichlorobenzene- - - - -
1 95-48-7---------2-Methylphenol
---...,,...,....---
! 108-60-l--------bis(2-Chloroisopropyl)ether
I 106-44-5--------4-Methylphenol -
I 621-64-7--------N-Nitroso-di-n-propylamine
I 67-72-1---------Hexachloroethane -
I 98-95-3---------Nitrobenzene- - - - - - - -
1 78-59-1---------Isophorone
1 88-75-5~--------2-Nitrophenol ---------
--------
1 105-67-9--------2,4-Dimethylphenol
-----
1 65-85-0---------Benzoic acid
--------
1 lll-91-1--------bis(2-Chloroethoxy)rnethane
I 120-83-2--------2,4-Dichlorophenol -
I 120-82-1--------1,2,4-Trichlorobenzene- - -
' 91-20-3---------Naphthalene_ _ _ _ _ _ _ __
I 106-47-8--------4-Chloroaniline-,--------
I 87-68-3---------Hexachlorobutadiene- - - - -
1 59-50-7---------4-Chloro-3-methylphenol
1 91-57-6---------2-Methylnaphthalene
---
I 77-47-4---------Hexachlorocyclopent_a_d_i_e_n_e_
I 88-06-2---------2,4,6-Trichlorophenol --
1 95-95-4---------2,4,5-Trichlorophenol
1
----
91-58-7---------2-Chloronaphthalene- - - - -
1 88-74-4---------2-Nitroaniline
1
-------
131-11-3--------Dimethylphthalate- - - - - -
' 208-96-8--------Acenaphthylene- - - - - - -
' 606-20-2--------2,6-Dinitrotoluene
I -----
ONE - 37 Revision 1
December 1987
10 EPA SAMPLE NO.
PESTICIDE ORGANICS ANALYSIS DATA SHEET
Contract: ______

---
% Moisture: not dee. dee. _ __ Date Extracted:

--- -----
GPC Cleanup: (Y/N)_ pH: _ _ Dilution Factor:
CAS NO. COMPOUND (ug/L or ug/Kg) _ _ __ Q
319-84-6--------alpha-BHC___________ - - - - - -
319-85-7--------beta-BHC ---
319-86-8--------delta-BHC
---------
58 - 89 - 9 - - - - - - - - - gamma - BHC (Lindane) _ _ _ _ - - - - - - _ __
76-44-8---------Heptachlor_ _ _ _ _ _ _ _ _ - - - - - - . . . . -
309-00-2--------Aldrin ---
1024-57-3~------Heptachlor epoxide_ _ _ _ _ - - - - - - -
959-98-8--------Endosulfan I ----
60-57-1---------Dieldrin
72-55-9---------4,4'-DDE_ ----------~
_________ - - - - - - -
72-20-8---------Endrin ----
33213-65-9------Endosulfan II _ _ _ _ _ _ _ - - - - - - - _ __
72-54-8---------4,4'-DDD_ _ _ _ _ _ _ _ _ _~ - - - - - - -
1031-07-8-------Endosulfan sulfate --
50-29-3---------4, 4 '-DDT_ _ _ _ _ _ _ _ _ _~------- ___
72-43-5---------Methoxychlor_ _ _ _ _ _ _ _ _ - - - - - - -
53494-70-5------Endrin ketone --
5103-71-9-------alpha-Chlordane _ _ _ _ _ _ _ - - - - - - - _ _
5103-74-2----~--gamma-Chlordane ________ - - - - - - - _ _
8001-35-2-------Toxaphene_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
12674-11-2------Aroclor-1016_ _ _ _ _ _ _ _ _ - - - - - - - - _ __
11104-28-2------Aroclor-1221_ _ _ _ _ _ _ _ _ - - - - - - - _ __
11141-16-5------Aroclor-1232 _ _ _ _ _ _ _ _ _ - - - - - - -
53469-21-9------Aroclor-1242 --
12672-29-6------Aroclor-1248 _ _ _ _ _ _ _ _ - - - - - - - ___
11097-69-1------Aroclor-1254
--------
11096-82-5------Aroclor-1260_ _ _ _ _ _ _ _ - - - - - - - ___
ONE - 38 Revision 1
December 1987
1E EPA SAMPLE NO.
VOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
Contract: _ _ _ __
Matrix: (soil/water) _ __ Lab Sample ID:
% Moisture: not dee. Date Analyzed:

---
Column: (pack/cap) Dilution Factor:
Number TICs found: (ug/L or ug/Kg) _ __
I
I CAS NUMBER I COMPOUND NAME I RT EST. CONC. I Q I
1================1============================1======== =============1=====1
1.
------ I ----
2.
------ I ----
3 ·------ I__
4·------ I__
5. - - - - - - I ----
6.
------ I ----
7 ·------ r__
s ·------ I__
9 ·------ I__
10.______ I__
11.______ I__
12.______ I__
13 ·
14 ._-_
-_-_
-_-_
- '
I_--
_ -
1s.______ I__
16.______ I__
17.______ I__
18.______ ·1 _ _
19. I
20.------ ,--
21. ------------- I
22. ---- ,--
23. ------I __
24. I
25. I--
-
-
I
26.
27. I --
28. I- -
29. --
) o. I
--
1
--
- - - - - - - - - - - - - - - - - - - - - - - - - - ______ I__
ONE - 39 Revision 1
December 1987
lF EPA SAMPLE NO.
SEMIVOLATILE ORGANICS ANALYSIS DATA SHEET
TENTATIVELY IDENTIFIED COMPOUNDS
Contract: _ _ _ __

---
% Moisture: not dee. dee. Date Extracted:

--- --- -----
GPC Cleanup: (Y/N)_ pH: _ _ Dilution Factor:
Number TICs found: (ug/L or ug/Kg)
---
I I
CAS NUMBER COMPOUND NAME I RT I EST. CONC. I Q I
================ ==============--=====--======= ========1=============1=====1
1. I I
2. ------ I I
3.------ I I
4. ------------- I I
5. I
6. ------ I
I I
7.
------ I
------ I
8. I I
9.------ I I
10. ------------- I I
11.
12.------ I I
I I
13. ------------- I I
14. - - - - - - I I
15.------
I I
16. ------------- I I
17. I I
18.
------ I
19.--....----
I
20.
------
------------- I
21.
------ I
22. I
23. ------ I
24.------
I
25. ------------- I
26. I
27. - - - - - - I
28.
------ I
29. ------ I
30. ------ I
------ I
ONE - 40 Revision 1
December 1987
2B
SOIL VOLATILE SURROGATE RECOVERY
Contract:~~~~~~
Level: (low/med)
I EPA I Sl I S2 I SJ IOTHER !TOTI

I SAMPLE NO. J(TOL)#J (BFB)#I (DCE)#J IOUTI
1============1======1======1====== ======1===1
01 I I I l_l
02 I I I I I
OJ I I I 1-1
04 I I I 1-1
05 I I I 1-1
06 I I I 1-1
07 I I I 1-1
oa I I I l=I
09 I I I l_I
10 I I l_I
11 I I l_I
12 I I l_I
13 I I l_I
14 I I l_I
15 I I l_I
16 I I l_I
11 I l_I
lB I l_I
19 I l_I
20 I l_I
211 I l_I
221 I l_I
231 I l_I
241 I l_I
25 I I I I
26 I I I I
271 I I I
2a 1 I I I
291 I l_I
301 I l_I
QC LIMITS
Sl (TOL) = Toluene-dB (81-117)
S2 (BFB} = Bromofluorobenzene (74-121}
SJ (DCE) = 1,2-Dichloroethane-d4 (70-121)
# Column to be used to flag recovery values
* Values outside of contract required QC limits

D Surrogates diluted out
page of
ONE - 41 Revision 1
December 1987
20
SOIL SEMIVOLATILE SURROGATE RECOVERY
Lab Name: Contract:

-----
Level: (low/med)
--
EPA I Sl I S2 I S3 I S4 I SS I S6 IOTHER ITOT
I SAMPLE NO. I (NBZ) #I (FBP) #I (TPH) #I (PHL) #I (2FP) #I (TBP) #I I OUT
1============1======1======1======1====== ====== ======1======1===
011 I I I I I I
021 I I I I I I
031 I I I I I I_
041 I I I I I I_
os I I I I I I
06 I I I I I I
07 I I I I I I
08 I I I I I I
09 I I I I I I
10 I I I I I I
11 I I I I I I
12 I I I I I I
13 I I I I I I
14 I I I I I 1-
15 I I I I I I 1-
16 I I I I I I I
17 I I I I I I I
18 I I I I I I I I
19 I I I I I I I I
20 I I I I I I I I
211 I I I I I I I
221 I I I I I I I
231 I I I I I I 1-
241 I I I I I I I
2s1 I I I I I I 1-
261 I I I l ___ I I I
271 I I I I I I I
28 I I I I I I I I
29 I I I I I I I I
30 I I I I I I I I
QC LIMITS
Sl (NBZ) = Nitrobenzene-d5 (23-120)
S2 (FBP) = 2-Fluorobiphenyl (30-115)
SJ (TPH) = Terphenyl-d14 (18-137)
S4 (PHL) = Phenol-d6 (24-113)
SS (2FP) = 2-Fluorophenol (25-121)
S6 (TBP) = 2,4,6-Tribromophenol (19-122)

* Values outside of contract required QC limits
page_ o f _
ONE - 42 Revision 1
December 1987
2F
SOIL. PESTICIDE SURROGATE RECOVERY
Lab Name: Contract:

------------ -----
Level: (low/med)
EPA I Sl !OTHER I
I SAMPLE NO. I (DBC)#I I
1============1======1======1
011 _ _ _ _ _ _ - - - - - -
021 ______ - - - - - -
03 I ______ - - - - - -
041 ______ - - - - - -
05 I ______ - - - - - -
061 _ _ _ _ _ _ - - - - - -
07 I ______ - - - - - -
08 I ______ - - - - - -
09 I ______ - - - - - -
lu I _ _ _ _ _ _ _ _ _ _ __
111 _ _ _ _ _ _ --- ---
121 _ _ _ _ _ _ --- ---
131 _ _ _ _ _ _ --- ---
141 _ _ _ _ _ _ --- ---
15 I ______ - - - - - -
161 _ _ _ _ _ _ - - - - - -
17 I ______ - - - - - -
181 _ _ _ _ _ _ - - - - - -
191 _ _ _ _ _ _ - - - - - -
20 I _ _ _ _ _ _ _ _ _ _ __
211 _ _ _ _ _ _ - - - - - -
221 _ _ _ _ _ _ - - - - - -
23 I ______ - - - - - -
24 I ______ - - - - - -
251 _ _ _ _ _ _ - - - - - -
261 _ _ _ _ _ _ - - - - - -
27 I ______ - - - - - -
281 _ _ _ _ _ _ - - - - - -
291 _ _ _ _ _ _ - - - - - -
301 _ _ _ _ _ _ - - - - - -
ADVISORY
QC LIMITS
Sl (DBC) = Dibutylchlorendate (24-150)
* Values outside of QC limits
page_ o f _ Revision 1
ONE - 43
December 1987
3B
SOIL VOLATILE MATRIX SPIKE/MATRIX SPIKE" DUPLICATE RECOVERY
Contract:
-----
Lab Code: Case No.: .SAS No.: SDG No.:
Matrix Spike - EPA Sample No.: Level: (low/med)
I SPIKE I SAMPLE I MS I MS I QC I
I ADDED ICONCENTRATIONjCONCENTRATIONI % ILIMITSI
I COMPOUND I (ug/Kg) I (ug/Kg) I (ug/Kg) I REC #I REC. I
1========================1=========1=============1=====--=======1======1====:=1
I 1,1-Dichloroethene I I I I 159-1721
I Trichloroethene I I I I 162-1371
I Benzene I I I I 166-1421
I Toluene I I I I 159-139 I
I Chlorobenzene I I I I 160-1331
I I I I I I I
I I SPIKE I MSD I MSD

I I ADDED I CONCENTRATION I % % QC LIMITS I
I COMPOUND I (ug/Kg) I (ug/Kg) I REC #I RPO #I RPO I REC. I
1========================1=========1=============1======1======1======1======1
I 1,1-Dichloroethene I I I I I 22 159-1721
I Trichloroethene I I I I I 24 162-1371
I Benzene I I I I I 21 166-142 I
I Toluene I I I I I 21 159-1391
I Chlorobenzene I I I I I 21 160-1331
I I I I I I I I
# Column to be used to flag recovery and RPO values with an asterisk
RPO: out of outside limits

Spike Recovery: ~~-o-ut of outside limits
COMMENTS:
ONE - 44 Revision 1
December 1987
30
SOIL SEMIVOLATILE MATRIX SPIKE/MATRIX SP!KE DUPLICATE RECOVERY
Contract=~---~
Matrix Spike - EPA Sample No.: Level:(low/rned)
I SPIKE I SAMPLE I MS I MS I QC I
I ADDED ICONCENTRATIONICONCENTRATIONI % ILIMITSI
f COMPOUND I (ug/Kg) I (ug/Kg) I (ug/Kg) I REC #I REC. I
1========================1=========1============= =============1======1======1
I Phenol I I I 126- 901
I 2-Chlorophenol I I I 125-1021
I 1,4-Dichlorobenzene I I I 128-1041
I N-Nitroso-di-n-prop:(l')I I I 141-1261
I 1,2,4-Trichlorobenzene I I I 138-1071
I 4-Chloro-3-methylphenoll I I 126-1031
I Acenaphthene I I I 131-1371
I 4-Nitrophenol I I I I 11-114 I
I 2, 4-Dinitrotoluene I I I I 28- 89 I
I Pentachlorophenol I I I 117-1091
I Pyrene I I I 135-142 I
I I I I I I

I I ADDED CONCENTRATION I % % QC LIMITS
I COMPOUND I (ug/Kg) (ug/Kg) I REC #I RPO #I RPO I REC. I
1========================1========= =============1======1======1======1======1
I Phenol I I I I 35 126- 901
I 2-Chlorophenol I I I I 50 125-102 I
I 1,4-Dichlorobenzene I I I I 27 128-1041
I N-Nitroso-di-n-prop:(l'}j I I I 38 I 41-126 I
I 1, 2, 4-Trichlorobenzene I I I I 23 I 38-107 I
I 4-Chloro-3-methylphenoll I I I 33 126-1031
I Acenaphthene I I I I 19 131-137 I
I 4-Nitrophenol I I I I so 111-114 I
I 2, 4-Dinitrotoluene I I I I 47 128- 89 I
I Pentachlorophenol I I I I 47 117-1091
I Pyrene I I I I 36 I 35-142 I
I I I I I I I
(1) N-Nitroso-di-n-propylamine

RPD: out of outside limits

Spike Recovery: --o-ut of outside limits
---
COMMENTS:
ONE - 45 Revision I
December 1987
3F
SOIL PESTICIDE MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Contract:
-----
Lab Code: case No.: SAS No.: SDG No.:
Matrix Spike - EPA Sample No.: Level: (low/med)
I I SPIKE I SAMPLE I MS I MS I QC. I

I I ADDED I CONCENTRATION I CONCENTRATION I % I LIMITS I
I COMPOUND I (ug/Kg) I (ug/Kg) I (ug/Kg) I REC #I REC. I
1========================1-----~1=============1=============1======1======1
I ganuna-BHC (Lindane) _ _ I I I I 146-1271
I Heptachlor I I I I 135-1301
I Aldrin I I I 11 I 34-132 I
I Dieldrin I I I :1 131-1341
I Endrin I I I I 142-1391
I 4,4'-DDT I I I I 123-1341
I I I I I I I

I I ADDED I CONCENTRATION I % % QC LIMITS
I COMPOUND I (ug/Kg) I (ug/Kg) I REC #I RPO #I RPO I REC. I
1========================1=======--=1=============1======1======1======1======1
I ganuna-BHC (Lindane) I I I I I 50 I 46-1271
I Heptachlor --1 I I I I 31 I 35-130 I
I Aldrin I I I I I 43 l 34-132 I
I Dieldrin I I I I I 38 I 31-134 I
I Endrin I I I I I 45 142-1391
I 4,4'-DDT I I I I I 50 123-1341
I I I I I I I I
RPO: out of outside limits

Spike Recovery: _ _-_-~-o-ut of outside limits
COMMENTS:
ONE - 46 Revision 1
December 1987
4A
VOLATILE METHOD BLANK SUMMARY
Contract: _ _ _ ___
Lab File ID: Lab Sample ID:
Date Analyzed: Time Analyzed:
Matrix: (soil/water) Level:(low/rned)
Instrument ID:
THIS METHOD BLANK APPLIES TO THE FOLLOWING SAMPLES, MS AND MSD:
I EPA LAB I LAB I TIME I

I SAMPLE NO. I SAMPLE ID I FILE ID I ANALYZED I
1============1==============1==============1==========1
011 ________ --------- - - - - - - - - - ----~
021 _______ --------- ---------- ----~
031 _______ --------- ---------- ----~
041 _________ ---------- ---------- - - - - -
OSI
061 ________ ------------ ---------- ----~

011 _________ - - - - - - - - - - - - - - - - - - - - - - - - - - -
081 _________ - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
091 _________ - - - - - - - - - -
101 -----------
111 --------
121
131 __________ ----------- ------------
141 ------
151 __________ ----------- ------------ ---------
161 ________ ---------- ------------ -------
171 __________ ---------- ------------ -------
181 ________ ----------- ----------- ------
191 _________ ---------- ----------- ------
201
211 _________ ------------ ------------ -----
221 __________ ----------- ------------ --------
241 ____~-----
231 -~-------- ------------ --------
251
261 __________ ------------ ---------~
271 --------
281 __________ ----------- - - - - - - - - - - - - -
291 __________ ----------- ----------- - - - - - -
JOI __________ - - - - - - - - - - - - - - - - - - - - - - - - - - -
COMMENTS:
page of ONE - 47 Revision 1

December 1987
48
SEMIVOLATILE METHOD BLANK SUMMARY
Contract:
-----
Lab File ID: Lab Sample ID:
Date Extracted: Extraction:(SepF/Cont/Sonc)
Date Analyzed: Time Analyzed:
Matrix: (soil/water) Level: (low/med)
Instrument ID:
I EPA I LAB LAB I DATE

I SAMPLE NO. I SAMPLE ID FILE ID I ANALYZED I
1============1============== ==============1==========1
011 I I I
021 I I I
031 I I I
041 I I I
051 I I I
061 I I I
071 I I I
081 I I I
091 I I I
101 I I I
111 I I I
121 I I I
131 I I I
141 I I I I
151 I I I I
161 I I I I
17 I I I I I
181 I I I I
191 I I I I
201 I I I I
211 I I I I
221 I I I I
231 I I I I
241 I I I I
251 I I I I
261 I I I I
271 I I I I
281 I I I I
291 I I I I
301 I I I I
COMMENTS:
page_ o f _
ONE - 48 Revision 1
December 1987
4C
PESTICIDE METHOD BLANK SUMMARY
Contract=---~-
Lab Sample ID: Lab File ID:
Matrix:(soil/water) Level: (low/med)
Date Extracted: Extraction: (SepF/Cont/Sonc)

--
Date Analyzed (1): Date Analyzed (2):
Time Analyzed (1): Time Analyzed (2):
Instrument ID (2): Instrument ID (2):
GC Column ID (1): GC Column ID (1):
I EPA I LAB DATE I DATE

I SAMPLE NO. I SAMPLE ID 21
!ANALYZED llANALYZED
1============1==============1==========1==========1
011 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - -
021 ______ - - - - - - - - - - - - - - - - - -
OJI _ _ _ _ _ _ - - - - - - - - - - - - - - - - -
041 ______ - - - - - - - - - - - - - - - - -
OSI _ _ _ _ _ _ - - - - - - - - - - - - - - - - -
061 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - -
071 ______ - - - - - - - - - - - - - - - - - -
08
09
10
11
------
------
i; ------ ------- ----- -----
14 - - - - - - - - - - - - - - - - - - - - - - -
15
16
------
17 - - - - - -
18 - - - - - - - - - - - - - - - - - - - - - - -
19 - - - - - - --~---- - - - - - - - - - -
20 - - - - - -
211 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - -
22 I ______ --~--------------
231 ______ --~---- ----- -----
241 _ _ _ _ _ _ - - - - - - - - - - - - - - - - -
251 ______ - - - - - - - - - - - - - - - - - -
261 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - -
COMMENTS:
page_ o f _
ONE - 49 Revision 1
December 1987
SA
VOIATILE ORGANIC GC/MS TUNING ANO MASS
CALIBRATION - BROMOFLUOROBENZENE (BFB)
Contract:
-----
Lab File ID: BFB Injection Date:

-----
Instrument ID: BFB Injection Time:
-----
Matrix:(soil/water) Level:(low/med) Column:(pack/cap)
---
I % REIATIVE
I m/e ION ABUNDANCE CRITERIA I ABUNDANCE I
1===== 1==============1
I 50 15.0 - 40.0% of mass 95_ _ _ _ _ _ _ _ _ _ _ _ _ _ 1 I
I 75 30.0 - 60.0% of mass 95 I I
I 95 Base peak, 100% relative abundance I I
I 96 5.0 - 9.0% of mass 95 I I
I 173 Less than 2.0% of mass 174 I ( )11
I 174 Greater than 50.0% of mass 95 I I
I 175 5.0 - 9.0% of mass 174 I ( )11
I 176 Greater than 95.0%, but less than 101.0% of mass 1741 ( )11
I 171 s • o - 9 • o% of mass 116 I C )2I
I___ ---~---,---,---------------------.---:--1
1-Value is % mass 174 2-Value is % mass 176
I
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS:
I
I EPA LAB IAB DATE TIME

I SAMPLE NO. I SAMPLE ID FILE ID I ANALYZED I ANALYZED I
t============I============== ==============l==========t==========I
011 _ _ _ _ __
021 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
031 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
041 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
OSI _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
061 _ _ _ _ _ _ ------- ------- ----- -----
071 - - - - - -
081
------
091 _ _ _ _ _ _ _ ------- ------- ----- -----
101 _ _ _ _ _ _ _ ------- ------- ----- -----
111 - - - - - -
121 _ _ _ _ _ _ ------- ------- ----- -----
131 _ _ _ _ _ _ ------- ------- ----- -----
141 _ _ _ _ _ _ _ ------- ------- ----- -----
151 _______ ------- ------- ----- -----
161 _________ ------- ------- ----- -----
17 I ______
181 _______ - - - - - - - - - - - - - - - - - - - - - - - -
191 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
·, 201
21 I ______
-------
221 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
page of
ONE - 50 Revision 1
December 1987
SB
SEMIVOLATILE ORGANIC GC/MS TUNING AND MASS
CALIBRATION - DECAFLUOROTRIPHENYLPHOSPHINE (OFTPP)
Contract: _ _ _ _~
Lab Code: Case No.: SAS No.: SOG No.:
Lab File ID: DFTPP Injection Date:

-----
Instrument ID: DFTPP Injection Time:
-----
% RELATIVE
I m/ e I ION ABUNDANCE CRITERIA I ABUNDANCE I
!===== =====================================================!==============!
I 51 30.0 - 60.0% of mass 198 I I
I 68 Less than 2.0% of mass 69 I ) 11
I 69 Mass 69 relative abundance I I
I 70 Less than 2.0% of mass 69 I ( ) 11
I 127 40.0 - 60.0% of mass 198 I I
I 197 Less than 1.0% of mass 198 I I
I 198 Base Peak, 100% relative abundance I I
I 199 5.0 to 9.0% of mass 198 I I
I 275 10.0 - 30.0% of mass 198 I I
I 441 Present, but less than mass 443 I I
I 443 17.0 - 23.0% of mass 442 I }21
I I I
1-Value is % mass 69 2-Value is % mass 442
THIS TUNE APPLIES TO THE FOLLOWING SAMPLES, MS, MSD, BLANKS, AND STANDARDS:
I EPA I LAB I LAB I DATE I TIME I

I SAMPLE NO. I SAMPLE ID I FILE ID I ANALYZED I ANALYZED
1============1==============1==============1==========1==========
011 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
021 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
031 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
041 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
OSI _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
061 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - - -
071
------
081 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - - - -
091 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
101 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
111
121 _
___________ - - - - - - - - - - - - - - - - - - - - - - - -
131 -------
141 -------
151 -----
16\ -----
171
------
181 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
191
201
211 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - - -
page 22
of1 - : - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
ONE - 51 Revision 1
December 1987
6A
VOIATILE ORGANICS INITIAL CALIBRATION DATA
Contract:
-----
Instrument ID: Calibration Date(s):

-----
Matrix:(soil/water) Level: (low/med) Column:(pack/cap)
---
Min RRF for SPCC(#) = 0.300 (0.250 for Bromoform) Max %RSD for CCC(*) = 30.0%
IAB FILE ID: RRF20 = RRF50 = - - - - - - - I

RRFlOO=_________ RRF150=------- RRF200=_______ I
---------------------------------,---~!I __
%
_
COMPOUND IRRF20 IRRF50 IRRFlOOIRRF150IRRF200I RRF I RSD I
===========================!======!====== ======1=----===1======1======1=====1
Chloromethane # I I I I I #
Bromomethane: I I I I I I ___
Vinyl Chloride * I I I I I *
Chloroethane I I I I I I_ _ I
Methylene Chloride I I I I I I I
Acetone I I I I I I I
carbon Disulfide I I I I I I I
1,1-Dichloroethene * I I I I *
(1,1-Dichloroethane # I I I I ____ #
11,2-Dichloroethene (total)_! I I I I
I Chloroform * I I I *
11, 2-Dichloroethane I I l__ I
I 2-Butanone I I I
11, 1, 1-Trichloroethane I I I
I Carbon Tetrachloride I I I
I Vinyl Acetate I I I
I Bromodichloromethane I I I
11,2-Dichloropropane * I *
I cis-1, 3-Dichloropropene I__
ITrichloroethene-..,...------
' Dibromochloromethane_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ i
11, 1, 2-Trichloroethane I
I Benzene I I
ttrans-1,3-Dichloropropene I I
I Bromoform -# JI
14-Methyl-2-Pentanone I
12-Hexanone ---
I _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
JTetrachloroethene I
11,1,2,2-Tetrachloroethane_ _ #-_ --_-_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 11JI
)Toluene * *
I Chlorobenzene #_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ #
I Ethylbenzene *---- __________________ •
I Styrene_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __
!Xylene (total) I I I
!===========================================================================!
!Toluene-dB I I I I I I I I
IBromofluorobenzene I I I I I I I I
11,2-oichloroethane-d4 I I I I I I I I
I I I I I I I I I
ONE - 52 Revision 1
December 1987
6B
SEMIVOLATILE ORGANICS INITIAL CALIBRATION DATA
Lab Name: _ _ _ _ _ _ _ _ _ _ __ Contract:

-----
Instrument ID: Calibration Date(s):

-----
Min RRF for SPCC(#) = 0.050 Max %RSD for CCC(*) = 30.0%
LAB FILE ID: RRF20 = RRF50 = I
RRFSO == RRF120= RRF160= I
---------------:------,----,-.---.,..---~----=----1--:%,--
I
COMPOUND IRRF20 RRFSO IRRFSO IRRF120 RRF160I RRF I RSD I
==========--======================!====== =======1==--===1====== ======1======1=====1
Phenol- - - - - - - - - -*- - - ---- - - - - - - - - - II- - - - -*
bis(2-Chloroethyl)ether I
2-Chlorophenol --1 1---
1,3-Dichlorobenzene I I- - -
--
1,4-Dichlorobenzene * I *
Benzyl alcohol I- - -
1,2-Dichlorobenzene I - - -
\2-Methylphenol I I- - -
lbis(2-Chloroisopropyl)etherl I- - -
14-Methylphenol I I- - -
IN-Nitroso-di-n-propylamine # I- - - #
I Hexachloroethane
INitrobenzene
-,
I
1---
I - - II
\Isophorone I 1, I
2-Nitrophenol * I *
2,4-Dimethylphenol I
Benzoic acid I I- - -
bis(2-Chloroethoxy)methane I ---
2,4-Dichlorophenol -.---
1,2,4-Trichlorobenzene I --- *
Naphthalene I- - -
4-Chloroaniline I- - -
Hexachlorobutadiene *--- ---
4-Chloro-3-methylphenol * - - **
2-Methylnaphthalene --,---
Hexachlorocyclopentadiene # ---
J 2, 4, 6-Trichlorophenol _* ___ - - "*
1!
12,4,5-Trichlorophenol I ---
12-Chloronaphthalene I- - -
12-Nitroaniline I- - -
I Dimethylphthalate 1---
\Acenaphthylene I ---
\2,6-Dinitrotoluene I- - -
13-Nitroaniline I- - -
IAcenaphthene *- -
--
- - *
(2,4-Dinitrophenol # #
14-Nitrophenol # - - - #
1 I-
_- - - - - - _ _ _ _ _ _ _ _ _ _ _ _ _ __
__
ONE - 53 Revision 1
December 1987
7A
VOLATILE CONTINUING CALIBRATION CHECK
Contract:
------
Instrument ID: Calibration Date: Time:
----- -----
Lab File ID: Init. Calib. Date(s):
-----
Matrix:(soil/water) _ _ _ Level:(low/med) Column:(pack/cap}
Min RRF50 for SPCC(#) = 0.300 (0.250 for Bromoform) Max tD for CCC(*) = 25.0%
I I_ I I
I COMPOUND I RRF RRFSO I %D I
I ==== I====== === I==== I
IChloromethane # #
(Bromomethane - - - - - - - I I
Vinyl Chloride * *
Chloroethane_ _ _ _ _ _ _ _ I_ _ _ _ _ _ _ _ _ I
Methylene Chloride I I
Acetone I I
Carbon Disulfide I I
1,1-Dichloroetbene * *
1,1-Dichloroethane
- - - - #I----
1, 2 - Di ch lo roe then e -(total)
#
---- ----I
Chloroform * *
1,2-Dichloroethane_________________ 11
2-Butanone I
1,1,1-Trichloroethane I
Carbon Tetrachloride I
!Vinyl Acetate I
Bromodichloromethane I
1,2-Dichloropropane * *
cis-1,3-Dichloropropene I___ I
Trichloroethene --1 ,--- 1
Dibromochloromethane I I ---I
1, 1, 2-Trichloroethane I I I
Benzene I I I
trans-1,3-Dichloropropene I I I
Bromoform -# I I ~
4-Methyl-2-Pentanone I I I I
2-Hexanone I I I 1
Tetrachloroethene I I I I
ll,1,2,2-Tetrachloroethane # I I #
!Toluene -. I I *---
IChlorobenzene # I I- - -#
1Ethylbenzene * I I_ _ _ *
I Styrene I I ___
I Xylene (total) I I I I
!================================================!
1Toluene-d8 I I I I
IBromofluorobenzene I I I I
ll,2-Dichloroethane-d4 I I I I
I I I I I
ONE - 54 Revision 1
December 1987
SA
VOLATILE INTERNAL STANDARD AREA SUMMARY
Contract: _ _ _ __
Lab File ID (Standard): Date Analyzed: _ _ _ __
Instrument ID: Time Analyzed: - - - - -
Matrix:(soil/water) Level: (low/med) Column:(pack/cap)
I ISl (BCM) I I IS2 (DFB) I IS3 (CBZ) I

I I AREA # I RT I AREA # I RT I AREA # I RT I
1============1==========1======1 1======1==========1======1
I 12 HOUR STDI I I I I I I
1============1==========1======1==========1====--=1==========1======1
I UPPER LIMIT I I I I I I
1============ ==========1======1==========1=--==--=1==========1======1
I LOWER LIMIT I I I I I
I============ ==========1======1==========1====--=I========== ======
I EPA SAMPLE I I I I
I NO. I I I I
I============ ========== ====== ========== ====== ========== ======
011 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
021 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
03 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
04 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
05
06
II ______ - - - - - - - - - - - - - - - - - - - - - - - -
071 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
08 I ______ - - - - - - - - - - - - - - - - - - - - - - - -
09 I ______ - - - - - - - - - - - - - - - - - - - - - - - -
10 I ______ - - - - - - - - - - - - - - - - - - - - -
11 I ---
121 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
13 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
14 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
15 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
16 I
171 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - -
18 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
19 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
20 I ______ - - - - - - - - - - - - - - - - - - - - - - - -
211 _ _ _ _ _ _ - - - - - - - - - - - - - - - - - - - - - - - - -
22 I ______ - - - - - - - - - - - - - - - - - - - - - - - - -
ISl (BCM} = Bromochloromethane 9
UPPER LIMIT • + 100%

IS2 (DFB} = 1,4-Difluorobenzene of internal standard area.
IS3 (CBZ) = Chlorobenzene-d5 LOWER LIMIT = - 50%
of internal standard area.
# Column used to flag internal standard area values with an asterisk
page_ o f _
ONE - 55 Revision 1
December 1987
SB
SEMIVOLATILE INTERNAL STANDARD AREA SUMMARY
Contract: ___ .......___
Lab File ID (Standard): Date Analyzed:

-----
Instrument ID: Time Analyzed:
-----
I ISl (DCB) I I IS2 (NPT) I I IS3 (ANT) I

I I AREA # I RT I AREA # I RT I AREA # I RT
1============1==========1======1==========1======1==========1======
I 12 HOUR STDI I I I I I
1=========--==1=-~-=====1======1==========1======1==========1-==~=~--~=
I UPPER LIMIT! I I I I I
l========--===1==========1 1==========1======1==========1======
I LOWER LIMITI I I I I I
1============1==========1=-~-===1==========1======1==========1======
I EPA SAMPLE I I I I I I
I NO. I I I I I I
1============1=======--==1======1==========1======1==========1======
011 I I I I I- - -
021 I I I I I__
031 I I I I I__
04 I I I I I I
OSI I I I I 1--
061 I I 1 I I_ _
071 I I I I_ _
081 I I I ___ - - - - - _ __
09 I I I I ___ - - - - - _ __
101 I I I _ _ _ _ _ _ _ _ _ __
111 I I I _ _ _ _ _ _ _ _ _ __
121 I I I _ _ _ _ _ _ _ _ _ __
13 I I I I ___ - - - - - _ __
141 I I I _ _ _ _ _ _ _ _ _ __
1s1 I I I _ _ _ _ _ _ _ _ _ __
161 I I I _ _ _ _ _ _ _ _ _ __
171 I I I _ _ _ _ _ _ _ _ _ __
181 I I I _ _ _ _ _ _ _ _ _ __
191 I I I _ _ _ _ _ _ _ _ _ __
201 I I I _ _ _ _ _ _ _ _ _ __
211 I I I ___ - - - - - _ __
221 I I I ___ - - - - - _ __
ISl (DCB) = 1,4-Dichlorobenzene-d4 UPPER LIMIT = + 100%
IS2 (NPT) = Naphthalene-dB of internal standard area.
IS3 (ANT) = Acenaphthene-dlO LOWER LIMIT c - 50%
of internal standard area.
# Column used to flag internal standard area values with an asterisk
page of
ONE - 56 Revision 1
December 1987
80
PESTICIDE EVALUATION STANDARDS SUMMARY
Lab Name: Contract:

-------~---~ -----
Instrument ID: - - - - - GC Column ID:
Oates of Analyses: to
-----
Evaluation Check for Linearity

CALIBRATION I CALIBRATION I CALIBRATION I %RSD I
PESTICIDE FACTOR I FACTOR I FACTOR I (<:./= I
I I EVAL MIX A I EVAL MIX B I EVAL MIX C I 10.0%) I
1=============1=============1=============1=============1======1
I Aldrin I I I I I
I Endrin I I I I I
I 4,4'-DDT I I I I I (1)
I DBC --, I I I I
I I I I I I
(1) If > 10.0% RSD, plot a standard curve and determine the ng
for each sample in that set from the curve.
Evaluation Check for 4,4'-DDT/Endrin Breakdown

(percent breakdown expressed as total degradation)
I DATE I TIME I ENDRIN 14,4'-DDTICOMBINEDI
I ANALYZED I ANALYZED I I I ( 2) I
I============ ==========1==========1========1========1========1
I INITIAL
011 EVAL MIX B
021 EVAL MIX B
031 EVAL MIX B
041 EVAL MIX B
051 EVAL MIX B
061 EVAL MIX B
071 EVAL MIX B
081 EVAL MIX B
091 EVAL MIX B
101 EVAL MIX B
111 EVAL MIX B
121 EVAL MIX B
131 EVAL MIX B
141 EVAL MIX B
I ______ - - - - - - - - - - -~--- - - - - - --~-
(2) See Form instructions.
ONE - 57 Revision 1
December 1987
SE
PESTICIDE EVALUA~ION STANDARDS SUMMARY
Evaluation of Retention Time Shift for Dibutylchlorendate
Contract:
-----
Instrument ID: GC Column ID:

-----
Dates of Analyses: to
-----
EPA LAB SAMPLE I DATE I TIME %
I SAMPLE NO. I ID I ANALYZED I ANALYZED I D I *
!============!=====~-====== ==========1==========1======1==
011 _ _ _ _ _ _ - - - - - - - - - - - - -------'-~-1-
021 I I_
031 I I_
041 I I_
051 I I_
061 I I_
011 I I_
oa1 I I_
091 I I_
101 I l_I
111 I l_I
121 I l_I
131 I l_I
141 I l_I
151 ~ l_I
161 I l_I
171 I l_I
181 I l_I
191 I l_I
201 I _I
211 I I
221 I _I
231 I _I
24 I I I
25 I I I
26 I I I
271 I I
28 I I I
29 I I I
30 I I I
311 I _I
321 I l_I
331 I l_I
341 I l_I
351 I l_I
361 I l_I
371 I l_I
381 I l_I
* Values outside of QC limits (2.0% for packed columns,
0.3% for capillary columns)
page _ of
ONE - 58 Revision 1
December 1987
9
PESTICIDE/PCB STANDARDS SUMMARY
Lab Name: Contract:

------------ -----
Instrument ID: _ _ _ __ GC Column ID:
I DATE(S) OF FROM: - - - - - I DATE OF ANALYSIS I

1 ANALYSIS TO: I TIME OF ANALYSIS I
I TIME(S) OF FROM:_____ I EPA SAMPLE NO. I
I ANALYSIS TO: I (STANDARD) I
I ---- I I
~----,~~~~~-R-T~~~,~~~-, I I I I
I COMPOUND I RT WINDOW !CALIBRATION! RT jCALIBRATIONjQNTI %D I
I I FROM TO I FACTOR I I FACTOR I Y/N I I
!=============!====== ====== 1===========1======1===========1===1=====1
lalpha-BHC I I I I l_I I
I beta-BHC - - , I I I I I
ldelta-BHC I I I I I_ I
lgamma-BHC--1 I I I I_ I
IHeptachlo_r_I I I I I_ I
I Aldrin -, I I I I_ I
IHept. epoxidel I I I I
IEndosulfan I I I I I= I
I Dieldrin -, I I I_ I
I 4 , 4 I -DOE I I I I_ I
IEndrin I I I I I_ I
!Endosulfan III I I I I_ I
I 4' 4 I -DOD I I I I I I I
!Endo. sulfate! I I I I I= I
I 4, 4 I -DDT I I I I I I I
IMethoxychlor I I I I I I= I
!Endrin ketone! I I I I I_ I
la. Chlordane I I I I I I_ I
lg. Chlordane-I I I I I I I
IToxaphene -, I I I I I I
IAroclor-1016 I I I I I I I
!Aroclor-1221-1 I I I I I I
!Aroclor-1232-1 I I I I I I
JAroclor-1242-1 I I I I I I
IAroclor-1248-I I I I I I I
IAroclor-1254 I I I I I 1- I
IAroclor-1260-I I I I I I I
I -, I I I I I I I
Under QNT Y/N: enter Y if quantitation was performed, N if not performed.
%D must be less than or equal to 15.0% for quantitation, and less than
or equal to 20.0% for confirmation.
Note: Determining that no compounds were found above the CRQL is a form of
quantitation, and therefore at least one column must meet the 15.0% criteria.
For multicomponent analytes, the single largest peak that is characteristic

of the component should be used to establish retention time and %D.
Identification of such analytes is based primarily on pattern recognition.
page_ o f _
ONE - 59 Revision 1
December 1987
10 EPA SAMPLE NO.
PESTICIDE/PCB IDENTIFICATION
Lab Name: Contract:

-----------~- ------
GC Column ID (1): GC Column ID (2):
Instrument ID (1): Instrument ID (2):
Lab Sample ID:
Lab File ID: (only if confirmed by GC/MS)
PESTICIDE/PCB RETENTION TIME RT WINDOW QUANT? GC/MS?

OF STANDARD (Y/N) (Y/N)
From TO
01 Column 1
02 Column 2
03 Column 1
04 Column 2
05 Column 1
06 Column 2
07 Column 1
08 Column 2
09 Column 1
10 Column 2
11 Column 1
12 Column 2
Comments:
page_ o f _ ONE - 60 Revision 1

December 1987
CHAPTER TWO
CHOOSING THE CORRECT PROCEDURE
2.1 PURPOSE
This chapter aids the analyst in choosing the appropriate methods for
samples, based upon sample matrix and the analytes to be determined.
2.1.1 Trace Analysis vs. Macroanalysis
The methods presented in SW-846 were designed through sample s1z1ng and
concentration procedures to address the problem of "trace" analyses (<1000 ppm),
and have been developed for an optimized working range. These methods are also
applicable to "minor" (1000 ppm - 10,000 ppm) and "major" (>10,000 ppm) analyses,
as well as to "trace" analyses, through use of appropriate sample preparation
techniques that result in analyte concentration within that optimized range. Such
sample preparation techniques include:
1) adjustment of size of sample prepared for analysis,
2) adjustment of injection volumes,
3) dilution or concentration of sample,
4) elimination of concentration steps prescribed for "trace" analyses,
5) direct injection {of samples to be analyzed for volatile constituents).
The performance data presented in each of these methods were generated from
"trace" analyses, and may not be applicable to "minor" and "major" analyses.
Generally, extraction efficiency improves as concentration increases.
CAUTION: Care should be taken when analyzing samples for trace analyses
subsequent to analysis of concentrated samples due to the
possibility of contamination.
2.1.2 Choice of Apparatus and Preparation of Reagents
Since many types and sizes of glassware and supplies are commercially
available, and since it is possible to prepare reagents and standards in many
different ways, those specified in these methods may be replaced by any similar
types as long as this substitution does not affect the overall quality of the
analyses.
2.2 REQUIRED INFORMATION

In order to choose the correct combination of methods to form the
appropriate analytical procedure, some basic information is required.
2.2.l Physical State(s) of Sample
The phase characteristics of the sample must be known. There are several
general categories of phases in which the sample may be categorized:
TWO - 1 Revision 2
November 1992
Aqueous Oil and Organic Liquid
Sludges Solids
Multiphase Samples EP and TCLP Extracts
Ground Water
2.2.2 Analytes
Analytes are divided into classes based on the determinative methods which
are used to identify and quantify them. Table 2-1 lists the organic analytes of
SW-846 methods, Table 2-2 lists the analytes that may be prepared using Method
3650, and Table 2-3 lists the analytes that are collected from stack gas
effluents using VOST methodology. Tables 2-4 through 2-31 list the target
analytes of each organic determinative method. Some of the analytes appear on
more than one table, as they may be determined using any of several methods.
Table 2-32 indicates which methods are applicable to inorganic target analytes.
2.2.3 Detection Limits Required
Regulations may require a specific sensitivity or detection limit for an
analysis, as in the determination of analytes for the Toxicity Characteristic
(TC} or for delisting petitions. Drinking water detection limits, for those
specific organic and metallic analytes covered by the National Interim Primary
Drinking Water Standards, are desired in the analysis of ground water.
2.2.4 Analytical Objective
Knowledge of the analytical objective will be useful in the choice of
aliquoting procedures and in the selection of a determinative method. This is
especially true when the sample has more than one phase. Knowledge of the
analytical objective may not be possible or desirable at all management levels,
but that information should be transmitted to the analytical laboratory
management to ensure that the correct techniques are being app 1i ed to the
analytical effort.
2.2.5 Detection and Monitoring
The strategy for detection of compounds in environmental or process samples
may be contrasted with the strategy for monitoring samples. Detection samples
define initial conditions. When there is little information available about the
composition of the sample source, e.g., a well or process stream, mass spectral
identification of organic analytes leads to fewer false positive results. Thus,
the most practical form of detection for organic analytes, given the analytical
requirements, is mass spectral identification. The choice of technique for
metals is governed by the detection limit requirements and potential
interferents.
Monitoring samples, on the other hand, are analyzed to confirm existing and
on-going conditions, tracking the presence or absence of constituents in an
environmental or process matrix. A less compound(s)-specific detection mode may
be used because the matrix and the analytical conditions are well defined and
stable.
TWO - 2 Revision 2
November 1992
2.2.6 Sample Containers. Preservations, and Holding Times
Appropriate sample containers, sample preservation techniques, and sample
holding times for aqueous matrices are listed in Table 2-32, near the end of this
chapter. Similar information may be found in Table 3-1 of Chapter Three
(inorganic analytes) and Table 4-1 of Chapter Four (organic analytes). Samples
must be extracted/analyzed within the specified holding times for the results to
be considered reflective of total concentrations. Analytical data generated
outside of the specified holding times must be considered to be minimum values
only. Such data may be used to demonstrate that a waste is hazardous where it
shows the concentration of a constituent to be above the regulatory threshold but
cannot be used to demonstrate that a waste is not hazardous.
2.3 IMPLEMENTING THE GUIDANCE

The choice of the appropriate sequence of methods depends on the
information required and on the experience of the analyst. Figure 2-1 summarizes
the organic analysis options available. Appropriate selection is confirmed by
the quality control results. The use of the recommended procedures, whether they
are approved or mandatory, does not release the analyst from demonstrating the
correct execution of the method.
2.3.1 Extraction and Sample Preparation Procedures
Methods for preparing organic analytes are shown in Table 2-34. Method
3500 and associated methods should be consulted for further details on preparing
the sample for analysis.
2.3.1.1 Aqueous Samples
The choice of a preparative method depends on the sample. Methods
3510 and 3520 may be used for extraction of the semivolatile organic
compounds. Method 3510, a separatory funnel extraction, is appropriate
for samples which will not form a persistent emulsion interphase between
the sample and the extraction solvent. The formation of an emulsion that
cannot be broken up by mechanical techniques will prevent proper
extraction of the sample. Method 3520, a l iquid-1 iquid continuous
extraction, may be used for any aqueous sample; this method will minimize
emulsion formation.
2.3.1.1.1 Basic or Neutral Extraction of Semivolatiles
The solvent extract obtained by performing either Method 3510
or 3520 at a neutral or basic pH wi 11 contain the compounds of
interest. Refer to Table 1 in the extraction methods (3510 and/or
3520) for guidance on the pH requirements for extraction prior to
analysis.
TWO - 3 Revision 2
November 1992
2.3.1.1.2 Acidic Extraction of Phenols and Acids
The extract obtained by performing either Method 3510 or 3520
at a pH less than or equal to 2 will contain the phenols and acid
extractables.
2.3.1.2 Solid Samples
Soxhlet (Method 3540) and ultrasonic (Method 3550) extractions are
used with solid samples. Consolidated samples should be ground finely
enough to pass through a 1 mm sieve. In limited applications, waste
dilution (Method 3580) may be used if the entire sample is soluble in the
specified solvent.
Method 3540 and 3550 are neutral-pH extraction techniques and
therefore, depending on the analysis requirements, acid-base partition
cleanup (Method 3650) may be necessary. Method 3650 will only be needed
if chromatographic interferences are severe enough to prevent detection of
the analytes of interest. This separation will be most important if a GC
method is chosen for analysis of the sample. If GC/MS is used, the ion
selectivity of the technique may compensate for chromatographic
interferences.
2.3.1.3 Oils and Organic Liquids
Method 3580, waste dilution, may be used and the resultant sample
analyzed directly by GC or GC/MS. To avoid overloading the analytical
detection system, care must be exercised to ensure that proper dilutions
are made. Method 3580 gives guidance on performing waste dilutions.
To remove interferences, Method 3611 may be performed on an oil
sample directly, without prior sample preparation.
Method 3650 is the only other preparative procedure for oils and
other organic liquids. This procedure is a back extraction into an
aqueous phase. It is generally introduced as a cleanup procedure for
extracts rather than as a preparative procedure. Oils generally have a
high concentration of semivolatile compounds and, therefore, preparation
by Method 3650 should be done on a relatively small aliquot of the sample.
Generally, extraction of 1 ml of oil will be sufficient to obtain a
saturated aqueous phase and avoid emulsions.
2.3.1.4 Sludge Samples
There is no set ratio of liquid to solid which enables the analyst
to determine which of the three extraction methods cited is the most
appropriate. If the sludge is an organic sludge (sol id material and
organic liquid, as opposed to an aqueous sludge), the sample should be
handled as a multiphase sample.
Determining the appropriate methods for analysis of sludges is
complicated because of the lack of precise definition of sludges with
TWO - 4 Revision 2
November 1992
respect to the relative percent of liquid and solid components. They may
be classified into three categories but with appreciable overlap.
2.3.1.4.1 Liquids
Use of Method 3510 or Method 3520 may be applicable to sludges
that behave like and have the consistency of aqueous liquids.
Ultrasonic extraction (Method 3550) and Soxhlet (Method 3540)
procedures will, most likely, be ineffective because of the
overwhelming presence of the liquid aqueous phase.
2.3.1.4.2 Solids
Soxhlet (Method 3540) and ultrasonic extraction (Method 3550)
will be more effective when applied to sludge samples that resemble
solids. Samples may be dried or centrifuged to form solid materials
for subsequent determination of semivolatile compounds.
Using Method 3650, Acid-Base Partition Cleanup, on the extract
may be necessary, depending on whether chromatographic interferences
prevent determination of the analytes of interest.
2.3.1.4.3 Emulsions
Attempts should be made to break up and separate the phases of
an emulsion. Several techniques are effective in breaking emulsions
or separating the phases of emulsions.
1. Freezing/thawing: Certain emulsions will separate if exposed to
temperatures below 0°C.
2. Salting out: Addition of a salt to make the aqueous phase of an
emulsion too polar to support a less polar phase promotes
separation.
3. Centrifugation: Centrifugal force may separate emulsion
components by density.
4. Addition of water or ethanol: Emulsion polymers may be
destabilized when a preponderance of the aqueous phase is added.
If techniques for breaking emulsions fail, use Method 3520.
If the emulsion can be broken, the different phases (aqueous, solid,
or organic liquid) may then be analyzed separately.
2.3.1.5 Multiphase Samples
Choice of the procedure for aliquoting multiphase samples is very
dependent on the objective of the analysis. With a sample in which some
of the phases tend to separate rapidly, the percent weight or volume of
each phase should be calculated and each phase should be individually
analyzed for the required analytes.
TWO - 5 Revision 2
November 1992
An alternate approach is to obtain a homogeneous sample and attempt
a single analysis on the combination of phases. This approach will give
no information on the abundance of the analytes in the individual phases
other than what can be implied by solubility.
A third alternative is to select phases of interest and to analyze
only those selected phases. This tactic must be consistent with the
·sampling/analysis objectives or it will yield insufficient information for
the time and resources expended. The phases selected should be compared
with Figure 2-1 and Tables 2-34 through 2-36 for further guidance.
2.3.2 Cleanup Procedures
Each category in Table 2-35, Cleanup of Organic Analyte Extracts,
corresponds to one of the possible determinative methods available in the manual.
Cleanups employed are determined by the analytes of interest within the extract.
However, the necessity of performing cleanup may also depend upon the matrix from
which the extract was developed. Cleanup of a sample may be done exactly as
instructed in the cleanup method for some of the analytes. There are some
instances when cleanup using one of the methods may only proceed after the
procedure is modified to optimize recovery and separation. Several cleanup
techniques may be possible for each analyte category. The information provided
is not meant to imply that any or all of these methods must be used for the
analysis to be acceptable. Extracts with components which interfere with
spectral or chromatographic determinations are expected to be subjected to
cleanup procedures.
The analyst's discretion must determine the necessity for cleanup
procedures, as there are no clear cut criteria for indicating their use. Method
3600 and associated methods should be consulted for further details on extract
cleanup.
2.3.3 Determinative Procedures
The determinative methods for organic analytes have been divided into three
categories, shown in Table 2-36: gas chromatography/mass spectrometry (GC/MS);
specific detection methods, i.e., gas chromatography (GC); and high performance
liquid chromatography (HPLC). This division is intended to help an analyst
choose which determinative method will apply. Under each analyte column, SW-846
method numbers have been indicated, if appropriate, for the determination of the
analyte. A blank has been left if no chromatographic determinative method is
available.
Generally, the MS procedures are more specific but less sensitive than the
appropriate gas chromatographic/specific detection method.
Method 8000 gives a general description of the technique of gas
chromatography. This method should be consulted prior to application of any ~f
the gas chromatographic methods.
Method 8080, for organochlorine pesticides and polychlorinated biphenyls,
Method 8140 and 8141, for organophosphorus pesticides, and Methods 8150 and 8151,
for chlorinated herbicides, are preferred over GC/MS because of the combination
TWO - 6 Revision 2
November 1992
of selectivity and sensitivity of the flame photometric, nitrogen-phosphorus, and
electron capture detectors.
Methods 8240 and 8260 are both GC/MS methods for volatile analytes. Method
8240 uses a packed column whereas Method 8260 employs a capillary column. Better
chromatographic separation of the volatile compounds may be obtained by using
Method 8260 rather than 8240. Performance criteria will be based on Method 8260.
Method 5030 has been combined with both Method 8240 and 8260, with which it was
used exclusively. A GC with a selective detector is al so useful for the
determination of volatile organic compounds in a monitoring scenario, described
in Section 2.2.5.
Methods 8250 and 8270 are both GC/MS methods for semivolatile analytes.
Method 8250 uses a packed column whereas Method 8270 employs a capillary column.
Better chromatographic separation of the semivolatile compounds may be obtained
by using Method 8270 rather than 8250. Performance criteria will be based on
Method 8270.
2.4 CHARACTERISTICS
Figure 2-2 outlines a sequence for determining if a waste exhibits one or
more of the characteristics of a hazardous waste.
2.4.1 EP and TCLP extracts
The leachate obtained from using either the EP (Figure 2-3A) or the TCLP
(Figure 2-38) is an aqueous sample, and therefore, requires further solvent
extraction prior to the analysis of semivolatile compounds.
The TCLP leachate is solvent extracted with methylene chloride at a pH > 11
by either Method 3510 or 3520. Method 3510 should be used unless the formation
of emulsions between the sample and the solvent prevent proper extraction. If
this problem is encountered, Method 3520 should be employed.
The solvent extract obtained by performing either Method 3510 or 3520 at
a basic or neutral pH will contain the base/neutral compounds of interest. Refer
to the specific determinative method for guidance on the pH requirements for
extraction prior to analysis.
Due to the high concentration of acetate in the TCLP extract, it is
recommended that purge-and-trap be used to introduce the volatile sample into the
gas chromatograph.
2.5 GROUND WATER

Appropriate analysis schemes for the determination of analytes in ground
water are presented in Figures 2-4A, 2-48, and 2-4C. Quantitation limits for the
metallic analytes should correspond to the drinking water limits which are
available.
TWO - 7 Revision 2
November 1992
2.5.l Special Techniques for Metal Analytes
All atomic absorption analyses should employ appropriate background
correction systems whenever spectral interferences could be present. Several
background correction techniques are emp 1oyed in modern atomic absorption
spectrometers. Matrix modification can complement background correction in some
cases. Since no approach to interference correction is completely effective in
all cases, the analyst should attempt to verify the adequacy of correction. If
the interferant is known {e.g. high concentrations of iron in the determination
of selenium), accurate analyses of synthetic solutions of the interferant {with
and without analyte) could establish the efficacy of the background correction.
If the nature of the i nterferant is not es tab 1i shed, good agreement of ana 1yt i ca 1
results using two substantially different wavelengths could substantiate the
adequacy of the background correction.
To reduce matrix interferences, all graphite furnace atomic absorption
{GFAA) analyses should be performed using techniques which maximize an isothermal
environment within the furnace cell. Data indicate that two such techniques,
L'vov platform and the Delayed Atomization Cuvette (DAC), are equivalent in this
respect, and produce high quality results.
~Cadmium and antimony should be determined by GFAA. These two elements are
analyzed by GFAA to achieve lower detection 1imits. Typical GFAA detection
limits for antimony and cadmium are 3 µg/L and 0.1 µg/L, compared to 60 µg/L and
3 µg/L by ICP.
All furnace atomic absorption analysis should be carried out using the
exact matrix modifiers listed below. {See also the appropriate methods.)
Element ( s) Modifier
As and Se Nickel Nitrate
Pb Phosphoric Acid
Cd Ammonium Phosphate
Sb Ammonium Nitrate
Tl Platinum/Palladium
The ICP calibration standards must match the acid composition and strength
of the acids contained in the samples. Acid strengths in the ICP calibration
standards should be stated in the raw data.
2.5.2 Special Techniques for Indicated Analytes and Anions
If an Auto-Analyzer is used to read the cyanide distillates, the
spectrophotometer must be used with a 50 mm path length cell. If a sample is
found to contain cyanide, the sample must be redistilled a second time and
analyzed to confirm the presence of the cyanide. The second distillation must
fall within the 14 day holding time.
TWO - 8 Revision 2
November 1992
2.6 REFERENCES
I. Barcelona, H.J. "TOC Determinations in Ground Water"; Ground Water 1984,
z.illl, 18-24.
2. Riggin, R.; et al. Development and Evaluation of Methods for Total Organic
Halide and Purgeable Organic Halide in Wastewater; U.S. Environmental
Protection Agency. Office of Research and Development. Environmental
Monitoring and Support Laboratory. ORD Publication Offices of Center for
Environmental Research Information: Cincinnati, OH, 1984; EPA-600/4-84-008.
3. McKee, G.; et al. Determination of Inorganic Anions in Water by Ion
Chromatography; {Technical addition to Methods for Chemical Analysis of
Water and Wastewater, EPA 600/4-79-020), U.S. Environmental Protection
Agency. Environmental Monitoring and Support Laboratory. ORD Publication
Offices of Center for Environmental Research Information: Cincinnati, OH,
1984; EPA-600/4-84-017.
TWO - 9 Revision 2
November 1992
TABLE 2-1
DETERMINATIVE ANALYTICAL METHODS FOR ORGANIC COMPOUNDS
Compound Applicable Method(s)
Acenaphthene 8100, 8250/8270, 8310, 8410

Acenaphthylene 8100, 8250/8270, 8310, 8410
Acetaldehyde 8315
Acetone 8240/8260, 8315
Acetoni tril e 8240/8260
Acetophenone 8250/8270
2-Acetylaminofluorene 8270
l-Acetyl-2-thiourea 8270
Aci fl uorfen 8151
Acrolein (Propenal) 8030, 8240/8260, 8315, 8316
Acrylamide 8032, 8316
Acryl oni tril e 8030, 8031, 8240/8260, 8316
Alachlor 8081
Aldicarb (Temi.k) 8318
Aldicarb Sulfone 8318
Aldrin 8080/8081, 8250/8270, 8275
Allyl alcohol 8240/8260
Allyl chloride 8010, 8240/8260
2-Aminoanthraquinone 8270
Aminoazobenzene 8270
4-Aminobiphenyl 8250/8270
2-Amino-4,6-dinitrotoluene (2-Am-DNT) 8330
4-Amino-2,6-dinitrotoluene (4-Am-DNT) 8330
3-Amino-9-ethylcarbazole 8270
Anilazine 8270
Aniline 8250/8270
o-Anisidine 8270
Anthracene 8100, 8250/8270, 8310, 8410
Aramite 8270
Aroclor-1016 (PCB-1016) 8080/8081, 8250/8270
Aroclor-1221 (PCB-1221) 8080/8081, 8250/8270
Aroclor-1232 (PCB-1232) 8080/8081, 8250/8270
Aroclor-1242 (PCB-1242) 8080/8081, 8250/8270
Aroclor-1248 (PCB-1248) 8080/8081, 8250/8270
Aroclor-1254 (PCB-1254) 8080/8081, 8250/8270
Aroclor-1260 (PCB-1260) 8080/8081, 8250/8270
Aspona 8141
Asulam 8321
Atrazine 8141
Azinphos-ethyl 8141
Azinphos-methyl 8140/8141, 8270
Barban 8270
Bentazon 8151
Benzal chloride 8121
TWO - 10 Revision 2
November 1992
TABLE 2-1.
(Continued)
:ompound Applicable Method(s)
Jenza l dehyde 8315

Jenz(a)anthracene 8100, 8250/8270, 8310, 8410
Jenzene 8020, 8021, 8240/8260
Jenzidine 8250/8270
Jenzoic acid 8250/8270, 8410
Jenzo(b)fluoranthene 8100, 8250/8270, 8310
!enzo(j)fluoranthene 8100
Benzo(k)fluoranthene 8100, 8250/8270, 8275, 8310
Benzo(g,h,i)perylene 8100, 8250/8270, 8310
Benzo(a)pyrene 8100, 8250/8270, 8275, 8310,
8410
p-Benzoquinone 8270
Benzotrichloride 8121
Benzyl alcohol 8250/8270
Benzyl benzoate 8061
Benzyl chloride 8010, 8121, 8240/8260
BHC (Hexachlorocyclohexane) 8120
1-BHC (alpha-Hexachlorocyclohexane) 8080/8081, 8121, 8250/8270
8-BHC (beta-Hexachlorocyclohexane) 8080/8081, 8121, 8250/8270
y-BHC (Lindane, garnma-Hexachlorocyclohexane) 8080/8081, 8121, 8250/8270
6-BHC (delta-Hexachlorocyclohexane) 8080/8081, 8121, 8250/8270
Bolstar (Sulprofos) 8140/8141
Bromoacetone 8010, 8240/8260
Bromobenzene 8010, 8021, 8260
Bromochloromethane 8021, 8240/8260
Bromodichloromethane 8010, 8021, 8240/8260
4-Bromofluorobenzene 8240/8260
Bromoform 8010, 8021, 8240/8260
Bromomethane 8010, 8021, 8240/8260
4-Bromophenyl phenyl ether 8110, 8250/8270, 8410
Bromoxynil 8270
Butanal 8315
n-Butanol 8260
2-Butanone (Methyl ethyl ketone, MEK) 8015, 8240/8260
n-Butylbenzene 8021, 8260
sec-Butyl benzene 8021, 8260
tert-Butylbenzene 8021, 8260
Butyl benzyl phthalate 8060/8061, 8250/8270, 8410
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb) 8040, 8150/8151, 8270, 8321
Captafol 8081, 8270
Capt an 8081, 8270
Carbaryl (Sevin) 8270, 8318
Carbazole 8275
Carbofuran (Furaden) 8270, 8318
TWO - 11 Revision 2
November 1992
TABLE 2-1.
(Continued)
Carbon disulfide 8240/8260

Carbon tetrachloride 8010, 8021, 8240/8260
Carbophenothion (Carbofenthion) 8141, 8270
Chloral hydrate 8240/8260
Chloramben 8151
Chlordane 8080, 8250/8270
a-Chlordane 8081
y-Chlordane 8081
Chlorfenvinphos 8141, 8270
Chloroacetaldehyde 8010
Chloroacetonitrile 8260
4-Chloroaniline 8250/8270, 8410
Chlorobenzene 8010, 8020, 8021, 8240/8260
Chlorobenzilate 8081, 8270
2-Chloro-1,3-butadiene 8260
1-Chlorobutane 8260
Chlorodibromomethane (Dibromochloromethane) 8010, 8021, 8240/8260
Chloroethane 8010, 8021, 8240/8260
2-Chloroethanol 8010, 8240/8260
bis(2-Chloroethoxy)methane 8010, 8110, 8250/8270, 8410
bis(2-Chloroethyl)ether 8110, 8250/8270, 8410
bis(2-Chloroethyl)sulfide 8240/8260
2-Chloroethyl vinyl ether 8010, 8240/8260
Chloroform 8010, 8021, 8240/8260
1-Chlorohexane 8010, 8260
bis(2-Chloroisopropyl) ether 8010, 8110, 8250/8270, 8410
Chloromethane 8010, 8021, 8240/8260
5-Chloro-2-methylaniline 8270
Chloromethyl methyl ether 8010
4-Chloro-3-methylphenol 8040, 8250/8270, 8275, 8410
Chloroneb 8081
3-(Chloromethyl)pyridine hydrochloride 8270
1-Chloronaphthalene 8250/8270, 8275
2-Chloronaphthalene 8120/8121, 8250/8270, 8410
2-Chlorophenol 8040, 8250/8270, 8275, 8410
4-Chlorophenol 8410
4-Chloro-1,2-phenylenediamine 8270
4-Chloro-1,3-phenylenediamine 8270
4-Chlorophenyl phenyl ether 8110, 8250/8270, 8410
Chloroprene 8010, 8240/8260
3-Chloropropene 8260
3-Chloropropionitrile 8240/8260
Chloropropylate 8081
Chlorothalon11 8081
TWO - 12 Revision 2
November 1992
TABLE 2-1.
(Continued)
;-Chlorotoluene 8021, 8260

-Chlorotoluene 8010, 8021, 8260
:h l orpyri fos 8140/8141
:hlorpyrifos methyl 8141
:hrysene 8100, 8250/8270, 8310, 8410
:oumaphos 8140/8141, 8270
:oumarin Dyes 8321
>-Cres idi ne 8270
>-Cresol (2-Methylphenol) 8250/8270, 8410
-Cresol (3-Methylphenol) 8270
>-Cresol (4-Methylphenol) 8250/8270, 8275, 8410
:resols (Methylphenols, Cresylic acids) 8040
:rotonaldehyde 8260, 8315
:rotoxyphos 8141, 8270
:ye l ohexanone 8315
?-Cyclohexyl-4,6-dinitrophenol 8040, 8270
?,4-D 8150/8151, 8321
lalapon 8150/8151, 8321
?,4-DB 8150/8151, 8321
lBCP 8081
2,4-D, butoxyethanol ester 8321
lCPA 8081
lCPA d1acid 8151
:.,4' -DDD 8080/8081, 8250/8270
:,4'-DDE 8080/8081, 8270
:.,4' -DDT 8080/8081, 8250/8270
lecanal 8315
lemeton-0, and -S 8140/8141, 8270
2,4-D,ethylhexyl ester 8321
lial 1ate 8081, 8270
2,4-Diaminotoluene 8270
>iazinon 8140/8141
libenz(a,h)acridine 8100
Dibenz(a,h)anthracene 8100, 8250/8270, 8310
Dibenz(a,j)acridine 8100, 8250/8270
7H-Dibenzo(c,g)carbazole 8100
Dibenzofuran 8250/8270, 8410
Dibenzo(a,e)pyrene 8100, 8270
Dibenzo(a,h)pyrene 8100
Dibenzo(a,i)pyrene 8100
Dibenzothiophene 8275
Dibromochloromethane (Chlorodibromomethane) 8010, 8021, 8240/8260
1,2-Dibromo-3-chloropropane 8010, 8011, 8240/8260, 8270
1,2-Dibromoethane (Ethylene dibromide) 8010, 8011, 8021, 8240/8260
TWO - 13 Revision 2
November 1992
TABLE 2-1.
(Continued)
01bromofluoromethane 8260
01bromomethane 8010, 8021, 8240/8260
tris(2,3-0ibromopropyl) phosphate (Tris-BP) 8270, 8321
Di-n-butyl phthalate 8060/8061, 8250/8270, 8410
Dicamba 8150/8151, 8321
Diehl one 8081, 8270
1,2-Dichlorobenzene 8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8250/8270, 8260, 8410
8250/8270, 8260, 8410
3,3'-Dichlorobenzidine 8250/8270
3,5-Dichlorobenzoic acid 8151
1,4-Dichloro-2-butene 8010, 8240
cis-1,4-Dichloro-2-butene 8260
trans-1,4-Dichloro-2-butene 8260
Dichlorodifluoromethane 8010, 8021, 8240/8260
1,1-Dichloroethane 8010, 8021, 8240/8260
1,2-Dichloroethane 8010, 8021, 8240/8260
1,1-0ichloroethene (Vinylidene chloride} 8010, 8021, 8240/8260
cis-1,2-Dichloroethene 8021, 8260
trans-1,2-Dichloroethene 8010, 8021, 8240/8260
Dichlorofenthion 8141
Dichloromethane (Methylene chloride) 8010, 8021, 8240/8260
2,4-Dichlorophenol 8040, 8250/8270, 8275, 8410
2,6-Dichlorophenol 8040, 8250/8270
Dichlorprop 8150/8151, 8321
1,2-Dichloropropane 8010, 8021, 8240/8260
1,3-Dichloropropane 8021, 8260
2,2-Dichloropropane 8021, 8260
1,3-Dichloro-2-propanol 8010, 8240/8260
1,1-Dichloropropene 8021, 8260
cis-1,3-Dichloropropene 8010, 8021, 8240/8260
trans-l,3-01chloropropene 8010, 8021, 8240/8260
Dichlorvos (Dichlorovos) 8140/8141, 8270, 8321
Dichrotophos 8141, 8270
Dicofol 8081
Oieldrin 8080/8081, 8250/8270
1,2,3,4-Diepoxybutane 8240/8260
Diethyl ether 8015, 8260
Diethyl phthalate 8060/8061, 8250/8270, 8410
Diethylstilbestrol 8270
Diethyl sulfate 8270
TWO - 14 Revision 2
November 1992
TABLE 2-1.
(Continued)
,4-Difluorobenzene 8240/8260
li hydrosaffrol e 8270
Jimethoate 8141, 8270, 8321
3,3'-Dimethoxybenzidine 8270
Jimethylaminoazobenzene 8250/8270
2,5-Dimethylbenzaldehyde 8315
7,12-0imethylbenz{a)anthracene 8250/8270
3,3'-Dimethylbenzidine 8270
1,a-Dimethylphenethylamine 8250/8270
2,4-Dimethylphenol 8040, 8250/8270
Jimethyl phthalate 8060/8061, 8250/8270, 8410
)i ni trobenzene 8090
1,2-Dinitrobenzene 8270
1,3-Dinitrobenzene (l,3-0NB) 8270, 8330
,4-Dinitrobenzene 8270
,,6-0initro-2-methylphenol 8250/8270, 8410
2,4-Dinitrophenol 8040, 8250/8270, 8410
2,4-Dinitrotoluene (2,4-0NT) 8090, 8250/8270, 8275, 8330,
8410
2,6-0initrotoluene (2,6-0NT) 8090, 8250/8270, 8330, 8410
Ji nocap 8270
Jinoseb (2-sec-Butyl-4,6-dinitrophenol, DNBP) 8040, 8150/8151, 8270, 8321
)i-n-octyl phthalate 8060/8061, 8250/8270, 8410
)i-n-propyl phthalate 8410
)ioxacarb 8318
1,4-Dioxane 8240/8260
lioxathion 8141, 8270
li phenyl amine 8250/8270, 8275
5,5-Diphenylhydantoin 8270
1,2-Diphenylhydrazine 8250/8270
)isperse Blue 3 8321
li sperse Blue 14 8321
li sperse Brown l 8321
Disperse Orange 3 8321
Disperse Orange 30 8321
Disperse Red l 8321
Disperse Red 5 8321
Disperse Red 13 8321
Disperse Red 60 8321
Disperse Yellow 5 8321
Disulfoton 8140/8141, 8270, 8321
Endosulfan I 8080/8081, 8250/8270
Endosul fan II 8080/8081, 8250/8270
Endosulfan sulfate 8080/8081, 8250/8270
TWO - 15 Revision 2
November 1992
TABLE 2-1.
(Continued)
Endrin 8080/8081, 8250/8270

Endrin aldehyde 8080/8081, 8250/8270
Endrin ketone 8081, 8250/8270
Epichlorohydrin 8010, 8240/8260
EPN 8141, 8270
Eth ion 8141, 8270
Ethoprop 8140/8141
Ethyl acetate 8260
Ethyl benzene 8020, 8021, 8240/8260
Ethyl carbamate 8270
Ethylene dibromide 8010, 8011, 8021, 8240/8260
Ethylene oxide 8240/8260
bis(2-Ethylhexyl) phthalate 8060/8061, 8250/8270, 8410
Ethyl methacrylate 8240/8260
Ethyl methanesulfonate 8250/8270
Ethyl parathion 8270
Etridiazole 8081
Famphur 8141, 8270, 8321
Fenithrothion 8141
Fensulfothion 8140/8141, 8270, 8321
Fenthion 8140/8141, 8270
Fluchloralin 8270
Fluoranthene 8100, 8250/8270, 8310, 8410
Fluorene 8100, 8250/8270, 8275, 8310,
8410
Fluorescent Brightener 61 8321
Fluorescent Brightener 236 8321
Fluorobenzene 8260
2-Fluorobiphenyl 8250/8270
2-Fl uoropheno 1 8250/8270
Fonophos 8141
Formaldehyde 8315
Halowax-1000 8081
Halowax-1001 8081
Halowax-1013 8081
Halowax-1014 8081
Halowax-1051 8081
Halowax-1099 8081
Heptachlor 8080/8081, 8250/8270
Heptachlor epoxide 8080/8081, 8250/8270
Heptanal 8315
Hexachlorobenzene 8081, 8120/8121, 8250/8270,
8275, 8410
TWO - 16 Revision 2
November 1992
TABLE 2-1.
(Continued)
Hexachlorobutadiene (1,3-Hexachlorobutadiene) 8021, 8120/8121, 8250/8270,

8260, 8410
Hexachlorocyclohexane 8120
Hexachlorocyclopentadiene 8081, 8120/8121, 8250/8270,
8410
Hexachloroethane 8120/8121, 8250/8270, 8260,
8410
Hexachlorophene 8270
Hexachloropropene 8270
Hexahydro-1,3,5-trinitro-l,3,5-triazine (ROX) 8330
Hexamethylphosphoramide (HMPA) 8141, 8270
Hexanal 8315
2-Hexanone 8240/8260
HMX 8330
1,2,3,4,6,7,8-HpCDD 8280/8290
1,2,3,4,6,7,8-HpCDF 8280/8290
1,2,3,4,7,8,9-HpCDF 8280/8290
1,2,3,4,7,8-HxCDD 8280/8290
1,2,3,6,7,8-HxCDD 8280/8290
1,2,3,7,8,9-HxCDD 8280/8290
1,2,3,4,7,8-HxCDF 8280/8290
1,2,3,6,7,8-HxCDF 8280/8290
1,2,3,7,8,9-HxCDF 8280/8290
2,3,4,6,7,8-HxCDF 8280/8290
Hydroquinone 8270
3-Hydroxycarbofuran 8318
5-Hydroxydicamba 8151
2-Hydroxypropionitrile 8240/8260
lndeno(l,2,3-cd)pyrene 8100, 8250/8270, 8310
lodomethane 8240/8260
Isobutyl alcohol (2-Methyl-1-propanol) 8240/8260
lsodrin 8081, 8270
lsophorone 8090, 8250/8270, 8410
Isopropylbenzene 8021, 8260
p-lsopropyltoluene 8021, 8260
Isosafrole 8270
Isovaleraldehyde 8315
Ke pone 8081, 8270
leptophos 8141, 8270
Malathion 8141, 8270
Maleic anhydride 8270
Malononitrile 8240/8260
MCPA 8150/8151, 8321
MCPP 8150/8151, 8321
TWO - 17 Revision 2
November 1992
TABLE 2-1.
(Continued)
Merphos 8140/8141, 8321

Mestranol 8270
Methacrylonitrile 8240/8260
Methanol 8260
Methapyrilene 8270
Methiocarb (Mesurol) 8318
Methomyl (Lannate) 8318, 8321
Methoxychlor (4,4'-Methoxychlor) 8080/8081, 8250/8270
Methyl acrylate 8260
Methyl-t-butyl ether 8260
3-Methylcholanthrene 8100, 8250/8270
2-Methyl-4,6-dinitrophenol 8040
4,4'-Methylenebis(2-chloroaniline) 8270
4,4'-Methylenebis(N,N-dimethylaniline) 8270
Methyl ethyl ketone (MEK, 2-Butanone) 8015, 8240/8260
Methylene chloride (Dichloromethane) 8010, 8021, 8240/8260
Methyl iodide 8010, 8240/8260
Methyl isobutyl ketone (4-Methyl-2-pentanone) 8015, 8240/8260
Methyl methacrylate 8240/8260
Methyl methanesulfonate 8250/8270
2-Methylnaphthalene 8250/8270, 8410
2-Methyl-5-nitroaniline 8270
Methyl parathion 8270, 8321
4-Methyl-2-pentanone (Methyl isobutyl ketone) 8015, 8240/8260
2-Methylphenol (o-Cresol) 8250/8270, 8410
3-Methylphenol (m-Cresol) 8270
4-Methylphenol (p-Cresol) 8250/8270, 8275, 8410
2-Methylpyridine 8270
Methyl-2,4,6-trinitrophenylnitramine (Tetryl) 8330
Mevinphos 8140/8141, 8270
Mexacarbate 8270
Mirex 8081, 8270
Monochrotophos 8141, 8270, 8321
Na led 8140/8141, 8270, 8321
Naphthalene 8021, 8100, 8250/8270, 8260,
8275, 8310, 8410
Naphthoquinone 8090
1,4-Naphthoquinone 8270
1-Naphthylamine 8250/8270
2-Naphthylamine 8250/8270
Nicotine 8270
5-Nitroacenaphthene 8270
2-Nitroaniline 8250/8270, 8410
3-Nitroani 1i ne 8250/8270, 8410
TWO - 18 Revision 2
November 1992
TABLE 2-1.
(Continued)
4-Nitroaniline 8250/8270, 8410

5-Nitro-o-anisidine 8270
Nitrobenzene (NB) 8090, 8250/8270, 8260, 8330,
8410
4-Nitrobiphenyl 8270
Nitrofen 8081, 8270
2-Nitrophenol 8040, 8250/8270, 8410
4-Nitrophenol 8040, 8151, 8250/8270, 8410
2-Nitropropane 8260
Nitroquinoline-1-oxide 8270
N-Nitrosodibutylamine 8250/8270
N-Nitrosodiethylamine 8270
N-Nitrosodimethylamine 8070, 8250/8270, 8410
N-Nitrosodiphenylamine 8070, 8250/8270, 8410
N-Nitrosodi-n-propylamine 8070, 8250/8270, 8410
N-Nitrosomethylethylamine 8270
N-Nitrosomorpholine 8270
N-Nitrosopiperidine 8250/8270
N-Nitrosopyrrolidine 8270
o-Nitrotoluene (2-NT} 8330
m-Nitrotoluene (3-NT) 8330
p-Nitrotoluene (4-NT) 8330
5-Nitro-o-toluidine 8270
trans-Nonachlor 8081
Nonanal 8315
OCDD 8280
OCDF 8280
Octahydro-l,3,5,7-tetranitro-1,3,5,7-tetrazocine
(HMX) 8330
Octamethyl pyrophosphoramide 8270
Octanal 8315
4,4'-0xydianiline 8270
Parathion 8270
Parathion, ethyl 8141
Parathion, methyl 8140/8141
PCB-1016 (Aroclor-1016) 8080/8081, 8250/8270
PCB-1221 (Aroclor-1221) 8080/8081, 8250/8270
PCB-1232 (Aroclor-1232) 8080/8081, 8250/8270
PCB-1242 (Aroclor-1242) 8080/8081, 8250/8270
PCB-1248 (Aroclor-1248) 8080/8081, 8250/8270
PCB-1254 (Aroclor-1254) 8080/8081, 8250/8270
PCB-1260 (Aroclor-1260) 8080/8081, 8250/8270
PCNB 8081
1,2,3,4,7-PeCDD 8280
TWO - 19 Revision 2
November 1992
TABLE 2-1.
(Continued)
1,2,3,7,8-PeCDD 8280/8290
1,2,3,7,8-PeCDF 8280/8290
2,3,4,7,8-PeCDF 8280/8290
Pentachlorobenzene 8121, 8250/8270
Pentachloroethane 8240/8260
Pentachlorohexane 8120
Pentachloronitrobenzene 8250/8270
Pentachlorophenol 8040, 8151, 8250/8270, 8410
Pentafluorobenzene 8260
Pentanal 8315
trans-Permethrin 8081
Perthane 8081
Phenacetin 8250/8270
Phenanthrene 8100, 8250/8270, 8275, 8310,
8410
Phenobarbital 8270
Phenol 8040, 8250/8270, 8410
1,4-Phenylenediamine 8270
Pho rate 8140/8141, 8270, 8321
Phosalone 8270
Phosmet 8141, 8270
Phosphamidion 8141, 8270
Phthalic anhydride 8270
Picloram 8151
2-Picoline 8240/8260, 8250/8270
Piperonyl sulfoxide 8270
Promecarb 8318
Pronamide 8250/8270
Propachlor 8081
Propanal 8315
Propargyl alcohol 8240/8260
B-Propiolactone 8240/8260
Propionitrile 8240/8260
Propoxur (Baygon) 8318
n-Propylamine 8240/8260
n-Propylbenzene 8021, 8260
Propylthiouracil 8270
Pyrene 8100, 8250/8270, 8275, 8310,
8410
Pyridine 8240/8260, 8270
ROX 8330
Resorcinol 8270
Ronnel 8140/8141
Safrole 8270
TWO - 20 Revision 2
November 1992
TABLE 2-1.
(Continued)
Simazine 8141
Solvent Red 3 8321
Solvent Red 23 8321
Stirophos (Tetrachlorvinphos) 8140/8141, 8270
Strabane 8081
Strychnine 8270, 8321
Styrene 8021, 8240/8260
Sul fal late 8270
Sul fotep 8141
2,4,5-T 8150/8151, 8321
2,4,5-T, butoxyethanol ester 8321
2,4,5-T, butyl ester 8321
1,2,3,4-TCDD 8280
1,2,7,8-TCDD 8280
1,2,8,9-TCDD 8280
1,3,6,8-TCDD 8280
1,3,7,8-TCDD 8280
1,3,7,9-TCDD 8280
2,3,7,8-TCDD 8280/8290
1,2,7,8-TCDF 8280
2,3,7,8-TCDF 8280/8290
TEPP 8141
Terbuphos (Terbufos) 8141, 8270
1,2,3,4-Tetrachlorobenzene 8121
1,2,3,5-Tetrachlorobenzene 8121
1,2,4,5-Tetrachlorobenzene 8121, 8250/8270
Tetrachlorobenzenes 8120
1,1,l,2-Tetrachloroethane 8010, 8021, 8240/8260
1,1,2,2-Tetrachloroethane 8010, 8021, 8240/8260
Tetrachloroethene 8010, 8021, 8240/8260
2,3,4,6-Tetrachlorophenol 8250/8270
Tetrachlorophenols 8040
Tetrachlorvinphos (Stirophos) 8140/8141, 8270
Tetraethyl dithiopyrophosphate 8270
Tetraethyl pyrophosphate 8270
Tetrazene 8331
Thiofanox 8321
Thionazine 8141, 8270
Thiophenol (Benzenethiol) 8270
TOCP (Tri-o-cresylphosphate) 8141
Tokuthion (Prothiofos) 8140/8141
m-Tolualdehyde 8315
o-Tolualdehyde 8315
p-Tolualdehyde 8315
TWO - 21 Revision 2
November 1992
TABLE 2-1.
(Continued)
Toluene 8020, 8021, 8240/8260

Toluene diisocyanate 8270
o-Toluidine 8270
Toxaphene 8080/8081, 8250/8270
2,4,5-TP (Silvex) 8150/8151, 8321
2,4,6-Tribromophenol 8250/8270
1,2,3-Trichlorobenzene 8021, 8121, 8260
1,2,4-Trichlorobenzene 8021, 8120/8121, 8250/8270,
8260, 8410
1,3,5-Trichlorobenzene 8121
1,1,1-Trichloroethane 8010, 8021, 8240/8260
1,1,2-Trichloroethane 8010, 8021, 8240/8260
Trichloroethene 8010, 8021, 8240/8260
Trichlorofluoromethane 8010, 8021, 8240/8260
Trichlorfon 8141, 8321
Trichloronate 8140/8141
2,4,5-Trichlorophenol 8250/8270, 8410
2,4,6-Trichlorophenol 8040, 8250/8270, 8410
Trichlorophenols 8040
1,2,3-Trichloropropane 8010, 8021, 8240/8260
0,0,0-Triethyl phosphorothioate 8270
Triflural in 8081, 8270
2,4,5-Trimethylaniline 8270
1,2,4-Trimethylbenzene 8021, 8260 '
1,3,5-Trimethylbenzene 8021, 8260
Trimethyl phosphate 8270
1,3,5-Trinitrobenzene (1,3,5-TNB) 8270, 8330
2,4,6-Trinitrotoluene (2,4,6-TNT) 8330
Tri-o-cresyl phosphate (TOCP) 8141
Tri-p-tolyl phosphate 8270
Vinyl acetate 8240/8260
Vinyl chloride 8010, 8021, 8240/8260
a-Xylene 8021, 8260
m-Xylene 8021, 8260
p-Xylene 8021, 8260
Xylene (Total) 8020, 8240
TWO - 22 Revision 2
November 1992
TABLE 2-2A.
METHOD 3650 - BASE/NEUTRAL FRACTION
Benz(a)anthracene Hexachlorobenzene
Benzo(a)pyrene Hexachlorobutadiene
Benzo(b)fluoranthene Hexachloroethane
Chlordane Hexachlorocyclopentadiene
Chlorinated dibenzodioxins Naphthalene
Chrysene Nitrobenzene
Creosote Pho rate
Dichlorobenzene(s) 2-Picoline
Dinitrobenzene Pyridine
2,4-Dinitrotoluene Tetrachlorobenzene(s)
Heptachlor Toxaphene
TABLE 2-28.
METHOD 3650 - ACID FRACTION
2-Chlorophenol 4-Nitrophenol
Cresol(s) Pentachlorophenol
Creosote Phenol
Dichlorophenoxyacetic acid Tetrachlorophenol(s)
Z,4-Dimethylphenol Trichlorophenol(s)
4,6-Dinitro-o-cresol 2,4,5-TP (Silvex}
TWO - 23 Revision 2
November 1992
TABLE 2-3.
METHOD 5041 - SORBENT CARTRIDGES FROM
VOLATILE ORGANIC SAMPLING TRAIN (VOST)
Acetone 1,2-Dichloropropane
Acrylonitrile cis-1,3-Dichloropropene
Benzene trans-1,3-Dichloropropene
Bromodichloromethane Ethylbenzenea
Bromoforma Iodomethane
Bromomethaneb Methylene chloride
Carbon disulfide Styrenea
Carbon tetrachloride 1,1,2,2-Tetrachloroethanea
Chlorobenzene Tetrachloroethene
Chlorodibromgmethane Toluene
Chloroethane 1,1,1-Trichloroethane
Chloroform 1,1,2-Trichloroethane
Chloromethaneb Trichloroethene
Dibromomethane Trichlorofluoromethane
1,1-Dichloroethane 1,2,3-Trichloropropanea
1,2-Dichloroethane Vinyl chloridell
1,1-Dichloroethene Xylenesa
trans-1,2-Dichloroethene
a Boiling point of this compound is above 132°C. Method 0030 is not

appropriate for quantitative sampling of this analyte.
b Boiling point of this compound is below 30°C. Special precautions must be
taken when sampling for this analyte by Method 0030. Refer to Section 1.3 of
Method 5041 for discussion.
TWO - 24 Revision 2
November 1992
TABLE 2-4.
METHOD 8010 - HALOGENATED VOLATILES
Allyl chloride 1,3-Dichlorobenzene

Benzyl chloride 1,4-Dichlorobenzene
Bromoacetone 1,4-Dichloro-2-butene
Bromobenzene Dichlorodifluoromethane
Bromodichloromethane 1,1-Dichloroethane
Bromoform 1,2-Dichloroethane
Bromomethane 1,1-Dichloroethene (Vinylidene chloride)
Carbon tetrachloride trans-1,2-Dichloroethene
Chloroacetaldehyde Dichloromethane (Methylene Chloride)
Chlorobenzene 1,2-Dichloropropane
Chloroethane 1,3-Dichloro-2-propanol
bis(2-Chloroethoxy)methane cis-1,3-Dichloropropene
2-Chloroethanol trans-1,3-Dichloropropene
2-Chloroethyl vinyl ether Epichlorhydrin
Chloroform Ethylene dibromide
1-Chlorohexane Methyl iodide
bis(2-Chloroisopropyl) ether 1,1,2,2-Tetrachloroethane
Chloromethane 1,1,1,2-Tetrachloroethane
Chloromethyl methyl ether Tetrachloroethene
Chloroprene 1,1,1-Trichloroethane
4-Chlorotoluene 1,1,2-Trichloroethane
Dibromochloromethane Trichloroethene
1,2-Dibromo-3-chloropropane Trichlorofluoromethane
Dibromomethane 1,2,3-Trichloropropane
1,2-Dichlorobenzene Vinyl chloride
TABLE 2-5. TABLE 2-6.

METHOD 8015 - NONHALOGENATED VOLATILES METHOD 8020 - AROMATIC VOLATILES
Diethyl ether Benzene

Ethanol Chlorobenzene
Methyl ethyl ketone (MEK) 1,2-Dichlorobenzene
Methyl isobutyl ketone (MIBK) 1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Xylenes
TWO - 25 Revision 2
November 1992
TABLE 2-7.
METHOD 8021 (METHOD 8011*) - HALOGENATED AND AROMATIC VOLATILES
Benzene 1,3-0ichloropropane
Bromobenzene 2,2-Dichloropropane
Bromochloromethane 1,1-Dichloropropene
Bromodichloromethane cis-1,3-Dichloropropene
Bromoform trans-1,3-Dichloropropene
Bromomethane Ethyl benzene
n-Butylbenzene Hexachlorobutadiene
sec-Butyl benzene Isopropylbenzene
tert-Butylbenzene p-lsopropyltoluene
Carbon tetrachloride Methylene chloride
Chlorobenzene Naphthalene
Chlorodibromomethane n-Propylbenzene
Chloroethane Styrene
Chloroform 1,1,1,2-Tetrachloroethane
Chloromethane 1,1,2,2-Tetrachloroethane
2-Chlorotoluene Tetrachloroethene
4-Chlorotoluene Toluene
1,2-Dibromo-3-chloropropane* 1,2,3-Trichlorobenzene
1,2-Dibromoethane* 1,2,4-Trichlorobenzene
Dibromomethane 1,1,1-Trichloroethane
1,2-Dichlorobenzene 1,1,2-Trichloroethane
1,3-Dichlorobenzene Trichloroethene
1,4-Dichlorobenzene Trichlorofluoromethane
Dichlorodifluoromethane 1,2,3-Trichloropropane
1,1-Dichloroethane 1,2,4-Trimethylbenzene
1,2-Dichloroethane 1,3,5-Trimethylbenzene
1,1-Dichloroethene Vinyl chloride
cis-1,2-Dichloroethene o-Xylene
trans-1,2-Dichloroethene m-Xylene
1,2-Dichloropropane p-Xylene
* Indicates the only two target analytes of Method 8011. These constituents are
also target analytes of Method 8021.
Table 2-8. TABLE 2-9

METHODS 8030/8031 - METHOD 8032 -
ACROLEIN, ACRYLONITRILE AC RY LAM IDE
Acrolein (Propenal)* Acrylamide
Acryl oni tril e
* Target analyte of Method 8030 only.
TWO - 26 Revision 2
November 1992
TABLE 2-10.
METHOD 8040 - PHENOLS
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb) 2-Methyl-4,6-dinitrophenol

4-Chloro-3-methylphenol 2-Nitrophenol
2-Chlorophenol 4-Nitrophenol
Cresols (Methylphenols) Pentachlorophenol
2-Cyclohexyl-4,6-dinitrophenol Phenol
2,4-Dichlorophenol Tetrachlorophenols
2,6-Dichlorophenol 2,4,6-Trichlorophenol
2,4-Dimethylphenol Trichlorophenols
2,4-Dinitrophenol

METHODS 8060/8061 - PHTHALATE ESTERS METHOD 8070 - NITROSAMINES
Benzyl benzoate* N-Nitrosodimethylamine
Butyl benzyl phthalate N-Nitrosodiphenylamine
Bis{2-ethylhexyl) phthalate N-Nitrosodi-n-propylamine
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
TWO - 27 Revision 2
November 1992
TABLE 2-13.
METHODS 8080/8081 - ORGANOCHLORINE PESTICIDES AND PCBs
Aroclor-1016 (PCB-1016) Chloropropylate* Halowax-1014*

Aroclor-1221 (PCB-1221) Chlorothalonil* Halowax-1051*
Aroclor-1232 (PCB-1232) DCBP* Halowax-1099*
Aroclor-1242 (PCB-1242) DCPA* Heptachlor
Aroclor-1248 (PCB-1248) Dial late* Heptachlor epoxide
Aroclor-1254 (PCB-1254) Diehl one* Hexachlorobenzene*
Aroclor-1260 (PCB-1260) Dicofol* Hexachlorocyclo-
Alachlor* 4,4'-DDD pentadiene*
Aldrin 4,4'-DDE Isodrin*
a-BHC 4,4'-DDT Ke pone*
P-BHC Dieldrin 4,4'-Methoxychlor
6-BHC Endosulfan I Mirex*
-y-BHC (Lindane) Endosul fan II Nitrofen*
Captafol* Endosulfan sulfate PCNB*
Capt an* Endrin Perthane*
Chlorobenzilate* Endrin aldehyde Propachlor*
Chlordane** Endrin ketone* Strobane*
a-Chlorodane* Etridiazole* Toxaphene
')'-Chlorodane* Halowax-1000* trans-Nonachlor*
Chloroneb* Halowax-1001* trans-Permethrin*
Halowax-1013* Triflural in*
** Target analyte of Method 8080 only.
TABLE 2-14.
METHOD 8090 - NITROAROMATICS AND
CYCLIC KETONES
Dinitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Naphthoquinone
Nitrobenzene
TWO - 28 Revision 2
November 1992
TABLE 2-15.
METHODS 8100 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene 7H-Dibenzo{c,g)carbazole
Acenaphthylene Dibenzo(a,e)pyrene
Anthracene Dibenzo(a,h)pyrene
Benzo(a)anthracene Dibenzo(a,i}pyrene
Benzo(a)pyrene Fluoranthene
Benzo(b)fluoranthene Fluorene
Benzo(j)fluoranthene Indeno(l,2,3-cd)pyrene
Benzo(k)fluoranthene 3-Methylcholanthrene
Benzo (g,h,i)perylene Naphthalene
Chrysene Phenanthrene
Dibenz(a,h)acridine Pyrene
Dibenz{a,j)acr;dine
Dibenzo(a,h)anthracene
TABLE 2-16
METHOD 8110 - HALOETHERS
bis(2-Chloroethyl) ether 4-Bromophenyl phenyl ether
bis(2-Chloroethoxy)methane 4-Chlorophenyl phenyl ether
bis(2-Chloroisopropyl) ether
TABLE 2-17.
METHODS 8120/8121 - CHLORINATED HYDROCARBONS
Benzal chloride* gamma-Hexachlorocyclohexane (ganvna-BHC)*

Benzotrichloride* delta-Hexachlorocyclohexane (delta-BHC)*
Benzyl chloride* Hexachlorocyclopentadiene
2-Chloronaphthalene Hexachloroethane
1,2-Dichlorobenzene Pentachlorobenzene*
1,3-0ichlorobenzene Pentachlorohexane**
1,4-0ichlorobenzene Tetrachlorobenzenes**
Hexachlorobenzene 1,2,3,4-Tetrachlorobenzene*
Hexachlorobutadiene 1,2,3,5-Tetrachlorobenzene*
Hexachlorocyclohexane** 1,2,4,5-Tetrachlorobenzene*
alpha-Hexachlorocyclohexane (alpha-BHC)* 1,2,3-Trichlorobenzene*
beta-Hexachlorocyclohexane (beta-BHC)* 1,2,4-Trichlorobenzene
1,3,5-Trichlorobenzene*

TWO - 29 Revision 2
November 1992
TABLE 2-18.
METHODS 8140/8141 - ORGANOPHOSPHORUS COMPOUNDS
(PACKED AND CAPILLARY COLUMNS)
Aspon* Fenthion
Atrazine* Fonophos*
Azinphos ethyl* Hexamethylphosphoramide*
Azinphos methyl (HMPA)
Bolstar (Sulprofos) Leptophos*
Carbophenothion* Malathion*
Chlorofenvinphos* Merphos
Chlorpyrifos Mevinphos
Chlorpyrifos methyl* Monochrotophos*
Coumaphos Na led
Crotoxypos* Parathion, ethyl*
Demeton-0, and -S Parathion, methyl
Diazinon Phorate
Oichlorofenthion* Phosmet*
Dichlorvos (DDVP) Phosphamidon*
Oichrotophos* Ronnel
Dimethoate* Simazine*
Dioxathion* Stirophos (Tetrachlorvinphos)
Disulfoton Sulfotepp*
EPN* TEPP*
Eth ion* Terbufos*
Ethoprop Thionazin*
Famphur* Tri-o-cresylphosphate (TOCP)*
Fenithrothion* Tokuthion (Prothiofos)
Fensulfothion Trichlorfon*
Trichloronate
TABLE 2-19.
METHODS 8150/8151 - CHLORINATED HERBICIDES
Ac i fl uorfen* Dicamba MCPA

Bentazon* 3,5-Dichlorobenzoic acid* MCPP
Chloramben* Dichlorprop 4-Nitrophenol*
2,4-0 Dinoseb Pentachlorophenol*
Dalapon 5-Hydroxydicamba* Picloram*
2,4-DB 2,4,5-TP (Silvex}
DCPA diacid* 2,4,5-T
TWO - 30 Revision 2
November 1992
TABLE 2-20.
METHODS 8240/8260 - VOLATILES
Acetone 1,2-Dibromo-3- lsopropylbenzene*

Acetoni tril e chloropropane p-Isopropyltoluene*
Acrolein (Propenal) 1,2-Dibromoethane Malononitrile
Acryl oni tril e Dibromomethane Methacrylonitrile
A11 yl al coho l Dibromofluoromethane* Methanol*
Allyl chloride 1,2-Dichlorobenzene* Methyl acrylate*
Benzene 1,3-Dichlorobenzene* Methyl-t-butyl ether*
Benzyl chloride 1,4-Dichlorobenzene* Methylene chloride
Bromoacetone 1,4-Dichloro-2-butene Methyl iodide
Bromobenzene* cis-1,4-Dichloro- Methyl methacrylate
Bromochloromethane 2-butene* 4-Methyl-2-pentanone
Bromodichloromethane trans-1,4-Dichloro-2- (MIBK)
4-Bromofluorobenzene butene* Naphthalene*
Bromoform 1,4-Dichloro-2-butene** Nitrobenzene*
Bromomethane Dichlorodifluoromethane 2-Nitropropane*
n-Butanol* 1,1-Dichloroethane Pentachloroethane
2-Butanone (Methyl ethyl 1,2-Dichloroethane Pentafluorobenzene*
ketone) 1,1-Dichloroethene 2-Picoline
n-Butylbenzene* cis-1,2-Dichloroethene* Propargyl alcohol
sec-Butyl benzene* trans-1,2-Dichloroethene B-Propiolactone
tert-Butylbenzene* 1,2-Dichloropropane Propionitrile
Carbon disulfide 1,3-Dichloropropane* n-Propylamine
Carbon tetrachloride 2,2-Dichloropropane* n-Propylbenzene*
Chloral hydrate 1,3-Dichloro-2-propanol Pyridine
Chloroacetonitrile* 1,1-Dichloropropene* Styrene
Chlorobenzene cis-1,3-Dichloropropene 1,1,1,2-Tetrachloroethane
2-Chloro-1,3-butadiene* trans-1,3-Dichloropropene 1,1,2,2-Tetrachloroethane
1-Chlorobutane* 1,2,3,4-Diepoxybutane Tetrachloroethene
Chlorodibromomethane Diethyl ether* Toluene
Chloroethane 1,4-Difluorobenzene 1,2,3-Trichlorobenzene*
2-Chloroethanol 1,4-Dioxane 1,2,4-Trichlorobenzene*
bis(2-Chloroethyl) sulfide Epichlorohydrin 1,1,1-Trichloroethane
2-Chloroethyl vinyl ether Ethanol 1,1,2-Trichloroethane
Chloroform Ethyl acetate* Trichloroethene
1-Chlorohexane* Ethyl benzene Trichlorofluoromethane
Chloromethane Ethylene oxide 1,2,3-Trichloropropane
Chloroprene Ethyl methacrylate 1,2,4-Trimethylbenzene*
3-Chloropropene* Fluorobenzene* 1,3,5-Trimethylbenzene*
3-Chloropropionitrile Hexachlorobutadiene* Vinyl acetate
2-Chlorotoluene* Hexachloroethane* Vinyl chloride
4-Chlorotoluene* 2-Hexanone Xylene (Total}**
Crotonaldehyde* 2-Hydroxypropionitrile o-Xylene*
lodomethane m-Xylene*
lsobutyl alcohol p-Xylene*

TWO - 31 Revision 2
November 1992
TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES
Acenaphthene Carbophenothion*
Acenaphthylene Chlordane
Acetophenone Chlorfenvinphos*
2-Acetylaminofluorene* 4-Chloroanil ine
l-Acetyl-2-thiourea* Chlorobenzilate*
Aldrin 5-Chloro-2-methylaniline*
2-Aminoanthraquinone* 4-Chloro-3-methylphenol
Aminoazobenzene* 3-(Chloromethyl)pyridine hydrochloride*
4-Aminobiphenyl 1-Chloronaphthalene
3-Amino-9-ethylcarbazole* 2-Chloronaphthalene
Anilazine* 2-Chlorophenol
Aniline 4-Chloro-1,2-phenylenediamine*
o-Anisidine* 4-Chloro-1,3-phenylenediamine*
Anthracene 4-Chlorophenyl phenyl ether
Aramite* Chrysene
Aroclor-1016 Coumaphos*
Aroclor-1221 p-Cresidine*
Aroclor-1232 Crotoxyphos*
Aroclor-1242 2-Cyclohexyl-4,6-dinitrophenol*
Aroclor-1248 4, 4' -ODD
Aroclor-1254 4, 4 -ODE*
I
Aroclor-1260 4,4'-DDT
Azinphos-methyl* Demeton-0*
Barban* Demeton-S*
Benz(a)anthracene Diallate (cis or trans)*
Benzi dine 2,4-Diaminotoluene*
Benzo(b)fluoranthene Dibenz(a,j)acridine
Benzo(k)fluoranthene Dibenz(a,h)anthracene
Benzoic acid Dibenzofuran
Benzo(g,h,i)perylene Dibenzo(a,e)pyrene*
Benzo(a)pyrene 1,2-Dibromo-3-chloropropane*
p-Benzoquinone* Di-n-butyl phthalate
Benzyl alcohol Diehl one*
a-BHC 1,2-Dichlorobenzene
(3-BHC 1,3-Dichlorobenzene
o-BHC 1,4-Dichlorobenzene
-y-BHC (Lindane) 3,3'-Dichlorobenzidine
Bis(2-chloroethoxy)methane 2,4-Dichlorophenol
Bis(2-chloroethyl) ether 2,6-Dichlorophenol
Bis(2-chloroisopropyl) ether Dichlorovos*
Bis(2-ethylhexyl) phthalate Dicrotophos*
4-Bromophenyl phenyl ether Dieldrin
Bromoxynil* Diethyl phthalate
Butyl benzyl phthalate Diethylstilbestrol*
2-sec-Butyl-4,6-dinitrophenol (Dinoseb)* Diethyl sulfate*
Captafol* Dihydrosaffrole*
Capt an* Dimethoate*
Carbaryl* 3,3'-Dimethoxybenzidine*
Carbofuran* Dimethylaminoazobenzene
TWO - 32 Revision 2
November 1992
TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES {CONTINUED)
7,12-D;methylbenz(a)anthracene Indeno{l,2,3-cd)pyrene
3,3'-D;methylbenzidine* lsodrin*
a,a-Dimethylphenethylamine lsophorone
2,4-Dimethylphenol Isosafrole*
Dimethyl phthalate Kepone*
1,2-Dinitrobenzene* Leptophos*
1,3-Dinitrobenzene* Malathion*
1,4-Dinitrobenzene* Maleic Anhydride*
4,6-Dinitro-2-methylphenol Mestranol*
2,4-Dinitrophenol Methapyrilene*
2,4-Dinitrotoluene Methoxychlor
2,6-Dinitrotoluene 3-Methylcholanthrene
Dinocap* 4,4'-Methylenebis{2-chloroaniline)*
Dioxathion* 4,4'-Methylenebis{N,N-dimethylaniline)*
Di phenyl amine Methyl methanesulfonate
5,5-Diphenylhydantoin* 2-Methylnaphthalene
1,2-Diphenylhydrazine 2-Methyl-5-nitroaniline*
Di-n-octyl phthalate Methyl parathion*
Disulfoton* 2-Methylphenol {o-Cresol)
Endosulfan I 3-Methylphenol (m-Cresol)*
Endosulfan II 4-Methylphenol (p-Cresol)
Endosulfan sulfate 2-Methylpyridine*
Endrin Mevinphos*
Endrin aldehyde Mexacarbate*
Endrin ketone Mirex*
EPN* Monocrotophos*
Eth ion* Na led*
Ethyl carbamate* Naphthalene
Ethyl methanesulfonate 1,4-Naphthoquinone*
Ethyl parathion* 1-Naphthylamine
Famphur* 2-Naphthylamine
Fensulfothion* Nicotine*
Fenthion* 5-Nitroacenaphthene*
Fluchloralin* 2-Nitroani 1i ne
Fluoranthene 3-Nitroani line
Fl uorene 4-Nitroaniline
2-Fluorobiphenyl 5-Nitro-o-anisidine*
2- Fl uoropheno 1 Nitrobenzene
Heptachlor 4-Nitrobiphenyl*
Heptachlor epoxide Nitrofen*
Hexachlorobenzene 2-Nitrophenol
Hexachlorobutadiene 4-Nitropheno 1
Hexachlorocyclopentadiene Nitroquinoline-1-oxide*
Hexachloroethane N-Nitrosodibutylamine
Hexachlorophene* N-Nitrosodiethylamine*
Hexachloropropene* N-Nitrosodimethylamine
Hexamethylphosphoramide* N-Nitrosodiphenylamine
Hydroquinone* N-Nitrosodi-n-propylamine
TWO - 33 Revision 2
November 1992
TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
N-Nitrosomethylethylamine* Terbuphos*
N-Nitrosomorpholine* 1,2,4,S-Tetrachlorobenzene
N-Nitrosopiperidine 2,3,4,6-Tetrachlorophenol
N-Nitrosopyrrolidine* Tetrachlorvinphos (Stirophos)*
S-Nitro-o-toluidine* Tetraethyl dithiopyrophosphate*
Octamethyl pyrophosphoramide* Tetraethyl pyrophosphate*
4,4'-0xydianiline* Thionazine*
Parathion* Thiophenol (Benzenethiol)*
Pentachlorobenzene Toluene diisocyanate*
Pentachloronitrobenzene o-Toluidine*
Pentachlorophenol Toxaphene
Phenacetin 2,4,6-Tribromophenol-
Phenanthrene l ,2,4-Trichlorobenzene
Phenobarbital* 2,4,5-Trichlorophenol
Phenol 2,4,6-Trichlorophenol
1,4-Phenylenediamine* Triflural in*
Pho rate* 2,4,5-Trimethylaniline*
Phosalone* Trimethyl phosphate*
Phosmet* 1,3,5-Trinitrobenzene*
Phosphamidion* Tris(2,3-dibromopropyl) phosphate*
Phthalic anhydride* Tri-p-tolyl phosphate*
2-Picoline 0,0,0-Triethyl phosphorothioate*
Piperonyl sulfoxide*
Pronamide
Propylthiouracil*
Pyrene
Pyridine*
Resorcinol*
Sa fro le*
Strychnine*
Sul fall ate*
TABLE 2-22.
METHOD 8275 - SEMIVOLATILES (SCREENING)
2-Chlorophenol 2,4-Dinitrotoluene Carbazole
4-Methylphenol Fl uorene Aldrin
2,4-Dichlorophenol Diphenylamine Pyrene
Naphthalene Hexachlorobenzene Benzo(k}fluoranthene
4-Chloro-3-methylphenol Dibenzothiophene Benzo(a)pyrene
1-Chloronaphthalene Phenanthrene
TWO - 34 Revision 2
November 1992
TABLE 2-23.
METHODS 8280/8290 - DIOXINS AND DIBENZOFURANS
2,3,7,8-TCDD 1,2,3,4,7-PeCDD* 1,2,7,8-TCDF*
1,2,3,4-TCDD* 1,2,3,7,8-PeCDD 2,3,7,8-TCDF
1,3,6,8-TCDD* 1,2,3,4,7,8-HxCDD 1,2,3,7,8-PeCDF
1,3,7,9-TCDD* 1,2,3,6,7,8-HxCDD 2,3,4,7,8-PeCDF
1,3,7,8-TCDD* 1,2,3,7,8,9-HxCDD 1,2,3,4,7,8-HxCDF
1,2,7,8-TCDD* 1,2,3,4,6,7,8-HpCDD 1,2,3,6,7,8-HxCDF
1,2,8,9-TCDD* OCDD* 1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF*
* Target analyte of 8280 only
TABLE 2-24.
METHOD 8310 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene Chrysene
Acenaphthylene Dibenzo(a,h)anthracene
Anthracene Fluoranthene
Benzo(a)anthracene Fluorene
Benzo(a)pyrene Indeno(l,2,3-cd)pyrene
Benzo(b)fluoranthene Naphthalene
Benzo(g,h,i)perylene Phenanthrene
Benzo(k)fluoranthene Pyrene
TWO - 35 Revision 2
November 1992
TABLE 2-25.
METHOD 8315 - CARBONYL COMPOUNDS
Acetaldehyde Heptanal
Acetone Hexanal (Hexaldehyde)
Acrolein Isovaleraldehyde
Benzaldehyde Nonanal
Butanal (Butyraldehyde) Octanal
Crotonaldehyde Pentanal (Valeraldehyde)
Cyclohexanone Propanal (Propionaldehyde)
Decanal m-Tolualdehyde
2,5-Dimethylbenzaldehyde o-Tolualdehyde
Formaldehyde p-Tolualdehyde

METHOD 8316 - ACRYLAMIDE, METHOD 8318 - N-METHYLCARBAMATES
ACRYLONITRILE AND ACROLEIN
Aldicarb (Temik)
Acrylamide Aldicarb Sulfone
Acrylonitrile Carbaryl (Sevin)
Acrolein Carbofuran (Furadan)
Dioxacarb
3-Hydroxycarbofuran
Methiocarb (Mesurol)
Methomyl (Lannate)
Promecarb
Propoxur (Baygon)
TWO - 36 Revision 2
November 1992
TABLE 2-28.
METHOD 8321 - NONVOLATILES
Azo Dves Alkaloids
Disperse Red 1 Caffeine
Disperse Red 5 Strychnine
Disperse Red 13
Disperse Yellow 5 Organophosphorus Compounds
Disperse Orange 3 Methomyl
Disperse Orange 30 Thiofanox
Disperse Brown 1 Famphur
Solvent Red 3 Asulam
Solvent Red 23 Dichlorvos
Dimethoate
Anthraguinone Dyes Disulfoton
Disperse Blue 3 Fensulfothion
Disperse Blue 14 Merphos
Disperse Red 60 Methyl parathion
Coumarin Dyes Monocrotophos
Na led
(Fluorescent Brighteners) Phorate
Fluorescent Brightener 61 Trichlorfon
Fluorescent Brightener 236 tris-(2,3-Dibromopropyl) phosphate,
(Tris-BP)
Chlorinated Phenoxyacid Compounds
Dalapon
Dicamba
2,4-D
MCPA
MCPP
Dichlorprop
2,4,5-T
Silvex (2,4,5-TP)
Dinoseb
2,4-DB
2,4-D, butoxyethanol ester
2,4-D, ethylhexyl ester
2,4,5-T, butyl ester
2,4,5-T, butoxyethanol ester
TWO - 37 Revision 2
November 1992
TABLE 2-29.
METHOD 8330 - NITROAROMATICS AND NITRAMINES
Octahydro-l,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX)
Hexahydro-1,3,5-trinitro-l,3,5-triazine (ROX)
1,3,5-Trinitrobenzene (1,3,5-TNB)
1,3-Dinitrobenzene (1,3-DNB)
Methyl-2,4,6-trinitrophenylnitramine (Tetryl)
Nitrobenzene {NB)
2,4,6-Trinitrotoluene (2,4,6-TNT)
4-Amino-2,6-dinitrotoluene (4-Am-DNT)
2-Amino-4,6-dinitrotoluene (2-Am-DNT)
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
2-Nitrotoluene (2-NT)
TABLE 2-30.
METHOD 8331 - TETRAZENE
Tetrazene
TWO - 38 Revision 2
November 1992
TABLE 2-31
METHOD 8410 - SEMIVOLATILES
Acenaphthene 2,4-Dinitrotoluene
Acenaphthylene 2,6-Dinitrotoluene
Anthracene Di-n-octyl phthalate
Benzo(a)anthracene Fluoranthene
Benzo(b)pyrene Fluorene
Benzoic acid Hexachlorobenzene
Bis(2-chloroethoxy)methane 1,3-Hexachlorobutadiene
Bis(2-chloroethyl)ether Hexachlorocyclopentadiene
Bis(2-chloroisopropyl)ether Hexachloroethane
Bis(2-ethylhexyl)phthalate Isophorone
4-Bromophenyl phenyl ether 2-Methylnaphthalene
Butyl benzyl phthalate 2-Methylphenol
4-Chloroaniline 4-Methylphenol
4-Chloro-3-methylphenol Naphthalene
2-Chloronaphthalene 2-Nitroanil ine
2-Chlorophenol 3-Nitroanil i ne
4-Chlorophenol 4-Nitroanil ine
4-Chlorophenyl phenyl ether Nitrobenzene
Chrysene 2-Nitrophenol
Dibenzofuran 4-Nitrophenol
1,2-Dichlorobenzene N-Nitrosodimethylamine
1,3-Dichlorobenzene N-Nitrosodiphenylamine
1,4-Dichlorobenzene N-Nitroso-di-n-propylamine
2,4-Dichlorophenol Pentachlorophenol
Diethyl phthalate Phenanthrene
Dimethyl phthalate Phenol
Di-n-butyl phthalate Pyrene
Di-n-propyl phthalate 1,2,4-Trichlorobenzene
4,6-Dinitro-2-methylphenol 2,4,5-Trichlorophenol
2,4-Dinitrophenol 2,4,6-Trichlorophenol
TWO - 39 Revision 2
November 1992
TABLE 2-32.
ANALYSIS METHODS FOR INORGANIC COMPOUNDS

Aluminum 6010, 6020, 7020
Antimony 6010, 6020, 7040, 7041, 7062
Arsenic 6010, 6020, 7060, 7061, 7062
Barium 6010, 6020, 7080, 7081
Beryllium 6010, 6020, 7090, 7091
Bromide 9056
Cadmium 6010, 6020, 7130, 7131
Calcium 6010, 7140
Chloride 9056, 9250, 9251, 9252, 9253
Chromium 6010, 6020, 7190, 7191
Chromium, hexavalent 7195, 7196, 7197' 7198
Cobalt 6010, 6020, 7200, 7201
Copper 6010, 6020, 7210, 7211
Cyanide 9010, 9012, 9013
Fluoride 9056
Iron 6010, 7380, 7381
Lead 6010, 6020, 7420, 7421
Lithium 6010, 7430
Magnesium 6010, 7450
Manganese 6010, 6020, 7460, 7461
Mercury 7470, 7471
Molybdenum 6010, 7480, 7481
Nickel 6010, 6020, 7520
Nitrate 9056, 9200
Nitrite 9056
Osmium 7550
Phosphate 9056
Phosphorus 6010
Potassium 6010, 7610
Selenium 6010, 7740, 7741, 7742
Silver 6010, 6020, 7760, 7761
Sodium 6010, 7770
Strontium 6010, 7780
Sulfate 9035, 9036, 9038, 9056
Sulfide 9030, 9031
Thallium 6010, 6020, 7840, 7841
Tin 7870
Vanadium 6010, 7910, 7911
Zinc 6010, 6020, 7950, 7951
TWO - 40 Revision 2
November 1992
TABLE 2-33.
CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES FOR AQUEOUS MATRICESA
Name Container 1 Preservation Maxi111.111 holding time

Bacterial Tests:
Coliform, total P, G 6 hours
Inorganic Tests:
Chloride P, G None required 28 days
Cyanide, total and amenable P, G Cool, 4°C; if oxidizing 14 days
to chlorination agents present add 5 ml
0.1N NaAs02 per Lor 0.06 g
of ascorbic acid per L;
adjust pH>12 with 50% NaOH.
See Method 9010 for other
interferences.
Hydrogen ion CpH) P, G None required 24 hours
Nitrate P, G Cool, 4°C 48 hours
Sulfate P, G Cool, 4°C 28 days
Sulfide P, G Cool, 4°C, add zinc acetate 7 days
Metals:
Chromi1.111 VI P, G Cool, 4°C 24 hours
Mercury P, G HN03 to pH<2 28 days
Metals, except chromi1.111 VI P, G HN03 to pH<2 6 months
and mercury
Organic Tests:
Acrolein and acrylonitrile G, Teflon-lined Cool, 4°C, 0.008% Na 2S203 3 , 14 days
sept I.Ill Adjust pH to 4-5
Benzi dines G, Teflon-lined Cool, 4°C, 0.008% Na 2s203 3 , 7 days until extraction, 40 days
cap Adjust pH to 6-9, store in after extraction
dark
Chlorinated hydrocarbons G, Teflon-lined Cool, 4°C, 0.008% Na 2S203 3 7 days ll"ltil extraction, 40 days
cap after extraction
Dioxins and Furans G, Teflon- lined Cool, 4°C, 0.008% Na 2 S 2~ 3
7 days ll"ltil extraction, 40 days
Haloethers G, Teflon-lined Cool , 4•c, 0. 008% Na 2S203 3 7 days until extraction, 40 days
3
Nitroaromatics and G, Teflon- lined Cool, 4°C, 0.008% Na 2S203 7 days ll"ltil extraction, 40 days
cyclic ketones cap store in dark after extraction
3
Nitrosamines G, Teflon-Lined Cool, 4°C, 0.008% Na 2S203 , 7 days until extraction, 40 days
cap store in dark after extraction
Oil and grease G cool 4°C 2 28 days
Organic carbon, total CTOC) P, G cool 1, 4°C 2 28 days
PCBs G, Teflon-lined Cool, 4°C 7 days ll"ltil extraction, 40 days
Pesticides G, Teflon-lined Cool, 4°C 7 days ll"ltil extraction, 40 days
Phenols G, Teflon-lined 7 days ll"ltil extraction, 40 days
Phthalate esters G, Teflon-lined cool, 4°C 7 days ll"ltil extraction, 40 days
Polynuclear aromatic G, Teflon-lined Cool, 4°C, 0.008% Na 2 s20/ 7 days until extraction, 40 days
hydrocarbons cap store in dark after extraction
Purgeable aromatic G, Teflon-lined Cool, 4•c, 0. 008% Na 2s 20/· 3 14 days
hydrocarbons sept I.Ill
Purgeable Halocarbons G, Teflon-lined Cool, 4•c, 0. 008% Na 2S203 3 14 days
septum
2
Total organic halides CTOX) G, Teflon-lined Cool, 4°C 28 days
cap
Radiological Tests:
Alpha, beta and radii.Ill P, G HN03 to pH<2 6 months
A Table excerpted, in part, from Table II, 49 FR 209, October 26, 1984, p 28.
1
Polyethylene CP) or Glass CG)
2
Adjust to pH<2 with H2S04 , HCl or solid NaHS04 •
3
Free chlorine must be removed prior to addition of HCl by the appropriate addition of Na 2S203 •
TWO - 41 Revision 2
November 1992
Table 2-34.
PREPARATION METHODS FOR ORGANIC ANALYTES
Aqueous Solids Sludges Oils
Emulsions 1
(pH)3 (pH)3
Acids 3510 3540 3520 36502
3520 35502 3580
«2) 3580 (<2)
Acrolein 5030 5030 5030 5030
AcrylonHrile
Acetonitrile
Aromatic Volatiles 5030 5030 5030 5030
Base/Neutral 3510 3540 3520 3650
3520 35502 35802
(>11) 3580 (>11)
Chlorinated 8150 81502 8150 35802
Herbicides (<2) 3580 (<2)
Chlorinated 3510 3540 3520 3580 2
Hydrocarbons 3520 35502
(Neutral) 3580 (Neutral)
Halo~enated 5030 5030 5030 5030
Vola iles
Nitroaromatic and 3510 3540 3520 3580 2
Cyclic Ketones 3520 35502
(5-9) 3580 (5-9)
Non-halogenated 5030 5030 5030 5030
Volatiles
Organochlorine 3510 3540 3520 3580 2
Pesticides and PCBs 3520 35502
3665 3580
3665
(5-9) 3541* (5-9)
Organophosphorus 3510 3540 3520 3580 2
Pesticides 3520 35502
(6-8) 3580 (6-8)
Phenols 3510 3540 3520 36502
3520 35502 3580
(<2) 3580 (<2)
Phthalate Esters 3510 3540 3520 35802
3520 35502
(Neutral) 3580 (Neutral)
Polynuclear 3510 3540 3520 35602
Aromatic 3520 35502 3580
Hydrocarbons (Neutral) 3580 (Neutral)
Volatile Organics 5030 5030 5030 5030
1
If attempts to break up emulsions are unsuccessful, these methods may be used.
2 Waste dilution, Method 3580, is only appropriate if the sample is soluble in the
§Pecified solvent.
pH at which extraction should be performed.
*Method 3541 is appropriate if the sample is to be analyzed for PCBs only.
TWO - 42 Revision 2
November 1992
TABLE 2-35.
CLEANUP OF ORGANIC ANALYTE EXTRACTS
Ana lyte lvoe Method(s)

Acids 3650
Base/Neut ra 1 3650
Chlorinated 8150
Herbicides
Chlorinated 3620
Hydrocarbons 3640
Nitroaromatics & 3620
Cvclic Ketones 3640
Organophosphorus 3620
Pesticides
Organochlorine 3620
Pesticides & 3640
PCBs 3660
3665
Phenols 3630
3640
3650
Phthalate 3610
Esters 3620
3640
Polynuclear 3611
Aromatic 3630
Hydrocarbons 3640
TWO - 43 Revision 2
November 1992
TABLE 2-36.
DETERMINATION OF ORGANIC ANALYTES
GC/MS Determination Specific GC Detection

Methods Methods HPLC
SEMI VOLATILES
Acids 8270
8250
Base/Neutral 8270
8250
Carbamates 8318
Chlorinated Herbicides 8270* 8150
8151
Chlorinated Hydrocarbons 8270 8120
8250 8121
Dves 8321
Explosives 8330
8331
Haloethers 8270 8110
- 8250
Nitroaromatics and Cyclic 8270 8090
Ketones 8250
Nitrosoamines 8270 8070
8250
Organochlorine Pesticides and 8270* 8080
PCBs 8081
Organophosphorous Pesticides 8270* 8140 8321
8141
Phenols 8270 8040
8250
Phthalate Esters 8270 8060
8250 8061
Polynuclear Hydrocarbons 8270 8100 8310
8250
VOLATILES
Acrolein, Acrylonitrile, or 8240 8030 8316
Acetonitrile 8031 8315
Acrvlamide 8032 8316
Aromatic Volatiles 8240 8020
8260 8021
Forma 1dehvde 8315
Halogenated Volatiles 8240 8010
8260 8011
8021
Non-haloaenated Volatiles 8240 8015
Volatile Organics 8240 8021
8260
*This method is an alternative confirmation method. It is not the method of choice.
TWO - 44 Revision 2
November 1992
FIGURE 2-1.
ORGANIC ANALYSIS OPTIONS
----
Sample
A~ Kl I Physical
Character1&bc
I Solid, Oil, or Sludge
'
A Samole Physical
CharactenstlC
of Sample of Sample
Aqueous L.tquKl I Solid

'
Sample Sample Extraction Extraction ExtractJOn Extractton
Preparatllln: 5030. PNp81'•ion: 5030 Prooedww: 3520, Proc:edul8: 351 O Prooedu19: 3540, Proc:edul8: 3650
5040, or 8011 3540, or 3550 or3520 3550, or 3580 or 3580
-c::
HPLC GCIMS Analysis
Procedu19:
Packed Column: 8240
Capillary Column: 8260
Cleanup Prooedu19:
GC Alumina Column: 3610
Alumina Column for Petroleum Was11BS: 3611
Floriall Column: 3620
SllJCB Gel Column: 3630
GC Analysis Prooadure Gel PermeatJOn: 3640
Halogenated Volatile Organics: 8010 AcKl Bae PartitJOn1ng: 3660
EDB and DBCP: 8011 Sulfur: 3660
Nonhalogenated Volalile OiganJCS 8015
Aromatic Volatile Organa: 8020
Halogenated Volal1te Compounds: 8021 GC Analysis Prooadures:
Acrolem. Acrylomtnte: 8030 HPLC Analysis Procedu19s: ~ "" 1 Phenols: 8040
Acrylamide 8032 8310,8318,8321,8330,8331 Phthala• Esteis: 8060
NJtrosamines: 8070
Organochlorine Pesbcldes and PC&: 8080
NJtroaromata and Cyclic Ketones: 8090
HPLC Analys• Procedul9s: Polynuclaar Aromatic Hydrocarbona: 8100
Aaoleln, Acrylonitr1te, Acrylamide: 8316 Haloethers: 8110
GCIMS Prooadure&:
Fonnaldehyde: 8315 Chlorinated Hydrocarbona: 8120. 8121
Packed Column: 8250
Ceptllary Column. 8270 Organophosphorua Pesticlda&: 8140,8141
Chlorinated Helbicides: 8150, 8151
TW0-45 Revision 2
November 1992
FIGURE 2-2.
SCHEMATIC OF SEQUENCE TO DETERMINE
IF A WASTE IS HAZARDOUS BY CHARACTERISTIC
Hazardous
Liquid
· uid Perform Paint Solid

Filter Test
(Method 9095)
Yes
Hazardous
Methods 1010 or 1020
TWO - 46 Revision 2
November 1992
FIGURE 2-2.
(Continued)
No
TWO - 47 Revision 2
November 1992
FIGURE 2-3A.
EP
Samo le
I
1310
I
3010
(7760 Aal
6010 7470 3510 8150

Hg Neutral 8151
Herbicides
-- As
Ba-- 8080
8081
Pesticides
-- Cd
Cr --
-- Pb
Ag --
-- Se
TWO - 48 Revision 2
November 1992
FIGURE 2-3B.
RECOMMENDED SW-846 METHODS OF ANALYSIS FOR TCLP LEACHATES
Samo le
TCLP
I I I I
8240 3510 8150
3010 7470 3510 8260 (Acidic 8151
Hg Neutral Volatile and Herbie-
Orqanics Basic) ides
I
8080 8270
6010 8081 Semi vol-
Pestic- atile
ides Orqanics
- As
Ba -
- Cd
Cr -
- Pb
Ag -
- Se
TWO - 49 Revision 2
November 1992
FIGURE 2-4A.
GROUND WATER ANALYSIS
Organic
Sample
I
,, I • ' I
VOA Semivolatiles Pesticides Herbicides Dioxins
., ., .' ·r •
3510 or 3510 or
8240or 8150 8280
3520
8260 3520
Neutral
1 Ir
8270or 1
3620, 3640
8250 and/or 3660
,,
8080
1 . Optional: Cleanup required only if interferences prevent analysis
TWO - 50 Revision 2
November 1992
FIGURE 2-48.
INDICATOR ANALYTE
lndicaflDI'
Analyte(s)
POC
9060
TOC FieldTeslS
9021
POX
9020
TOX 9050 ~1
Specific 90458
9056 Conduclance pH
Br. 9250/9251
925219253
9056
ca·
9035r'9036
903&'9056
5042 9056
N02fN03
2
NH 3
9010/9012
CN-
9056
F- 9066
9067
Phenolic&
1 - Barcelona, 1984, (See Reterenoe 1)

2 ·Riggin, 1984, (See Reference 2)
TWO - 51 Revision 2
November 1992
FIGURE 2-4C.
GROUND WATER
SAMPLE PREPARATION SAMPLE PREPARATION

30050R3015 30150R 3020
Ag, Al, As, Ba, Be, Ag, Al, As, Ba. Be, Ag. 7760 Al. 7020 Ag. 7761* Mn· 7461* 7060, 7061,
Cd, Co, Cr, Cu, Fe, Ba. 7080 Be. 7090 Ba. 7081* Mo. 7"81 OR 7062
Cd, Co, Cr, Cu, Mn,
Mg, Mn, Mo, NI, Pb, Ni, Pb, Sb, Tl, Zn Cd. 7130 Co. 7200 Be. 7091 Pb. 7421 As
Sb,se, v.
TI, Zn Cr· 7190 Cu. 7210 Cd. 7131 Tl. 7841
Fe -7380 Mg· 7450 Co. 7201 Sb-7041*
Mn· 7.eo Mo· 7480 Cr. 7191 7062*
Ni. 7520 Pb· 7420
Cu. 1211· v. 7911 77400R 7741
Sb. 7040 Sn. 7870 Fe· 7381* Zn· 7951• OR 7742
Tl. 7840 v.7910 se
Zn. 7950
• Follow lhe digestion procedures as detailed in lhe incividual

deaminative melhods.
1
When analyzing for btal dlsaolved metals, digestion is not
necessary if lhe samples are filtered at lhe lime of
colleclion, and lhen acidified to lhe same ccncentration as lhe standards.
TWO - 52 Revision 2
November 1992
CHAPTER THREE
METALLIC ANALYTES
3.1 SAMPLING CONSIDERATIONS

3.1.1 Introduction
This manual contains procedures for the analysis of metals in a variety of
matrices. These methods are written as specific steps in the overall analysis
scheme -- sample handling and preservation, sample digestion or preparation, and
sample analysis for specific metal components. From these methods, the analyst
must assemble a total analytical protocol which is appropriate for the sample to
be analyzed and for the information required. This introduction discusses the
options available in general terms, provides background information on the
analytical techniques, and highlights some of the considerations to be made when
selecting a total analysis protocol.
3.1.2 Definition of Terms

Optimum concentration range: A range, defined by limits expressed in
concentration, below which scale expansion must be used and above which curve
correction should be considered. This range will vary with the sensitivity of
the instrument and the operating conditions employed.
Sensitivity: a) Atomic Absorption: The concentration in milligrams of
metal per liter that produces an absorption of 1%; b) Inductively Coupled Plasma
(ICP): The slope of the analytical curve, i.e., the functional relationship
between emission intensity and concentration.
Method detection limit (MDL): The minimum concentration of a substance
that can be measured and reported with 99% confidence that the analyte
concentration is greater than zero. The MDL is determined from analysis of a
sample in a given matrix containing analyte which has been processed through the
preparative procedure.
Total recoverable metals: The concentration of metals in an unfiltered
sample following treatment with hot dilute mineral acid (Method 3005).
Dissolved metals: The concentration of metals determined in sample after
the sample is filtered through a 0.45-um filter (Method 3005).
Suspended metals: The concentration of metals determined in the
portion of a sample that is retained by a 0.45-um filter (Method 3005).
Total metals: The concentration of metals determined in a sample following
digestion by Methods 3010, 3015, 3020, 3050 or 3051.
THREE - 1 Revision 2
November 1992
Instrument detection limit (IDL): The concentration equivalent to a signal
due to the analyte which is equal to three times the standard deviation of a
series of 7 replicate measurements of a reagent blank's signal at the same
wavelength.
Interference check sample (ICS): A solution containing both interfering
and analyte elements of known concentration that can be used to verify background
and interelement correction factors.
Initial calibration verification standard {ICV): A certified (EPA or
other) or independently prepared solution used to verify the accuracy of the
initial calibration. For ICP analysis, it must be run at each wavelength used
in the analysis.
Continuing calibration verification (CCV): Used to assure calibration
accuracy during each analysis run. It must be run for each analyte as described
in the particular analytical method. At a minimum, it should be analyzed at the
beginning of the run and after the last analytical sample. Its concentration
should be at or near the mid-range levels of the calibration curve.
Calibration standards: A series of known standard solutions used by the
analyst for calibration of the instrument (i.e., preparation of the analytical
curve).
Linear dynamic range: The concentration range over which the analytical
curve remains linear.
Method blank: A volume of reagent water processed through each sample
preparation procedure.
Calibration blank: A volume of reagent water acidified with the same
amounts of acids as were the standards and samples.
Laboratory control standard: A volume of reagent water spiked with known
concentrations of analytes and carried through the preparation and analysis
procedure as a sample. It is used to monitor loss/recovery values.
Method of standard addition (MSA): The standard-addition technique
involves the use of the unknown and the unknown plus several known amounts of
standard. See Method 7000, Section 8.7 for detailed instructions.
Sample holding time: The storage time allowed between sample collection
and sample analysis when the designated preservation and storage techniques are
employed.
November 1992
3.1.3 Sample Handling and Preservation
Sample holding times, digestion procedures and suggested collection volumes
are listed in Table l. The sample volumes required depend upon the number of
different digestion procedures necessary for analysis. This may be determined
by the application of graphite-furnace atomic absorption spectrometry (GFAA),
flame atomic absorption spectrometry (FLAA), inductively coupled argon plasma
emission spectrometry (ICP), hydride-generation atomic absorption spectrometry
{HGAA), inductively coupled plasma mass spectrometry (ICP-MS) or cold-vapor
atomic absorption spectrometry (CVAA) techniques, each of which may require
different digestion procedures. The indicated volumes in Table 3-1 refer to that
required for the individual digestion procedures and recommended sample
collection volumes.
In the determination of trace metals, containers can introduce either
positive or negative errors in the measurement of trace metals by (a)
contributing contaminants through leaching or surface desorption, and (b)
depleting concentrations through adsorption. Thus the collection and treatment
of the sample prior to analysis require particular attention. The following
cleaning treatment sequence has been determined to be adequate to minimize
contamination in the sample bottle, whether borosilicate glass, linear
polyethylene, polypropylene, or Teflon: detergent, tap water, 1:1 nitric acid,
tap water, 1:1 hydrochloric acid, tap water, and reagent water.
NOTE: Chromic acid should not be used to clean glassware, especially if
chromium is to be included in the analytical scheme. Commercial, non-
chromate products (e.g., Nochromix) may be used in place of chromic
acid if adequate cleaning is documented by an analytical quality
control program. (Chromic acid should also not be used with plastic
bottles.)
3.1.4 Safety
The toxicity or carcinogenicity of each reagent used in this method has
not been precisely defined. However, each chemical compound should be treated
as a potential health hazard. From this viewpoint, exposure to these chemicals
must be reduced to the lowest possible level by whatever means available. The
laboratory is responsible for maintaining a current awareness file of OSHA
regulations regarding the safe handling of the chemicals specified in this
method. A reference file of material data-handling sheets should also be made
available to all personnel involved in the chemical analysis. Additional
references to laboratory safety are available. They are:
November 1992
TABLE 3-1.
SAMPLE HOLDING TIMES, REQUIRED DIGESTION VOLUMES ANO RECOMMENDED COLLECTION
VOLUMES FOR METAL DETERMINATIONS IN AQUEOUS AND SOLID SAMPLES
Digestion Treatment/
Vol. Req. a Collection Preservative
Measurement (ml) Volume (ml) a Holding Timec
Metals (except hexavalent chromium and mercury):
Aqueous
Total 100 600 HN0 3 to pH <2
6 months
Dissolved 100 600 Filter on site;
HN0 3 to pH <2
6 months
Suspended 100 600 Filter on site
6 months
Solid
Total 2g 200g 6 months
Chromium VI:b
Aqueous 100 400 24 hr
Solid 200g
Mercury:
Aqueous
Total 100 400 HN0 3 to pH <2
28 days
Dissolved 100 400 Filter;
HN0 3 to pH <2
28 days
Solid
Total 0.2g 200g 28 days
8
Unless stated otherwise.
bThe holding time for the analysis of hexavalent chromium in solid samples has
not yet been determined. A holding time of "as soon as possible" is recommended.
cAll samples must be stored at 4°C until analyzed, either glass or plastic
containers may be used.
November 1992
1. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
2. "OSHA Safety and Health Standards, General Industry" (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, revised
January 1976.
3. "Proposed OSHA Safety and Health Standards, Laboratories," Occupational
Safety and Health Administration, Federal Register, July 24, 1986, p. 26660.
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd edition, 1979.
3.2 SAMPLE PREPARATION METHODS

The methods in SW-846 for sample digestion or preparation are as
follows:
Method 3005 prepares ground water and surface water samples for total
recoverable and dissolved metals determination by FLAA or ICP. The unfiltered
or filtered sample is heated with dilute HCl and HN0 3 prior to metal determi-
nation.
Method 3010 prepares waste samples for total metal determination by
FLAA and ICP. The samples are vigorously digested with nitric acid followed by
dilution with hydrochloric acid. The method is applicable to aqueous samples,
EP and mobility-procedure extracts.
Method 3015 prepares aqueous samples, mobility-procedure extracts, and
wastes that contain suspended solids for total metal determination by FLAA, GFAA,
ICP-AES, or ICP-MS. Nitric acid is added to the sample in a Teflon digestion
vessel and heated in a microwave unit prior to metals determination.
Method 3020 prepares waste samples for total metals determination by
furnace GFAA. The samples are vigorously digested with nitric acid followed by
dilution with nitric acid. The method is applicable to aqueous samples, EP and
mobility-procedure extracts.
Method 3040 prepares oily waste samples for soluble metals
determination by AA and ICP methods. The samples are dissolved and diluted in
organic solvent prior to analysis. The method is applicable to the organic
extract in the oily waste EP procedure and other samples high in oil, grease, or
wax content.
Method 3050 prepares waste samples for total metals determination by
November 1992
AA and ICP. The samples are vigorously digested in nitric acid and hydrogen
peroxide followed by dilution with either nitric or hydrochloric acid. The
method is applicable to soils, sludges, and solid waste samples.
Method 3051 prepares sludges, sediments, soils and oils for total
metals determination by FLAA, GFAA, ICP-AES and ICP-MS. Nitric acid is added to
the representative sample in a Teflon digestion vessel and heated in a microwave
unit prior to metals determination.
November 1992
3.3 METHODS FOR DETERMINATION OF METALS
This manual contains seven analytical techniques for trace metal
determinations: inductively coupled argon plasma emission spectrometry (ICP-
AES), inductively coupled plasma mass spectrometry (ICP-MS), direct-aspiration
or flame atomic absorption spectrometry (FLAA), graphite-furnace atomic
absorption spectrometry (GFAA), hydride-generation atomic absorption spectrometry
{HGAA), cold-vapor atomic absorption spectrometry (CVAA), and several procedures
for hexavalent chromium analysis. Each of these is briefly discussed below in
terms of advantages, disadvantages, and cautions for analysis of wastes.
ICP's primary advantage is that it allows simultaneous or rapid
sequential determination of many elements in a short time. The primary
disadvantage of ICP is background radiation from other elements and the plasma
gases. Although all ICP instruments utilize high-resolution optics and back-
ground correction to minimize these interferences, analysis for traces of metals
in the presence of a large excess of a single metal is difficult. Examples would
be traces of metals in an alloy or traces of metals in a limed (high calcium)
waste. ICP and Flame AA have comparable detection limits (within a factor of 4)
except that ICP exhibits greater sensitivity for refractories (Al, Ba, etc.).
Furnace AA, in general, will exhibit lower detection limits than either ICP or
FLAA. Detection limits are drastically improved when ICP-MS is used. In general
ICP-MS exhibits greater sensitivity than either GFAA of FLAA for most elements.
The greatest disadvantage of ICP-MS is isobaric elemental interferences. These
are caused by different elements forming atomic ions with the same nominal mass-
to-charge ratio. Mathematical correction for interfering ions can minimize these
interferences.
Flame AAS (FLAA) direct aspiration determinations, as opposed to ICP,
are normally completed as single element analyses and are relatively free of
interelement spectral interferences. Either a nitrous-oxide/acetylene or
air/acetylene flame is used as an energy source for dissociating the aspirated
sample into the free atomic state making analyte atoms available for absorption
of light. In the analysis of some elements the temperature or type of flame used
is critical. If the proper flame and analytical conditions are not used,
chemical and ionization interferences can occur.
Graphite Furnace AAS (GFAA) replaces the flame with an electrically
heated graphite furnace. The furnace allows for gradual heating of the sample
aliquot in several stages. Thus, the processes of desolvation, drying,
decomposition of organic and inorganic molecules and salts, and formation of
atoms which must occur in a flame or ICP in a few milliseconds may be allowed to
occur over a much longer time period and at controlled temperatures in the
furnace. This allows an experienced analyst to remove unwanted matrix components
by using temperature programming and/or matrix modifiers. The major advantage
of this technique is that it affords extremely low detection limits. It is the
easiest to perform on relatively clean samples. Because this technique is so
sensitive, interferences can be a real problem; finding the optimum combination
of digestion, heating times and temperatures, and matrix modifiers can be a
challenge for complex matrices.
November 1992
Hydride AA utilizes a chemical reduction to reduce and separate arsenic
or selenium selectively from a sample digestate. The technique therefore has the
advantage of being able to isolate these two elements from complex samples which
may cause interferences for other analytical procedures. Significant
interferences have been reported when any of the following is present: 1) easily
reduced metals {Cu, Ag, Hg); 2) high concentrations of transition metals {>200
mg/L); 3) oxidizing agents {oxides of nitrogen) remaining following sample
digestion.
Cold-Vapor AA uses a chemical reduction to reduce mercury selectively.
The procedure is extremely sensitive but is subject to interferences from some
volatile organics, chlorine, and sulfur compounds.
November 1992
CHAPTER FOUR
ORGANIC ANALYTES
4.1 GENERAL CONSIDERATIONS

4.1.1 Introduction
Following the initial and critical step of designing a sampling plan
(Chapter Nine) is the implementation of that plan such that a representative
sample of the solid waste is collected. Once the sample has been collected it
must be stored and preserved to maintain the chemical and physical properties
that it possessed at the time of collection. The sample type, type of containers
and their preparation, possible forms of contamination, and preservation methods
are a11 items which must be thoroughly examined in order to maintain the
integrity of the samples. This section highlights considerations which must be
addressed in order to maintain a sample's integrity and representativeness. This
section is, however, applicable only to trace analyses.
Quality Control requirements need not be met for all compounds presented
in the Table of Analytes for the method in use, rather, they must be met for all
compounds reported. A report of non-detect is considered a quantitative report,
and must meet all applicable QC requirements for that compound and the method
used.
4.1.2 Sample Handling and Preservation
This section deals separately with volatile and semivolatile organics.
Refer to Chapter Two and Table 4-1 of this section for sample containers, sample
preservation, and sample holding time information.
Volatile Organics
Standard 40 ml glass screw-cap VOA vials with Teflon lined silicone septa
may be used for both liquid and solid matrices. The vials and septa should be
washed with soap and water and rinsed with distilled deionized water. After
thoroughly cleaning the vials and septa, they should be placed in an oven and
dried at 100°C for approximately one hour.
NOTE: Do not heat the septa for extended periods of time (i.e. more than one
hour, because the silicone begins to slowly degrade at 105°C).
When collecting the samples, liquids and solids should be introduced into
the vials gently to reduce agitation which might drive off volatile compounds.
In general, liquid samples should be poured into the vial without introducing any
air bubbles within the vial as it is being filled. Should bubbling occur as a
result of violent pouring, the sample must be poured out and the vial refilled.
The vials should be completely filled at the time of sampling, so that when the
septum cap is fitted and sealed, and the vial inverted, no headspace is visible.
The sample should be hermetically sealed in the vial at the time of sampling, and
must not be opened prior to analysis to preserve their integrity.
FOUR - 1 Revision 2
November 1992
due to differing solubility and diffusion properties of gases in
LIQUID matrices at different temperatures, it is possible for the
sample to generate some headspace during storage. This headspace
will appear in the form of micro bubbles, and should not invalidate
a sample for volatiles analysis.
The presence of a macro bubble in a sample vial generally indicates
either improper sampling technique or a source of gas evolution
within the sample. The latter case is usually accompanied by a
buildup of pressure within the vial, (e.g. carbonate-containing
samples preserved with acid). Studies conducted by the USEPA
(EMSL-Ci, unpublished data) indicate that "pea-sized" bubbles (i.e.
bubbles not exceeding 1/4 inch or 6 mm in diameter) did not
adversely affect volatiles data. These bubbles were generally
encountered in wastewater samples, which are more susceptible to
variations in gas solubility than are groundwater samples.
At the time of analysis, the aliquot to be analyzed should be taken from the
vial with a gas-tight syringe inserted directly through the septum of the vial.
Only one analytical sample can be taken from each vial. If these guidelines are
not followed, the validity of the data generated from the samples is suspect.
VOA vials for samples with solid or semi-solid matrices (e.g., sludges)
should be completely filled as best as possible. The vials should be tapped
slightly as they are filled to try and eliminate as much free air space as
possible. Two vials should also be filled per sample location.
At least two VOA vials should be filled and labeled immediately at the
point at which the sample is collected. They should NOT be filled near a running
motor or any type of exhaust system because discharged fumes and vapors may
contaminate the samples. The two vials from each sampling location should then
be sealed in separate plastic bags to prevent cross-contamination between
samples, particularly if the sampled waste is suspected of containing high levels
of volatile organics. (Activated carbon may also be included in the bags to
prevent cross-contamination from highly contaminated samples). VOA samples may
also be contaminated by diffusion of volatile organics through the septum during
shipment and storage. To monitor possible contamination, a trip blank prepared
from organic-free reagent water (as defined in Chapter One) should be carried
throughout the sampling, storage, and shipping process.
Semivolatile Organics (including Pesticides, PCBs and Herbicides.)
Containers used to collect samples for the determination of semivolatile
organic compounds should be soap and water washed followed by methanol (or
isopropanol) rinsing (see Section 4.1.4 for specific instructions on glassware
cleaning). The sample containers should be of glass or Teflon, and have screw-
caps with Teflon lined septa. In situations where Teflon is not available,
solvent-rinsed aluminum foil may be used as a liner. However, acidic or basic
samples may react with the aluminum foil, causing eventual contamination of the
sample. Plastic containers or lids may NOT be used for the storage of samples
due to the possibility of sample contamination from the phthalate esters and
other hydrocarbons within the plastic. Sample containers should be filled with
care so as to prevent any portion of the collected sample coming in contact with
the sampler's gloves, thus causing contamination. Samples should not be
FOUR - 2 Revision 2
November 1992
collected or stored in the presence of exhaust fumes. If the sample comes in
contact with the sampler (e.g. if an automatic sampler is used), run organic-free
reagent water through the sampler and use as a field blank.
4 .1. 3 Safety
Safety should always be the primary consideration in the collection of
samples. A thorough understanding of the waste production process, as well as
all of the potential hazards making up the waste, should be investigated whenever
possible. The site should be visually evaluated just prior to sampling to
determine additional safety measures. Minimum protection of gloves and safety
glasses should be worn to prevent sample contact with the skin and eyes. A
respirator should be worn even when working outdoors if organic vapors are
present. More hazardous sampling missions may require the use of supplied air
and special clothing.
4.1.4 Cleaning of Glassware
In the analysis of samples containing components in the parts per billion
range, the preparation of scrupulously clean glassware is mandatory. Failure to
do so can lead to a myriad of problems in the interpretation of the final
chromatograms due to the presence of extraneous peaks resulting from
contamination. Particular care must be taken with glassware such as Soxhlet
extractors, Kuderna-Dani sh evaporative concentrators, sampling-train components,
or any other glassware coming in contact with an extract that will be evaporated
to a smaller volume. The process of concentrating the compounds of interest in
this operation may similarly concentrate the contaminating substance(s), which
may seriously distort the results.
The basic cleaning steps are:
1. Removal of surface residuals immediately after use;
2. Hot soak to loosen and float most particulate material;
3. Hot water rinse to flush away floated particulates;
4. Soak with an oxidizing agent to destroy traces of organic compounds;
5. Hot water rinse to flush away materials loosened by the deep penetrant
soak;
6. Distilled water rinse to remove metallic deposits from the tap water;
7. Alcohol, e.g., isopropanol or methanol, rinse to flush off any final
traces of organic materials and remove the water; and
8. Flushing the item immediately before use with some of the same solvent
that will be used in the analysis.
FOUR - 3 Revision 2
November 1992
Each of these eight fundamental steps are discussed here in the order in
which they appeared on the preceeding page.
1. As soon possible after glassware (i.e. beakers, pipets, flasks, or
bottles) has come in contact with sample or standards, the glassware
should be flushed with alcohol before it is placed in the hot
detergent soak. If this is not done, the soak bath may serve to
contaminate all other glassware placed therein.
2. The hot soak consists of a bath of a suitable detergent in water of
50°C or higher. The detergent, powder or liquid, should be entirely
synthetic and not a fatty acid base. There are very few areas of the
country where the water hardness is sufficiently low to avoid the
formation of some hard-water scum resulting from the reaction between
calcium and magnesium salts with a fatty acid soap. This hard-water
scum or curd would have an affinity particularly for many chlorinated
compounds and, being almost wholly water-insoluble, would deposit on
all glassware in the bath in a thin film.
There are many suitable detergents on the wholesale and retail market.
Most of the common liquid dishwashing detergents sold at retail are
satisfactory but are more expensive than other comparable products
sold industrially. Alconox, in powder or tablet form, is manufactured
by Alconox, Inc., New York, and is marketed by a number of laboratory
supply firms. Sparkleen, another powdered product, is distributed by
Fisher Scientific Company.
3. No comments required.
4. The most common and highly effective oxidizing agent for removal of
traces of organic compounds is the traditional chromic acid solution
made up of concentrated sulfuric acid and potassium or sodium
dichromate. For maximum efficiency, the soak solution should be hot
(40-50°C). Safety precautions must be rigidly observed in the
handling of this solution. Prescribed safety gear should include
safety goggles, rubber gloves, and apron. The bench area where this
operation is conducted should be covered with fluorocarbon sheeting
because spattering will disintegrate any unprotected surfaces.
The potential hazards of using chromic sulfuric acid mixture are great
and have been well publicized. There are now commercially available
substitutes that possess the advantage of safety in handling. These
are biodegradable concentrates with a claimed cleaning strength equal
to the chromic acid solution. They are alkaline, equivalent to ca.
0.1 N NaOH upon dilution, and are claimed to remove dried blood,
silicone greases, distillation residues, insoluble organic residues,
etc. They are further claimed to remove radioactive traces and will
not attack glass or exert a corrosive effect on skin or clothing. One
such product is "Chem Solv 2157," manufactured by Mallinckrodt and
available through laboratory supply firms. Another comparable product
is "Detex," a product of Borer-Chemie, Solothurn, Switzerland.
5, 6, and 7. No comments required.
FOUR - 4 Revision 2
November 1992
8. There is always a possibility that between the time of washing and the
next use, the glassware could pick up some contamination from either
the air or direct contact. To ensure against this, it is good
practice to flush the item immediately before use with some of the
same solvent that will be used in the analysis.
The drying and storage of the cleaned glassware is of critical importance
to prevent the beneficial effects of the scrupulous cleaning from being
nullified. Pegboard drying is not recommended. It is recommended that
laboratory glassware and equipment be dried at 100°C. Under no circumstances
should such small items be left in the open without protective covering. The
dust cloud raised by the daily sweeping of the laboratory floor can most
effectively recontaminate the clean glassware.
As an alternate to solvent rinsing, the glassware can be heated to a
minimum of 300°C to vaporize any organics. Do not use this high temperature
treatment on volumetric glassware, glassware with ground glass joints, or
sintered glassware.
4.1.5 High Concentration Samples
Cross contamination of trace concentration samples may occur when
prepared in the same laboratory with high concentration samples. Ideally,
if both type samples are being handled, a laboratory and glassware
dedicated solely to the preparation of high concentration samples would be
available for this purpose. If this is not feasible, as a minimum when
preparing high concentration samples, disposable glassware should be used
or, at least, glassware dedicated entirely to the high concentration
samples. Avoid cleaning glassware used for both trace and high
concentration samples in the same area.
FOUR - 5 Revision 2
November 1992
TABLE 4-1.
SAMPLE CONTAINERS, PRESERVATION, TECHNIQUES, AND HOLDING TIMES
Analyte Class Container Preservative Holding Time
Volatile Organics
Concentrated Waste Samples 125 ml widemouth glass None 14 days
container with Teflon
lined lid
Liquid Samples
No Residual Chlorine 2 X 40 ml vials with Cool 4°C 1 14 days
Present Teflon lined septum caps '
Residual Chlorine Present 2 X 40 ml vials with Collect sample in a 125 ml 14 days
Teflon lined septum caps container which has been pre-
preserved with 4 drops of 10%
sodium thiosulfate solution.
Gently swirl to mix sample and
transfer to a 40 ml VOA vial . 1
Cool, 4°C
Acrolein and 2 X 40 ml vials with Adjust to pH 4-5; cool, 4°C 14 days
Acrylonitrile Teflon lined septum caps
Soil/Sediments and 125 ml widemouth glass Cool, 4°C 14 days
Sludges container sealed with a
septum
1
Adjust pH <2 with H2S0 4 , HCl or solid NaHS0 4 •
FOUR - 6 Revision 2
November 1992
Analyte Class Container Preservative Holding Time
Table 4-1 Continued
Semivolatile Organics/Orqanochlorine Pesticides/PCBs and Herbicides
Concentrated Waste Samples 125 ml widemouth glass None Samples must be
with Teflon lined lid extracted within 14
days and extracts
analyzed within 40
days following
extraction.
Water Samples
No Residual Chlorine 1-gal. or 2 x 0.5-gal. Cool, 4°C Samples must be
Present amber glass container with extracted within 7
Teflon l i ned l id days and extracts
analyzed within 40
days following
extraction.
Residual Chlorine Present 1-gal. or 2 x 0.5-gal. Add 3 ml 10% sodium thiosulfate Samples must be
amber glass container with solution per gallon. 2 Cool, 4°C extracted within 7
Teflon lined lid days and extracts
analyzed within 40
days following
extraction.
Soil/Sediments and Sludges 250 ml widemouth glass Cool, 4°C Samples must be
container with Teflon extracted within 14
lined lid days and extracts
analyzed within 40
days fo 11 owing
extraction.
2
Pre-preservation may be performed in the laboratory prior to field use.
FOUR - 7 Revision 2
November 1992
4.2.1 EXTRACTIONS AND PREPARATIONS
FOUR - 8 Revision 2
November 1992
4.2.2 CLEANUP
FOUR - 9 Revision 2
November 1992
4.3 DETERMINATION OF ORGANIC ANALYTES
4.3.1 GAS CHROMATOGRAPHIC METHODS
FOUR - 10 Revision 2
November 1992
4.3.2 GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC METHODS
November 1992
4.3.3 HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC METHODS
November 1992
4.3.4 FOURIER TRANSFORM INFRARED METHODS
November 1992
4.4. MISCELLANEOUS SCREENING METHODS
November 1992
CHAPTER SEVEN
INTRODUCTION AND REGULATORY DEFINITIONS
7.1 IGNITABILITY
7.1.1 Introduction
This section discusses the hazardous characteristic of ignitability. The
regulatory background of this characteristic is summarized, and the regulatory
definition of ig.nitability is presented. The two testing methods associated with
this characteristic, Methods 1010 and 1020, can be found in Chapter Eight.
The objective of the ignitability characteristic is to identify wastes that
either present fire hazards under routine storage, disposal, and transportation
or are capable of severely exacerbating a fire once started. Use the pressure
filtration technique specified in Method 1311 (TCLP) to determine free liquid for
the purpose of ignitability testing.
7.1.2 Regulatory Definition
The following definitions have been taken nearly verbatim from the RCRA
regulations (40 CFR 261.21) and the DOT regulations (49 CFR §§ 173.300 and
173.151).
Characteristics Of lgnitability Regulation
A solid waste exhibits the characteristic of ignitability if a
representative sample of the waste has any of the following properties:
1. It is a liquid, other than an aqueous solution, containing < 24%
alcohol by volume, and it has a flash point < 60°C (140°F), as
determined by a Pensky-Martens Closed Cup Tester, using the test
method specified in ASTM Standard D-93-79 or D-93-80, or a Setaflash
Closed Cup Tester, using the test method specified in ASTM standard
D-3278-78, or as determined by an equivalent test method approved by
the Administrator under the procedures set forth in Sections 260.20
and 260.21. (ASTM standards are available from ASTM, 1916 Race
Street, Philadelphia, PA 19103.)
2. It is not a liquid and is capable, under standard temperature and
pressure, of causing fire through friction, absorption of moisture,
or spontaneous chemical changes and, when ignited, burns so
vigorously and persistently that it creates a hazard.
3. It is an ignitable compressed gas, as defined in 49 CFR 173.300 and
as determined by the test methods described in that regulation or by
equivalent test methods approved by the Administrator under Sections
260.20 and 260.21.
4. It is an oxidizer, as defined in 49 CFR 173.151.
SEVEN - 1 Revision 2
Noverber 1992
Ignitable Compressed Gas
For the purpose of this regulation the following terminology is defined:
1. Compressed gas. The term "compressed gas" shall designate any
material or mixture having in the container an absolute pressure
exceeding 40 psi at 21°C (70°F) or, regardless of the pressure at
21°C (70°F), having an absolute pressure exceeding 104 psi at 54°C
(130°F), or any liquid flammable material having a vapor pressure
exceeding 40 psi absolute at 38°C (l00°F), as determined by ASTM
Test D-323.
2. Ignitable compressed gas. Any compressed gas, as defined in
Paragraph 1, above, shall be classed as an "ignitable compressed
gas" if any one of the following occurs:
a. Either a mixture of 13% or less (by volume) with air forms a
flammable mixture, or the flammable range with air is wider than
12%, regardless of the lower limit. These limits shall be
determined at atmospheric temperature and pressure. The method
of sampling and test procedure shall be acceptable to the Bureau
of Explosives.
b. Using the Bureau of Explosives' Flame Projection Apparatus (see
Note, below), the flame projects more than 18 in. beyond the
ignition source with valve opened fully, or the flame flashes
back and burns at the valve with any degree of valve opening.
c. Using the Bureau of Explosives' Open Drum Apparatus (see Note,
below), there is any significant propagation of flame away from
the ignition source.
d. Using the Bureau of Explosives' Closed Drum Apparatus (see Note,
below), there is any explosion of the vapor-air mixture in the
drum.
NOTE: Descriptions of the Bureau of Explosives' Flame Projection
Apparatus, Open Drum Apparatus, Closed Drum Apparatus, and method of
tests may be procured from the Association of American Railroads,
Operations and Maintenance Dept., Bureau of Explosives, American
Railroad Building, Washington, DC. 20036; 202-293-4048.
Oxidizer
For the purpose of this regulation, an oxidizer is any material that yields
oxygen readily to stimulate the combustion of organic matter (~, chlorate,
permanganate, inorganic peroxide, or a nitrate).
Novenber 1992
7.2 CORROSIVITY
7.2.1 Introduction
The corrosivity characteristic, as defined in 40 CFR 261.22, is designed
to identify wastes that might pose a hazard to human health or the environment
due to their ability to:
1. Mobilize toxic metals if discharged into a landfill environment;
2. Corrode handling, storage, transportation, and management equipment;
or
3. Destroy human or animal tissue in the event of inadvertent contact.
In order to identify such potentially hazardous materials, EPA has selected
two properties upon which to base the definition of a corrosive waste. These
properties are pH and corrosivity toward Type SAE 1020 steel.
The following sections present the regulatory background and the regulation
pertaining to the definition of corrosivity. The procedures for measuring pH of
aqueous wastes are detailed in Method 9040, Chapter Six. Method 1110, Chapter
Eight, describes how to determine whether a waste is corrosive to steel. Use the
pressure filtration technique specified in Method 1311 (TCLP) to determine free
liquid.
The following material has been taken nearly verbatim from the RCRA
regulations.
1. A sol id waste exhibits the characteristic of corrosivity if a
representative sample of the waste has either of the following
properties:
a. It is aqueous and has a pH~ 2 or~ 12.5, as determined by a pH
meter using either the test method specified in this manual
(Method 9040) or an equivalent test method approved by the
Administrator under the procedures set forth in Sections 260.20
and 260. 21.
b. It is a liquid and corrodes steel (SAE 1020) at rate> 6.35 mm
(0.250 in.) per year at a test temperature of 55°C (130°F), as
determined by the test method specified in NACE (National
Association of Corrosion Engineers) Standard TM-01-69, as
standardized in this manual (Method 1110) or an equivalent test
method approved by the Administrator under the procedures set
forth in Sections 260.20 and 260.21.
Novenber 1992
7. 3 REACT! VITY
7.3.1 Introduction
The regulation in 40 CFR 261.23 defines reactive wastes to include wastes
that have any of the following properties: (1) readily undergo violent chemical
change; (2) react violently or form potentially explosive mixtures with water;
(3) generate toxic fumes when mixed with water or, in the case of cyanide- or
sulfide-bearing wastes, when exposed to mild acidic or basic conditions; (4)
explode when subjected to a strong initiating force; (5) explode at normal
temperatures and pressures; or (6) fit within the Department of Transportation's
forbidden explosives, Class A explosives, or Class B explosives classifications.
This definition is intended to identify wastes that, because of their
extreme instability and tendency to react violently or explode, pose a problem
at all stages of the waste management process. The definition is to a large
extent a paraphrase of the narrative definition employed by the National Fire
Protection Association. The Agency chose to rely almost entirely on a
descriptive, prose definition of reactivity because most of the available tests
for measuring the variegated class of effects embraced by the reactivity
definition suffer from a number of deficiencies.
7.3.2.1 Characteristic Of Reactivity Regulation
A solid waste exhibits the characteristic of reactivity if a
representative sample of the waste has any of the following
properties:
1. It is normally unstable and readily undergoes violent change
without detonating.
2. It reacts violently with water.
3. It forms potentially explosive mixtures with water.
4. When mixed with water, it generates toxic gases, vapors, or
fumes in a quantity sufficient to present a danger to human
health or the environment.
5. It is a cyanide- or sulfide-bearing waste which, when exposed to
pH conditions between 2 and 12. 5, can generate toxic gases,
vapors, or fumes in a quantity sufficient to present a danger to
human health or the environment. (Interim Guidance for Reactive
Cyanide and Reactive Sulfide, Steps 7.3.3 and 7.3.4 below, can
be used to detect the presence of reactive cyanide and reactive
sulfide in wastes.)
6. It is capable of detonation or explosive reaction if it is
subjected to a strong initiating source or if heated under
confinement.
Novamer 1992
7. It is readily capable of detonation or explosive decomposition
or reaction at standard temperature and pressure.
8. It is a forbidden explosive, as defined in 49 CFR 173.51, or a
Class A explosive, as defined in 49 CFR 173.53, or a Class B
explosive, as defined in 49 CFR 173.88.
7.3.3 Interim Guidance For Reactive Cyanide

7.3.3.1 The current EPA guidance level is:
Total releasable cyanide: 250 mg HCN/kg waste.
7.3.3.2 Test Method to Determine Hydrogen Cyanide Released from
Wastes
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to all wastes, with the condition that
wastes that are combined with acids do not form explosive mixtures.
1.2 This method provides a way to determine the specific rate of
release of hydrocyanic acid upon contact with an aqueous acid.
1.3 This test measures only the hydrocyanic acid evolved at the test
conditions. It is not intended to measure forms of cyanide other than those
that are evolvable under the test conditions.
2.0 SUMMARY OF METHOD
2.1 An aliquot of acid is added to a fixed weight of waste in a closed
system. The generated gas is swept into a scrubber. The analyte is
quantified. The procedure for quantifying the cyanide is Method 9010, Chapter
Five, starting with Step 7.2.7 of that method.
3.0 INTERFERENCES
3.1 Interferences are undetermined.
4.0 APPARATUS AND MATERIALS (See Figure 1)
4.1 Round-bottom flask - 500-ml, three-neck, with 24/40 ground-glass
joints.
4.2 Gas scrubber - 50 ml calibrated scrubber
4.3 Stirring apparatus - To achieve approximately 30 rpm. This may be
either a rotating magnet and stirring bar combination or an overhead motor-
dri ven propeller stirrer.
4.4 Addition funnel - With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve.
Novenber 1992
4.5 Flexible tubing For connection from nitrogen supply to
apparatus.
4. 6 Water-pumped or oil -pumped nitrogen gas With two-stage
regulator.
4.7 Rotometer - For monitoring nitrogen gas flow rate.
4.8 Analytical balance - capable of weighing to 0.001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals sha 11 be used in a11 tests. Un 1ess
otherwise indicated, it is intended that a11 reagents sha 11 conform to the
specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.
5. 2 Reagent water. Al 1 references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sulfuric acid (O.OlN), H S04 • Add 2.8 ml concentrated H2SOi to
reagent water and dilute to 1 L. Wittdraw 100 ml of this solution and di ute
to 1 L to make the O.OlN H2S04 .
5.4 Cyanide reference solution, (1000 mg/L). Dissolve approximately
2.5 g of KOH and 2.51 g of KCN in 1 liter of reagent water. Standardize with
0.0192N AgN03 • Cyanide concentration in this solution should be 1 mg/ml.
5.5 Sodium hydroxide solution (l.25N), NaOH. Dissolve 50 g of NaOH in
reagent water and dilute to 1 liter with reagent water.
5.6 Sodium hydroxide solution (0.25N), NaOH. Dilute 200 ml of l.25N
sodium hydroxide solution (Step 5.5) to 1 liter with reagent water.
5.7 Silver nitrate solution (0.0192N). Prepare by crushing
approximately 5 g of AgN03 crystals and drying to constant weight at 40°C.
Weigh 3.265 g of dried AgN03 , dissolve in reagent water, and dilute to 1
1 iter.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Samples containing, or suspected of containing, sulfide or a
combination of sulfide and cyanide wastes should be collected with a minimum
of aeration. The sample bottle should be filled completely, excluding all
head space, and stoppered. Analysis should commence as soon as possible, and
samples should be kept in a cool, dark place until analysis begins.
6. 2 It is suggested that samp 1es of cyanide wastes be tested as
quickly as possible. Although they can be preserved by adjusting the sample
pH to 12 with strong base, this will cause dilution of the sample, increase
the ionic strength, and, possibly, change other physical or chemical
Novenber 1992
characteristics of the waste which may affect the rate of re 1ease of the
hydrocyanic acid. Storage of samples should be under refrigeration and in the
dark.
6.3 Testing should be performed in a ventilated hood.
7. 0 PROCEDURE
7.1 Add 50 ml of 0.25N NaOH solution (Step 5.6) to a calibrated
scrubber and dilute with reagent water to obtain an adequate depth of liquid.
7.2 Close the system and adjust the flow rate of nitrogen, using the
rotometer. Flow should be 60 ml/min.
7.3 Add 10 g of the waste to be tested to the system.
7.4 With the nitrogen flowing, add enough sulfuric acid to fill the
flask half full. Start the 30 minute test period.
7.5 Begin stirring while the acid is entering the round-bottom flask.
The stirring speed must remain constant throughout the test.
NOTE: The stirring should not be fast enough to create a vortex.
7.6 After 30 minutes, close off the nitrogen and disconnect the
scrubber. Determine the amount of cyanide in the scrubber by Method 9010,
Chapter Five, starting with Step 7.2.7 of the method.
NOTE: Delete the "C" and "D" terms from the spectrophotometric procedure
calculation and the "E" and "F" terms from the titration procedure
calculation in Method 9010. These terms are not necessary for the
reactivity determination because the terms determine the amount of
cyanide in the entire sample, rather than only in the aliquot taken for
analysis.
8.0 CALCULATIONS
8.1 Determine the specific rate of release of HCN, using the following
parameters:
X = Concentration of HCN in diluted scrubber solution (mg/L)
(This is obtained from Method 9010.)
L = Volume of solution in scrubber (L)
W= Weight of waste used (kg)
S =Time of measurement (sec.) =Time N2 stopped - Time N2 started
X• L
R = specific rate of release (mg/kg/sec.)
w• s
Total releasable HCN (mg/kg) = R x S
Novenber 1992
9.0 METHOD PERFORMANCE
9.1 The operation of the system can be checked and verified using the
cyanide reference solution (Step 5.4). Perform the procedure using the
reference solution as a sample and determine the percent recovery. Evaluate
the standard recovery based on historical laboratory data, as stated in
Chapter One.
10.0 REFERENCES
10.1 No references are available at this time.
Noventer 1992
FIGURE 1.
APPARATUS TO DETERMINE HYDROGEN CYANIDE RELEASED FROM WASTES
Flow meter
Reaction Flask
Noverber 1992
7.3.4 Interim Guidance For Reactive Sulfide
7.3.4.1 The current EPA guidance level is:
Total releasable sulfide: 500 mg H2S/kg waste.
7.3.4.2 Test Method to Determine Hydrogen Sulfide Released from

Wastes
1.1 This method is applicable to all wastes, with the condition that
waste that are combined with acids do not form explosive mixtures.
1.2 This method provides a way to determine the specific rate of
release of hydrogen sulfide upon contact with an aqueous acid.
1.3 This procedure releases only the hydrogen sulfide evolved at the
test conditions. It is not intended to measure forms of sulfide other than
those that are evolvable under the test conditions.
2.1 An aliquot of acid is added to a fixed weight of waste in a closed
system. The generated gas is swept into a scrubber. The analyte is
quantified. The procedure for quantifying the sulfide is given in Method
9030, Chapter Five, starting with Step 7.3 of that method.
3.0 INTERFERENCES
3.1 Interferences are undetermined.
4.0 APPARATUS AND MATERIALS (See Figure 2)
4.1 Round-bottom fl ask - 500-ml, three-neck, with 24/40 ground-glass
joints.
4.2 Gas scrubber - 50 ml calibrated scrubber.
4.3 Stirring apparatus - To achieve approximately 30 rpm. This may be
either a rotating magnet and stirring bar combination or an overhead motor-
dri ven propeller stirrer.
4.4 Addition funnel - With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve.
4.5 Flexible tubing For connection from nitrogen supply to
apparatus.
Novenber 1992
4. 6 Water-pumped or oi 1-pumped nitrogen gas With two- stage
regulator.
4.7 Rotometer - For monitoring nitrogen gas flow rate.
4.8 Analytical balance - capable of weighing to 0.001 g.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all reagents shall conform to the
Chemical Society, where such specifications are available. Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
determination.
5.2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sulfuric acid (O.OlN), H S04 . Add 2.8 ml concentrated H~S0 4
to reagent water and dilute to 1 L Withdraw 100 ml of this solution and
dilute to 1 L to make the O.OlN H2S04 •
5.4 Sulfide reference solution - Dissolve 4.02 g of Na 2S • 9H 0 in
1.0 liter of reagent water. This solution contains 570 mg/L hydrogen sullide.
Dilute this stock solution to cover the analytical range required (100-570
mg/L).
5.5 Sodium hydroxide solution (l.25N), NaOH. Dissolve 50 g of NaOH in
reagent water and dilute to 1 liter with reagent water.
5.6 Sodium hydroxide solution (0.25N), NaOH. Dilute 200 ml of l.25N
sodium hydroxide solution (Step 5.5) to 1 liter with reagent water.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING

6.1 Samples containing, or suspected of containing, sulfide wastes
should be collected with a minimum of aeration. The sample bottle should be
filled completely, excluding all head space, and stoppered. Analysis should
commence as soon as possible, and samples should be kept in a cool, dark place
until analysis begins.
6. 2 It is suggested that samples of sulfide wastes be tested as
quickly as possible. Although they can be preserved by adjusting the sample
pH to 12 with strong base and adding zinc acetate to the sample, these will
cause dilution of the sample, increase the ionic strength, and, possibly,
change other physical or chemical characteristics of the waste which may
affect the rate of release of the hydrogen sulfide. Storage of samples should
be under refrigeration and in the dark.
6.3 Testing should be performed in a ventilated hood.
Noventer 1992
7. 0 PROCEDURE
7.1 Add 50 ml of O. 25N NaOH solution to a calibrated scrubber and
dilute with reagent water to obtain an adequate depth of liquid.
7.2 Assemble the system and adjust the flow rate of nitrogen, using
the rotometer. Flow should be 60 ml/min.
7.3 Add 10 g of the waste to be tested to the system.
7.4 With the nitrogen flowing, add enough sulfuric acid to fill the
flask half full, while starting the 30 minute test period.
7.5 Begin stirring while the acid is entering the round-bottom flask.
The stirring speed must remain constant throughout the test.
NOTE: The stirring should not be fast enough to create a vortex.
7.6 After 30 minutes, close off the nitrogen and disconnect the
scrubber. Determine the amount of sulfide in the scrubber by Method 9030,
Chapter Five, starting with Step 7.3 of that method.
7. 7 Substitute the fo 11 owing for Step 7. 3. 2 in Method 9030: The
trapping solution must be brought to a pH of 2 before proceeding. Titrate a
sma 11 aliquot of the trapping solution to a pH 2 end point with 6N HCl and
calculate the amount of HCl needed to acidify the entire scrubber solution.
Combine the small acidified aliquot with the remainder of the acidified
scrubber solution.
8.0 CALCULATIONS
8.1 Determine the specific rate of release of H2S, using the following
parameters:
X = Concentration of H~S in scrubber (mg/L)

(This is obtained from Method 9030.)
L = Volume of solution in scrubber (L)
W= Weight of waste used (kg)
S =Time of experiment (sec.) =Time N2 stopped - Time N2 started
X• L
R = specific rate of release (mg/kg/sec.) = - - -
w• s
Total releasable H2S (mg/kg) = R x S
Novenber 1992
9.1 The operation of the system can be checked and verified using the
sulfide reference solution (Step 5.4). Perform the procedure using the
reference solution as a sample and determine the percent recovery. Evaluate
the standard recovery based on historical laboratory data, as stated in
Chapter One.
10. 0 REFERENCES
10.1 No references are available at this time.
Noverrber 1992
FIGURE 2.
APPARATUS TO DETERMINE HYDROGEN SULFIDE RELEASED FROM WASTES
Flowmeter
Gas Scrubber
Reaction Flask
•
NovE!lber 1992
7.4 TOXICITY CHARACTERISTIC LEACHING PROCEDURE
7.4.1 Introduction
The Toxicity Characteristic Leaching Procedure (TCLP) is designed to
simulate the leaching a waste will undergo if disposed of in a sanitary
landfill. This test is designed to simulate leaching that takes place in a
sanitary landfill only. The extraction fluid employed is a function of the
alkalinity of the solid phase of the waste. A subsample of a waste is
extracted with the appropriate buffered acetic acid solution for 18 ± 2 hours.
The extract obtained from the TCLP (the "TCLP extract") is then analyzed to
determine if any of the thresholds established for the 40 Toxicity
Characteristic (TC) constituents (listed in Table 7-1) have been exceeded or
if the treatment standards established for the constituents listed in 40 CFR
§268.41 have been met for the Land Disposal Restrictions (LOR) program. If
the TCLP extract contains any one of the TC constituents in an amount equal to
or exceeding the concentrations specified in 40 CFR §261.24, the waste
possesses the characteristic of toxicity and is a hazardous waste. If the
TCLP extract contains LOR constituents in an amount exceeding the
concentrations specified in 40 CFR §268.41, the treatment standard for that
waste has not been met, and further treatment is necessary prior to land
disposal.
7.4.2 Summary of Procedure
The TCLP consists of five steps (refer to Figure 3):
1. Separation Procedure
For liquid wastes (i.e., those containing less than 0.5% dry solid
material), the waste, after filtration through a 0.6 to 0.8 µm glass fiber
filter, is defined as the TCLP extract.
For wastes containing greater than or equal to 0.5% solids, the liquid,
if any, is separated from the solid phase and stored for later analysis.
2. Particle Size Reduction
Prior to extraction, the solid material must pass through a 9.5-mm
(0.375-in.) standard sieve, have a surface area per gram of material equal to
or greater than 3.1 cm 2 , or, be smaller than 1 cm in its narrowest dimension.
If the surface area is smaller or the particle size larger than described
above, the solid portion of the waste is prepared for extraction by crushing,
cutting, or grinding the waste to the surface area or particle size described
above. (Special precaut i ans must be taken if the solids are prepared for
organic volatiles extraction.)
3. Extraction of Solid Material
The solid material from Step 2 is extracted for 18 ± 2 hours with an
amount of·extraction fluid equal to 20 times the weight of the solid phase.
The extraction fluid employed is a function of the alkalinity of the solid
Novmber 1992
phase of the waste. A special extractor vessel is used when testing for
volatile analytes.
4. Final Separation of the Extraction from the Remaining Solid
Following extraction, the liquid extract is separated from the solid
phase by filtration through a 0.6 to 0.8 µm glass fiber filter. If
compatible, the initial liquid phase of the waste is added to the liquid
extract, and these are analyzed together. If incompatible, the liquids are
analyzed separately and the results are mathematically combined to yield a
volume-weighted average concentration.
5. Testing (Analysis) of TCLP Extract
Inorganic and organic species are identified and quantified using
appropriate methods in the 6000, 7000, and 8000 series of methods in this
manual or by equivalent methods.
Under the Toxicity Characteristic, a solid waste exhibits the
characteristic of toxicity if the TCLP extract from a subsample of the waste
contains any of the contaminants iisted in Table 7-1 at a concentration
greater than or equal to the respective value given in that table. If a waste
contains <0.5% filterable solids, the waste itself, after filtering, is
considered to be the extract for the purposes of analysis.
Under the Land Disposal Restrictions program, a restricted waste
identified in 40 CFR §268.41 may be land disposed only if a TCLP extract of
the waste or a TCLP extract of the treatment residue of the waste does not
exceed the values shown in Table CCWE of 40 CFR §268.41 for any hazardous
constituent listed in Table CCWE for that waste. If a waste contains <0.5%
filterable solids, the waste itself, after filtering, is considered to be the
extract for the purposes of analysis.
Novenber 1992
TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC
Regulatory Level
Contaminant (mg/l)
Arsenic 5.0
Barium 100.0
Benzene 0.5
Cadmium 1.0
Carbon tetrachloride 0.5
Chlordane 0.03
Chlorobenzene 100.0
Chloroform 6.0
Chromium 5.0 1
o-Cresol 200. 0
m-Cresol 200. 01
p-Cresol 200. 01
Cresol 200. 01
2,4-D 10.0
1,4-Dichlorobenzene 7.5
1,2-0ichloroethane 0.5
1,1-Dichloroethylene 0.7
2,4-Dinitrotoluene 0.13 2
Endrin 0.02
Heptachlor (and its hydroxide) 0.008
Hexachlorobenzene 0.13 2
Hexachloro-1,3-butadiene 0.5
Hexachloroethane 3.0
Lead 5.0
Lindane 0.4
Mercury 0.2
Methoxychlor 10.0
Methyl ethyl ketone 200.0
Nitrobenzene 2.0
Pentachlorophenol 100.0
Pyridine 5.0 2
Selenium 1.0
Silver 5.0
Tetrachloroethylene 0.7
Toxaphene 0.5
Novent>er 1992
TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC
Regulatory Level
Contaminant (mg/L)
Trichloroethylene 0.5
2,4,5-Trichlorophenol 400.0
2,4,6-Trichlorophenol 2.0
2,4,5-TP (Silvex) 1.0
Vinyl chloride 0.2
1
If o-, m-, and p-cresol concentrations cannot be differentiated, the total
cresol (0026) concentration is used. The regulatory level of total cresol is
200 mg/L.
2
Quantitation limit is greater than the calculated regulatory level. The
quantitation limit therefore becomes the regulatory level.
Novent>er 1992
FIGURE 3.
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE FLOWCHART
START
Use a
sub·••mple of
w~sle
0
Separ•le Sep•r•le
l1qu1ds from < 0 Sll. > 0 Sll. l1qu1d• from
_ _ _ _,.. sohds w1lh 0 6
sohd• •uln 0 6 i-----<
- 0 8 um gl••• · 0 8 um gla••
f•ber fdler f•ber fdter
Sohd
100!1.
Exam1ne
1ol1d•
No
Extract w/
appropr1•le f lu1d
11 Bollie exlr•clor Reduce
for non-vol•l1le• part.cl e • • z e
2) ZHE: dev1ce for to <'J 5 mm
vol•ldes
Novent>er 1992
FIGURE 3.
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE FLOWCHART
Store l H1u1d
al 4 C
Measure amount of
Separate 11qu1d and analyze
Discard
•olids ----1
Sol1d e•tract from
•olids w/ 0 6
0 8 um gla•s
(malhemat1cally
comb1ne re•ull w/
result of ••tract
f1ber filter analysa)
Comb1ne
••tract w/
llqu1d phase
of waste
STOP
NovE!l'Der 1992
*U.S. G.P.0.:1993-342-139:83252
METHOD 3005
ACID DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY

1.1 Method 3005 is an acid digestion procedure used to prepare surface
water and ground water samples for analysis by flame atomic absorption
spectroscopy (FLAA) or by inductively coupled argon plasma spectroscopy (ICP).
Samples prepared by Method 3005 may be ana 1yzed by AAS or ICP for the
following metals:
Aluminum Magnesium
Antimon~** Manganese
Arsenic Molybdenum
Barium Nickel
Beryllium Potassium
Cadmium Selenium*
Calcium Silver
Chromium Sodium
Cobalt Thallium
Copper Vanadium
Iron Zinc
Lead
*rep only
**May be analyzed by ICP, FLAA, or GFAA
1.2 For the analysis of total dissolved metals, the sample is filtered
at the time of collection, prior to acidification with nitric acid.
2.1 Total recoverable metals - The entire sample is acidified at the
time of collection with nitric acid. At the time of analysis the sample is
heated with acid and substantially reduced in volume. The digestate is
filtered and diluted to volume, and is then ready for analysis.
2.2 Dissolved metals - The sample is filtered through a 0.5-um filter at
the time of collection and the liquid phase is then acidified at the time of
collection with nitric acid. At the time of analysis the sample is heated
with acid and substantially reduced in volume. The digestate is again
filtered (if necessary) and diluted to volume and is then ready for analysis.
3.0 INTERFERENCES
3.1 The analyst should be cautioned that this digestion procedure may
not be sufficiently vigorous to destroy some metal complexes.
3005 - 1 Revision 1
December 1987
4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers of assorted sizes.
4.2 Watch glasses.
4.3 Qualitative filter paper and filter funnels.
5.0 REAGENTS
5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise
i nd i cat e d , i t i s i ntended that a 11 reagents sh a 11 conform to the
Chemical Society, where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of sufficiently
determination.
5.2 ASTM Type II Water (ASTM 01193-77 (1983)). All references to water
in the method refer to ASTM Type II unless otherwise specified.
5.3 Nitric acid (concentrated), HN03. Acid should be analyzed to
determine level of impurities. If method blank is < MDL, then acid can be
used.
5.4 Hydrochloric acid (concentrated), HCl. Acid should be analyzed to
determine level of impurities. If method blank is < MDL, then acid can be
used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
water. Plastic and glass containers are both suitable.
6.3 Sampling
6.3.1 Total recoverable metals - All samples must be acidified at
the time of collection with HN03 (5 mL/L).
6. 3. 2 Dissolved meta 1s - A11 samples must be filtered through a
0.5-um filter and then acidified at the time of collection with
HN03 ( 5 mL/L).
7.0 PROCEDURE
7.1 Transfer a 100-mL aliquot of well-mixed sample to a beaker.
3005 - 2 Revision 1
December 1987
7.2 For metals that are to be analyzed by FLAA or ICP, add 2 ml of
concentrated HN03 and 5 ml of concentrated HCl. The sample is covered with a
ribbed watch glass and heated on a steam bath or hot plate at 90 to 95°C until
the volume has been reduced to 15-20 ml.
CAUTION: Do not boil. Antimony is easily lost by volatilization from
hydrochloric acid media.
7. 3 Remove the beaker and a11 ow to coo 1 . Wash down the beaker wa 11 s
and watch glass with water and, when necessary, filter or centrifuge the
sample to remove silicates and other insoluble material that could clog the
nebulizer. Filtration should be done only if there is concern that insoluble
materials may clog the nebulizer; this additional step is liable to cause
sample contamination unless the filter and filtering apparatus are thoroughly
cleaned and prerinsed with dilute HN03.
7.4 Adjust the final volume to 100 ml with water.
8.0 QUALITY CONTROL
8 .1 A11 qua l i ty control measures described in Chapter One should be
foll owed.
8.2 For each analytical batch of samples processed, blanks {calibration
and reagent) should be carried throughout the entire sample preparation and
analytical process. These blanks will be useful in determining if samples are
being contaminated.
8.3 Replicate samples should be processed on a routine basis. A
replicate sample is a sample brought through the whole sample preparation and
analytical process. Replicate samples will be used to determine precision.
The sample load will dictate the frequency, but 20% is recommended.
8.4 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be included with each group of
samples processed and whenever a new sample matrix is being analyzed.
9.1 No data provided.
10.0 REFERENCES
1. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
2. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification
for Reagent Water"; ASTM: Philadelphia, PA, 1985; Dll93-77.
3005 - 3 Revision 1
December 1987
METHOD 3005
ACID DIGESTION OF ~ATERS l'OA TOTAL RECOVERABLE OR
DISSOLVED METALS FOA ANALYSIS 8Y FLAA CA ICP SPECTAOSCOPY
St•rt
7.l I
Tr•ncter
•11QUOt Of
••mol• to
De•k•r
1.2 I concen.
Add
HNOi •nd
concen. HC tor
••tel• analyz•cS
Cly l'LAA or tCP
1.2 I
He•t sample to
reduce woluiae
7., r
Cool ll••kar:
fl l ter 1t
neca•••ry
7.4 I
ACllU•t final
volu••
Stoo
3005 - 4 Revision I
December 1987
METHOD 3010
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS FOR
TOTAL METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY

1.1 This digestion procedure is used for the preparation of aqueous
samples, EP and mobility-procedure extracts, and wastes that contain suspended
solids for analysis, by flame atomic absorption spectroscopy (FLAA) or
inductively coupled argon plasma spectroscopy (ICP). The procedure is used to
determine total metals.
1.2 Samples prepared by Method 3010 may be analyzed by FLAA or ICP for
the following:
Aluminum Magnesium
*Arsenic Manganese
Barium Molybdenum
Beryllium Nickel
Cadmium Potassium
Calcium *Selenium
Chromium Sodium
Cobalt Thallium
Copper Vanadium
Iron Zinc
Lead
* Analysis by ICP
NOTE: See Method 7760 for FLAA preparation for Silver.
1.3 This digestion procedure is not suitable for samples which will be
analyzed by graphite furnace atomic absorption spectroscopy because
hydrochloric acid can cause interferences during furnace atomization.
2.1 A mixture of nitric acid and the material to be analyzed is refluxed
in a covered Griffin beaker. This step is repeated with additional portions
of nitric acid until the digestate is light in color or until its color has
stabilized. After the digestate has been brought to a low volume, it is
refluxed with hydrochloric acid and brought up to volume. If sample should go
to dryness, it must be discarded and the sample reprepared.
3.0 INTERFERENCES
3.1 Interferences are discussed in the referring analytical method.
3010 - 1 Revision 1
December 1987
4.1 Griffin beakers - 150-ml.
4.2 Watch glasses - Ribbed and plain.
4.3 Quantitative filter paper or centrifugation equipment.
5.0 REAGENTS
indicated, it is intended that all reagents shall conform to the
determination.
5.2 ASTM Type II Water (ASTM Dll93-77 (1983)). All references to water in
the method refer to ASTM Type II unless otherwise specified.
determine levels of impurities. If method blank is < MDL, the acid can be
used.
5. 4 Hydrochloric acid ( 1: 1), HCl . Prepared from water and hydrochloric
acid. Hydrochloric acid should be analyzed to determine level of impurities.
If method blank is < MDL, the acid can be used.
water. Plastic and glass containers are both suitable. See Chapter Three,
Step 3.1.3, for further information.
6.3 Aqueous wastewaters must be acidified to a pH of < 2 with HN03.
6.4 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Transfer a 100-ml representative aliquot of the well-mixed sample to
a 150-ml Griffin beaker and add 3 ml of concentrated HN03. Cover the beaker
with a ribbed watch glass. Place the beaker on a hot plate and cautiously
evaporate to a low volume (5 ml), making certain that the sample does not boil
and that no portion of the bottom of the beaker is a11 owed to go dry. Cool
the beaker and add another 3-ml portion of concentrated HN03. Cover the
3010 - 2 Revision 1
December 1987
beaker with a nonribbed watch glass and return to the hot plate. Increase the
temperature of the hot plate so that a gentle reflux action occurs.
NOTE: If a sample is allowed to go to dryness, low recoveries will
result. Should this occur, discard the sample and reprepare.
7.2 Continue heating, adding additional acid as necessary, until the
digestion is complete (generally indicated when the digestate is light in
co 1or or does not change in appearance with continued refluxing) . Again,
uncover the beaker or use a ribbed watch glass, and evaporate to a low volume
(3 ml), not allowing any portion of the bottom of the beaker to go dry. Cool
the beaker. Add a small quantity of 1:1 HCl (10 ml/100 ml of final solution),
cover the beaker, and reflux for an additional 15 minutes to dissolve any
precipitate or residue resulting from evaporation.
7.3 Wash down the beaker walls and watch glass with water and, when
necessary, filter or centrifuge the sample to remove silicates and other
insoluble material that could clog the nebulizer. Filtration should be done
only if there is concern that i nso l ub le materials may clog the nebu l i zer.
This add it i ona 1 step can cause samp 1e contamination un 1ess the filter and
filtering apparatus are thoroughly cleaned and prerinsed with dilute HN03.
Adjust to the final volume of 100 ml with water. The sample is now ready for
analysis.
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One should be
foll owed.
8.2 For each analytical batch of samples processed, blanks (calibration
and reagent) should be carried throughout the entire sample-preparation and
being contaminated.
8.3 Replicate samples should be processed on a routine basis. A
replicate sample is a sample brought through the whole sample preparation and
analytical process. A replicate sample should be processed with each
analytical batch or every 20 samples, whichever is greater.
8.5 The method of standard addition shall be used for the analysis of all
EP extracts (see Method 7000, Step 8.7).
3010 - 3 Revision 1
December 1987
10.0 REFERENCES
1. Rohrbaugh, W. G. ; et al . Reagent Chemicals, American Chemical Society
for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3010 - 4 Revision 1
December 1987
Mf:THOO 3010
AClO OlGCSTlON flAOCCDUAf: ~OR ~~AMC ATOMIC A8SOAPTION SPCCTAOSCOPY
Stert
7. 1
Tr•n•t•,.
•llQUOt ot
••11101• to
beeke,.; eCICI
cone. MNOJ
7.t
Me•t end
eveoo,.•t•
to 10 ..
volu ..•: cool:
•CICI cone. MNOj
7.t
R•l'leet.
snc,.••••
t.••o.
t.o
e,.••t• gentle
,.•flu• •ct.ton
7.2 Conttnue
l'leettno
unt11 dlO••tlon
1• COlllOlete;
eveoar•t•: •OCI
MCl;wer• D••k•,.
7.l
~llter 1f
nec••••'"Y eno
•dJu•t volu.,•
3010 - 5 Revision I
December 1987
METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
SAMPLES AND EXTRACTS
.. 0 SCOPE AND APPLICATION

I.I This digestion procedure is used for the preparation of aqueous
;amples, mobility-procedure extracts, and wastes that contain suspended solids
~or analysis, by flame atomic absorption spectroscopy (FLAA), graphite furnace
.bsorption spectroscopy (GFAA), inductively coupled argon plasma spectroscopy
:ICP), or inductively coupled argon plasma mass spectrometry (ICP-MS). The
lrocedure is a hot acid leach for determining available metals.
1.2 Samples prepared by Method 3015 using nitric acid digestion may be
nalyzed by FLAA, GFAA, ICP, or ICP-MS for the following:
Aluminum Lead
Antimony Magnesium
*Arsenic Manganese
Barium Molybdenum
Beryllium Nickel
Cadmium Potassium
Calcium *Selenium
Chromium Silver
Cobalt Sodium
Copper Thallium
Iron Vanadium
Zinc
*Cannot be analyzed by FLAA

2.1 Nitric acid is added to an aqueous sample in a 120 ml Teflon
digestion vessel. The vessel is capped and heated in a microwave unit. After
cooling, the vessel contents are filtered, centrifuged, or allowed to settle in
a clean sample bottle for analysis.
3.0 INTERFERENCES
3.1 Very reactive or volatile materials that may create high pressures
when heated may cause venting of the vessels with potential loss of sample and
analytes. Samples that contain carbonates or other carbon dioxide generating
compounds may cause enough pressure to vent the vessel. If this situation is
anticipated the analyst may wish to use a smaller sample.
3015 - 1 Revision 0
November 1992
4.1 Microwave apparatus requirements
4.1.1 The microwave unit provides programmable power with <
minimum of 574 Wand can be programmed to within ± 10 Wof the requirec
power.
4.1.2 The microwave unit cavity is corrosion resistant anc
we 11 ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires Teflon PFA digestion vessels (120 ml
capacity) capable of withstanding pressures up to 7.5 ± 0.7 atm (110 ±
10 psi) and capable of controlled pressure relief at pressures exceedin~
7.5 ± 0.7 atm (110 ± 10 psi).
4.1.5 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum of 3 rpm.
4.1.6 Those laboratories now using or contemplating the use of
kitchen type microwave ovens for this method should be aware of several
significant safety issues. First, when an acid such as nitric is used
to assist sample digestion in microwave units in open vessels, or sealed
vessels equipped with venting features, there is the potential for the
acid gases released to corrode the safety devices that prevent the
microwave magnetron from shutting off when the door is opened. This can
result in operator exposure to microwave energy. Use of a unit with
corrosion resistant safety devices prevents this from occurring.
The second safety concern rel ates to the use of sealed containers
without pressure relief valves in the unit. Temperature is the impor-
tant variable controlling the reaction. Pressure is needed to attain
elevated temperatures but must be safely contained. However, many
digestion vessels constructed from certain Teflons may crack, burst, or
explode in the oven under certain pressures. Only unlined PFA Teflon
containers with pressure relief mechanisms are considered acceptable at
present.
Users are therefore advised not to use kitchen type microwave ovens or
to use sealed containers without pressure relief valves for microwave
acid digestions by this method. Use of laboratory grade microwave
equipment is required to prevent safety hazards. For further informa-
tion consult reference 1.
4.2 Plastic ware graduated cylinder, 50 or 100 ml capacity.
3015 - 2 Revision 0
November 1992
4.3 Quantitative filter paper, Whatman No. 41 or S&S White label or
quivalent.
,. 4.4 Analytical balance, 300 g capacity, minimum ± 0.01 g.
4.5 Disposable polypropylene filter funnel.
4.6 Polyethylene bottles, 125 ml, with caps
·. 0 REAGENTS
therwise indicated, it is intended that all reagents shall conform to the
pecifications of the Committee on Analytical Reagents of the American Chemical
ociety, where such specifications are available. All acids should be
ub-boiling distilled where possible to minimize the blank levels due to metallic
ontamination. Other grades may be used, provided it is first ascertained that
he reagent is of sufficiently high purity to permit its use without lessening
he accuracy of the determination.
5.2 Reagent Water. Reagent water shall be interference free. All
eferences to water in the method refer to reagent water unless otherwise specif-
ed (Ref. 2).
5.3 Concentrated Nitric acid, HN03 • Acid should be analyzed to
etermine levels of impurities .
. 0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

ddresses the considerations discussed in Chapter Nine of this manual.
ater. Plastic containers are preferable. See Chapter Three, Step 3.1.3 of this
anual, for further information.
6.3 Aqueous waste waters must be acidified to a pH of < 2 with HN0 3 •
. 0 PROCEDURE
7.1 Calibration of Microwave Equipment
7.1.1 Measurement of the available power for heating is
evaluated so that absolute power in watts may be transferred from one
microwave unit to another. For cavity type microwave equipment, this
is accomplished by measuring the temperature rise in 1 kg of water
3015 - 3 Revision O
November 1992
exposed to microwave radiation for a fixed period of time. The analys1
can relate power in watts to the partial power setting of the unit. ThE
calibration format required for laboratory microwave units depends or
the type of electronic system used by the manufacturer to provi.dE
partial microwave power. Few units have an accurate and precise lineal
relationship between percent power settings and absorbed power. Where
linear circuits have been utilized, the calibration curve can be deter-
mined by a three-point calibration method {7.1. 3), otherwise, the
analyst must use the multiple point calibration method {7.1.2).
7.1.2 The multiple point calibration involves the measuremen·
of absorbed power over a large range of power settings. Typically, fo
a 600 W unit, the following power settings are measured; 100,99,98,97,9·
5,90,80,70,60,50, and 40% using the procedure described in sectior
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of thE
calibration. If the unit's electronics are known to have nonlinea
deviations in any region of proportional power control, it will b
necessary to make a set of measurements that bracket the power to bi
used. The final calibration point should be at the partial powe
setting that will be used in the test. This setting should ·be checkec
periodically to evaluate the integrity of the calibration. If •
significant change is detected {±10 W}, then the entire calibratio
should be reevaluated.
7.1.3 The three-point calibration involves the measurement o·
absorbed power at three different power settings. Measure the power a·
100% and 50% using the procedure described in section 7.1.4, anc
calculate the power setting corresponding to the required power in watt:
specified in the procedure from the (2-point) line. Measure th·
absorbed power at that partial power setting. If the measured absorbe 1
power does not correspond to the specified power within ±10 W, use th
multiple point calibration in 7.1.2. This point should also be used t
periodically verify the integrity of the calibration.
7.1. 4 Equilibrate a large volume of water to room temperatur 1
(23 ± 2 °C). One kg of reagent water is weighed (1,000.0 g ± 0.1 g,

into a Teflon beaker or a beaker made of some other material that doe:
not significantly absorb microwave energy (glass absorbs mi crowav·
energy and is not recommended). The initial temperature of the wate
should be 23 ± 2 °C measured to ± 0.05 °C. The covered beaker i:
circulated continuously (in the normal sample path) through th·
microwave field for 2 minutes at the desired partial power setting wit
the unit's exhaust fan on maximum (as it will be during norma·
operation). The beaker is removed and the water vigorously stirred
Use a magnetic stirring bar inserted immediately after microwav
irradiation and record the maximum temperature within the first 3
seconds to± 0.05 °C. Use a new sample for each additional measurement
If the water is reused both the water and the beaker must have returne 1
to 23 ± 2 °C. Three measurements at each power setting should be made

3015 - 4 Revision 0
November 1992
The absorbed power is determined by the following relationship
P = (K) (Cp) (m) (6T)
Eq. l
t
P = the apparent power absorbed by the sample in watts (W).

(W=joul e·sec· )
K = the conversion factor for thermochemical cal ori es·sec· 1 to watts
(=4.184)
Cp = the heat capacity, thermal capacity, or specific heat

(cal·g· 1 · c 1 ), of water
0
m =the mass of the water sample in grams (g),

~T =the final temperature minus the initial temperature ( °C), and
t =the time in seconds (s).
Using the experimental conditions of 2 minutes and l kg of distilled
water (heat capacity at 25 °C is 0.9997 cal·g· 1·°C 1 ) the calibration
equation simplifies to:
P = (6T) (34.86) Eq. 2
NOTE: Stable line voltage is necessary for accurate and reproducible
calibration and operation. The line voltage should be within
manufacturer's specification, and during measurement and operation not
vary by more than ±2 V. A constant power supply may be necessary for
microwave use if the source of the line voltage is unstable.
Electronic components in most microwave units are matched to the
units' function and output. When any part of the high voltage
circuit, power source, or control components in the unit have been
serviced or replaced, it will be necessary to recheck the units'
calibration power. If the power output has changed significantly
(±10 W), then the entire calibration should be reevaluated.
7.2 All digestion vessels and volumetric ware must be carefully acid
~ashed and rinsed with reagent water. When switching between high solids
:concentrated) samples and low solids (low concentration) samples all digestion
1essels should be cleaned by leaching with hot (1:1) hydrochloric acid for a
inimum of two hours followed with hot (1:1) nitric acid for a minimum of two
ours and rinsed with reagent water and dried in a clean environment. This
:leaning procedure should also be used whenever the prior use of the digestion
3015 - 5 Revision 0
November 1992
vessels is unknown or cross contamination from vessels is suspected. Polymeric
volumetric ware and storage containers should be cleaned by leaching with more
dilute acids appropriate for the specific plastics used and then rinsed with
reagent water and dried in a clean environment.
7.3 Sample Digestion
7.3.1 Weigh the Teflon PFA digestion vessel, valve and cap
assembly to 0.01 g prior to use.
7.3.2 A 45 ml aliquot of a well shaken sample is measured in a
graduated cylinder. This aliquot is poured into the Teflon digestion
vessel with the number of the vessel recorded on the preparation sheet.
7.3.3 A blank sample of reagent water is treated in the same
manner along with spikes and duplicates.
7.3.4 Add 5 ml of concentrated nitric acid to each vessel that
will be used. Check to make sure the pressure relief disks are in the
caps with the smooth side toward the sample and start the caps a fe~
turns on the vessels. Finish tightening the caps in the capping statior
which will tighten them to a uniform torque pressure of 12 ft.lbs. (16-~
m). Weigh each capped vessel to the nearest 0.01 g.
7.3.5 Place five vessels evenly distributed in the carousel.
Blanks are treated as samples for the purpose of balancing the power
input. When fewer than the recommended number of samples are digested,
the remaining vessels should be filled with 45 ml of reagent water anc
5 ml of nitric acid to achieve the full compliment of vessels. This
provides an energy balance since the microwave power absorbed is propor-
tional to the total mass in the cavity (Ref. 1).
7.3.6 Place the carousel in the unit; be sure to seat it
carefully on the turntable. Program the microwave unit for the
first-stage of the power program to give 545 Wfor 10 minutes and the
second-stage program to give 344 Wfor 10 minutes. This sequence bring!
the samples to 160°C ± 4°C in 10 minutes and permits a slow rise tc
165-170 °C during the second 10 minutes (Ref. 3). Start the turntablE
motor and be sure the vent fan is running on high and the turntable i~
turning. Start the microwave generator.
7.3.6.l Newer microwave units may be capable of higher
power that permit digestion of a larger number of samples per
batch. If the analyst wishes to digest more than 5 samples at ,
time, the analyst may use different power settings as long as the:
result in the same time and temperature conditions defined ir
7.3.6. That is, any sequence of power that brings the samples t<
160°C ± 4°C in 10 minutes and permits a slow rise to 165-170°(
during the second 10 minutes (Ref. 2).
3015 - 6 Revision 0
November 1992
Issues of safety, structural integrity (both temperature and
pressure limitations), heat loss, chemical compatibility,
microwave absorption of vessel material , and energy transport wil 1
be considerations made in choosing alternative vessels. If all
of the considerations are met and the appropriate power settings
are provided to reproduce the reaction condit i ans defined in
7.3.6, then these alternative vessels may be used (Ref. 1,2)
7.3.7 At the end of the microwave program, allow the vessels
;o cool for at least 5 minutes in the unit before removal to avoid
>ossible injury if a vessel vents immediately after microwave heating.
fhe samples may be cooled outside the unit by removing the carousel and
llowing the samples to cool on the bench or in a water bath. When the
vessels have cooled to room temperature, weigh and record the weight of
!ach vessel assembly. If the weight of the sample plus acid has
jecreased by more than 10% discard the sample.
7.3.8 Rinse virgin or acid-cleaned polyethylene 125 ml bottles
(or other suitable size) and caps with reagent water and shake out the
arge water drops. Label the bottles.
7.3.9 Complete the preparation of the sample by carefully
Jncapping and venting each vessel in a fume hood. Transfer the sample
:o an acid-cleaned polyethylene bottle. If the digested sample contains
>articulates which may clog nebulizers or interfere with injection of
:he sample into the instrument, the sample may be centrifuged, allowed
:o settle or filtered.
7.3.9.1 Centrifugation: Centrifugation at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.3.9.2 Settling: Allow the sample to stand until the
supernatant is clear. Allowing a sample to stand overnight will
usually accomplish this. If it does not, centrifuge or filter the
sample.
7.3.9.3 Filtering: The filtering apparatus must be
thoroughly cleaned and prerinsed with dilute nitric acid. Filter
the sample through quantitative filter paper into a second
acid-cleaned container.
7.3.10 The concentration values obtained from analysis must be
:orrected for the dilution factor from the acid addition. If the sample
~ill be analyzed by ICP-MS additional dilution will generally be
lecessary. For example, the sample may be diluted by a factor of 20
~ith reagent water and the acid strength adjusted back to 10% prior to
nalysis. The dilutions used should be recorded and the measured con-
:entrations adjusted accordingly.
3015 - 7 Revision 0
November 1992
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One, of this
Manual, should be followed.
8.2 For each analytical batch of samples processed, analytical reagent
blanks {also field blanks if they were taken) should be carried throughout the
entire sample preparation and analytical process. These blanks will be useful
in determining if samples are being contaminated.
8.3 Replicate samples should be processed on a routine basis. P
replicate sample is a real sample brought through the whole sample preparation
and analytical process. A replicate sample should be processed with each
analytical batch or every 20 samples, whichever is the greater number.
8.4 Spiked samples or standard reference materials should be employee
to determine accuracy. A spiked sample should be included with each group of
8.5 The method of standard addition shall be used for the analysis of
all EP extracts (see Method 7000, Step 8.7).

9.1 Refer to Reference 4.
10.0 REFERENCES
1. Introduction to Microwave Sample Preparation: Theory and Practice,
Kingston, H. M.; Jassie, L. B., Eds.; ACS Professional Reference Boo~
Series: American Chemical Society, Washington, DC, 1988; Ch 6 & 11.
2. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specificatior
for Reagent Water"; ASTM: Philadelphia, PA, 1985; 01193-77.·
3. Kingston, H. M., Final Report EPA IAG #DWI3932541-0l-I, September 30,
1988, Appendix A.
4. Shannon, M., Alternate Test Procedure Application, USEPA Region y_,
Central Regional Laboratory, 536 S. Clark Street, Chicago, IL 60606,
1989.
3015 - 8 Revision 0
November 1992
METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION
OF AQUEOUS SAMPLES AND EXTRACTS
Start
7.1 Calibrate
the microwave
•quipaent
7. 2 Acicl waah 7.3.l Meaaure 7.3.2 u.. blank

and H,O rin•• 45 aL aliquot •••plea o!
all di!J•ation into the r•agent H,O in
v••••l• and
glaaawar•
dig•ahon other digeation
veaaela
v••••l
7.3.3 Add
conc•ntrat•d
HNO, to ••ch
v••••l
7 3.4 Plac• 5
v••••l• in tha
carou.a•l; u.ae
blank• i! !•w•r
than S •ample•
7 3 S Pl•c•
the carou••l
l.n ov•n, h•at
accordin!J lo
pow•r progra•
7 3. 7 RinH 7. 3 6 Allow
virgin ••mpl•• to
poly•thyl•n• cool ao they
bottlH with ar• not hot
r••!J•nt wal•r to touch
7. 3. 8 Plac• 7.3.8 1-7.3 8.3

•••pl• in C•ntri!ug•,
acid-cl•an•d ••ttl•, and
poly•thyl•n• filter •••pl•
bottl•
No
7 3 9 Corr•ct
concentration
valu•a !or
th• dilution
!actor
Stop
3015 - 9 Revision 0
November 1992
METHOD 3020
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS FOR ANALYSIS BY GFAA SPECTROSCOPY

1.1 This digestion procedure is used for the preparation of aqueous
samples, mobility-procedure extracts, and wastes that contain suspended solids
for analysis by furnace atomic absorption spectroscopy (GFAA) for the metals
listed below. The procedure is used to determine the total amount of the
metal in the sample.
1.2 Samples prepared by Method 3020 may be analyzed by GFAA for the
following metals:
Beryllium Lead
Cadmium Molybdenum
Chromium Thallium
Cobalt Vanadium
NOTE: For the digestion and GFAA analysis of arsenic and selenium, see
Methods 7060 and 7740. For the digestion and GFAA analysis of
silver, see Method 7761.
2.1 A mixture of nitric acid and the material to be analyzed is refluxed
in a covered Griffin beaker. This step is repeated with additional portions
of nitric acid until the digestate is light in color or until its color has
stabilized. After the digestate has been brought to a low volume, it is
cooled and brought up in dilute nitric acid such that the final dilution
contains 3% (v/v) nitric acid. If the sample contains suspended solids, it
must be centrifuged, filtered, or allowed to settle.
3.0 INTERFERENCES
3.1 Interferences are discussed in the referring analytical method.
4.1 Griffin beakers - 150-mL.
4.2 Watch glasses.
4.3 Qualitative filter paper or centrifugation equipment.
3020 - 1 Revision 1
December 1987
5.0 REAGENTS
determination.
determine levels of impurities. If method blank is < MDL, the acid can be
used.
6.3 Aqueous wastewaters must be acidified to a pH of < 2 with HN03.
7.0 PROCEDURE
7.1 Transfer a 100-ml representative aliquot of the well-mixed sample to
a 150-ml Griffin beaker and add 3 ml of concentrated HN03. Cover the beaker
with a ribbed watch glass. Place the beaker on a hot plate and cautiously
evaporate to a low volume (5 ml), making certain that the sample does not boil
and that no portion of the bottom of the beaker is all owed to go dry. Cool
beaker with a non-ribbed watch glass and return to the hot plate. Increase
the temperature of the hot plate so that a gentle reflux action occurs.
7.2 Continue heating, adding additional acid as necessary, until the
digestion is complete (generally indicated when the digestate is light in
co 1or or does not change in appearance with continued refluxing) . When the
digestion is complete, evaporate to a low volume (3 ml); use a ribbed watch
glass, not allowing any portion of the bottom of the beaker to go dry. Remove
the beaker and add approximately 10 ml of water, mix, and continue warming the
beaker for 10 to 15 minutes to allow additional solubilization of any residue
to occur.
3020 - 2 Revision 1
December 1987
7.3 Remove the beaker from the hot plate and wash down the beaker walls
and watch glass with water. When necessary, filter or centrifuge the sample
to remove silicates and other insoluble material that may interfere with
injecting the sample into the graphite atomizer. (This additional step can
cause sample contamination unless the filter and filtering apparatus are
thoroughly cleaned and prerinsed with dilute HN03.) Adjust to the final
volume of 100 ml with water. The sample is now ready for analysis.
8.0 QUALITY CONTROL
foll owed.
8.2 For each group of samples processed, preparation blanks (water and
reagent) should be carried throughout the entire sample preparation and
being contaminated.
8.3 Replicate samples should be processed on a routine basis. Replicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% is recommended.
8.5 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.6 The method of standard addition shall be used for the analysis of
all EP extracts. See Method 7000, Step 8.7, for further information.
10.0 REFERENCES
1. Rohrbaugh, W.G.; et al. Reagent Chemicals, American Chemical Society
3020 - 3 Revision 1
December 1987
METHOO 3020
ACIO OJGESTION FOR AQUEOUS SAMP~ES ANO EXTRACTS
'OR TOTAL METALS FOA ANALYSIS BY GFAA SPECTROSCOPY
7. l Put
al1Quot
ot 1a111ol• 1t,
beaker: 1120 cone:
HNOJ: evaoorate
to low volum•
7.l Cool
Da1k1r;
ae2d cone. Ml'I0 1 :
he•t until
gentle reflux
act.ton occur•
7.2 He•t to
COlllDllte
a1;11t.1on:
1v1oor•t.• to
low volume:
cool
7.2
Add
Type II; w1r111
to a111olv1 1ny
prec101t1t1 or
restou•
7.3
Filter
01" c1ntl"lfuga
l t naca11al"y;
aasu1t. volu1111
3020 - 4 Revision l
December 1987
METHOD 3050
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS

1.1 This method is an acid digestion procedure used to prepare sediments,
sludges, and soil samples for analysis by flame or furnace atomic absorption
spectroscopy (FLAA and GFAA, respectively) or by inductively coupled argon
plasma spectroscopy (ICP). Samples prepared by this method may be analyzed by
ICP for all the listed metals, or by FLAA or GFAA as indicated below (see also
Step 2.1):
FLAA GFAA
Aluminum Magnesium Arsenic
Barium Manganese Beryllium
Beryllium Molybdenum Cadmium
Cadmium Nickel Chromium
Calcium Osmium Cobalt
Chromium Potassium Iron
Cobalt Silver Lead
Copper Sodium Molybdenum
Iron Thallium Selenium
Lead Vanadium Thallium
Zinc Vanadium
NOTE: See Method 7760 for FLAA preparation for Silver.
2.1 A representative 1- to 2-g (wet weight) sample is digested in nitric
acid and hydrogen peroxide. The digestate is then refluxed with either nitric
acid or hydrochloric acid. Dilute hydrochloric acid is used as the final
reflux acid for (1) the ICP analysis of As and Se, and (2) the flame AA or ICP
analysis of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Os,
Pb, Tl, V, and Zn. Dilute nitric acid is employed as the final dilution acid
for the furnace AA analysis of As, Be, Cd, Cr, Co, Fe, Pb, Mo, Se, Tl, and V.
The diluted samples have an approximate acid concentration of 5.0% (v/v). A
separate sample shall be dried for a total solids determination.
3.0 INTERFERENCES
3.1 Sludge samples can contain diverse matrix types, each of which may
present its own analytical challenge. Spiked samples and any relevant
standard reference material should be processed to aid in determining whether
Method 3050 is applicable to a given waste.
4.1 Conical Phillips beakers - 250-mL.
3050 - 1 Revision 1
December 1987
4.2 Watch glasses.
4.3 Drying ovens - That can be maintained at 30°C.
4.4 Thermometer - That covers range of 0-200°C.
4.5 Filter paper - Whatman No. 41 or equivalent.
4.6 Centrifuge and centrifuge tubes.
5.0 REAGENTS
determination.
determine level of impurities. If method blank is < MDL, the acid can be
used.
determine level of impurities. If method blank is < MDL, the acid can be
used.
5.4 Hydrogen peroxide (30%), H202. Oxidant should be analyzed to
determine level of impurities.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANpLING
6.3 Nonaqeuous samples shall be refrigerated upon receipt and analyzed as
soon as possible.
7.0 PROCEDURE
7.1 Mix the sample thoroughly to achieve homogeneity. For each digestion
procedure, weigh to the nearest 0.01 g and transfer to a c;onical beaker
1.00-2.00 g of sample.
3050 - 2 Revision 1
December 1987
7.2 Add 10 ml of 1:1 HN03, mix the slurry, and cover with a watch glass.
Heat the sample to 95°C and reflux for 10 to 15 minutes without boiling.
A11 ow the sample to cool , add 5 ml of con cent rated HN03, replace the watch
glass, and reflux for 30 minutes. Repeat this last step to ensure complete
oxidation. Using a ribbed watch glass, allow the solution to evaporate to
5 ml without boiling, while maintaining a covering of solution over the bottom
of the beaker.
7.3 After Step 7.2 has been completed and the sample has cooled, add 2 ml
of water and 3 ml of 30% H202. Cover the beaker with a watch glass and return
the covered beaker to the hot pl ate for warming and to start the peroxide
reaction. Care must be taken to ensure that losses do not occur due to
excessively vigorous effervescence. Heat until effervescence subsides and
cool the beaker.
7. 4 Continue to add 30% H202 in 1-ml aliquots with warming until the
effervescence is minimal or until the general sample appearance is unchanged.
NOTE: Do not add more than a total of 10 ml 30% H202.
7.5 If the sample is being prepared for (a) the ICP analysis of As and
Se, or (b) the flame AA or ICP analysis of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu,
Fe, K, Mg, Mn, Mo, Na, Ni, Os, Pb, Tl, V, and Zn, then add 5 ml of
concentrated HCl and 10 ml of water, return the covered beaker to the hot
plate, and reflux for an additional 15 minutes without boiling. After
cooling, dilute to 100 ml with water. Particulates in the digestate that may
clog the nebulizer should be removed by filtration, by centrifugation, or by
allowing the sample to settle.
r
7.5.1 Filtration - Filter through Whatman No. 41 filter paper (or

equivalent) and dilute to 100 ml with water.
7.5.2 Centrifugation - Centrifugation at 2,000-3,000 rpm for
10 minutes is usually sufficient to clear the supernatant.
7.5.3 The diluted sample has an approximate acid concentration of
5.0% (v/v) HCl and 5.0% (v/v) HN03. The sample is now ready for
analysis.
7.6 If the sample is being prepared for the furnace analysis of As, Be,
Cd, Co, Cr, Fe, Mo, Pb, Se, Tl, and V, cover the sample with a ribbed watch
glass and continue heating the acid-peroxide digestate until the volume has
been reduced to approximately 5 ml. After cooling, dilute to 100 ml with
water. Particulates in the digestate should then be removed by filtration, by
centrifugation, or by allowing the sample to settle.
7.6.1 Filtration - Filter through Whatman No. 41 filter paper (or
equivalent) and dilute to 100 ml with water.
7.6.2 Centrifugation - Centrifugation at 2,000-3,000 rpm for
10 minutes is usually sufficient to clear the supernatant.
3050 - 3 Revision 1
December 1987
7.6.3 The diluted digestate solution contains approximately 5%
{v/v) HN03. For analysis, withdraw aliquots of appropriate volume and
add any required reagent or matrix modifier. The sample is now ready for
analysis.
7.7 Calculations
7.7.1 The concentrations determined are to be reported on the basis
of the actual weight of the sample. If a dry weight analysis is desired,
then the percent solids of the sample must also be provided.
7.7.2 If percent solids is desired, a separate determination of
percent solids must be performed on a homogeneous aliquot of the sample.
8.0 QUALITY CONTROL
foll owed.
8.2 For each group of samples processed, preparation blanks {water and
reagent) should be carried throughout the entire samp 1e preparation and
being contaminated.
8.3 Replicate samples should be processed on a routine basis. Replicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% is recommended.
8.4 Spiked samples or standard reference materials must be employed to
8.5 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
10.0 REFERENCES
3050 - 4 Revision 1
December 1987
METMOO 30!50
ACID DIGESTION OF SEOIMENTS. SLUOGES. ANO SOILS
Start.
7. 1
Ml x
sample, take
l-2 g pa,.t1an
tor each
a111••t1on
7.2
APCI HNO.s
and retlux:
reflux w1tl\
concentrated
HNOs: repeat
7.2
E"aporete
solution to
' ... 1
7.l
ACid
Type II
water end HLOz;
... ,.., ror
pe,.oxtde react.
7.4
Add HaOz.
end war• untll
ef te,.vescence
l• 11lnl.,•l
3050 - 5 Revision 1
December 1987
METHOD 3050
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
{Continued)
ICP enelysls ot as end Se

or flame aa or IC?
Fur"nece enelys1s of ana1vs1s of a1. Ba. Be.
a•. Be. Co, C,.... Co. Ptl,
"40, Se. T 1. and V
Be. Ca. Cd. Cl"'. Cg. Cu.
_,,..__ _ _ _ ___,.._ Fe. Pt>. Mg, Mn. Mo I'll.
K.Na.Tl,V. eno Zn
7.6 7.5
aaa
Continue concentl"'eted
heat1n; to 1-tCL.. and Tyce I I
,... educ• vol u"'• watel"'; l"'e lu•
7 . t5 7.5 Cool:
d I lute
wlth Tyce II
Ollute with watel"'; flltCI"'
Tyo• II water" O•l"'t1culates In
the dl;estete
7.6 7.7.S Oetet"•ln•

pet"cant
•o11d• on
F 11 tel"' ho111ogeneous
O•l"'t1cul•tes s••Pl• •11ouot
Sn dS;estate tot" celcul•tlon
7.7.2
----oater"•lne
cone antt"• t lon•:
l"'eOOt"t pet"C•nt
•o11a• of
•••Ola
Stop
3050 - 6 Revision 1
December 1987
METHOD 3051
MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS.
SLUDGES. SOILS. AND OILS

1.1 This method is applicable to the microwave assisted acid digestion of
sludges, sediments, soils, and oils for the following elements:
Aluminum Cadmium Iron Molybdenum Sodium
Antimony Calcium Lead Nickel Strontium
Arsenic Chromium Magnesium Potassium Thallium
Boron Cobalt Manganese Selenium Vanadium
Barium Copper Mercury Silver Zinc
Beryllium
1. 2 This method is provided as an alternative to Method 3050. It is
intended to provide a rapid multielement acid leach digestion prior to analysis
so that decisions can be made about site cleanup levels, the need for TCLP
testing of a waste and whether a BOAT process is providing acceptable
performance. If a decomposition including hydrochloric acid is required for
certain elements, it is recommended that Method 3050A be used. Digests produced
by the method are suitable for analysis by flame atomic absorption (FLAA),
graphite furnace atomic absorption (GFAA), inductively coupled plasma emission
spectroscopy (ICP-ES) and inductively coupled plasma mass spectrometry (ICP-MS).

2.1 A representative sample of up to 0.5 g is digested in 10 ml of
concentrated nitric acid for 10 min using microwave heating with a suitable
laboratory microwave unit. The sample is placed in a Teflon PFA vessel with 10
ml of concentrated nitric acid. The vessel is capped and heated in the microwave
unit. After cooling, the vessel contents are diluted to volume and analyzed by
the appropriate SW-846 method (Ref. 1).
3.0 INTERFERENCES
3.1 Very reactive or volatile materials that may create high pressures
when heated may cause venting of the vessels with potential loss of sample and
ana lytes. The comp 1ete decomposition of either carbonates, or carbon based
samples, may cause enough pressure to vent the vessel if the sample size is
greater than 0.25 g when used in the 120 ml vessels with a pressure relief device
that has an upper limit of 7.5± 0.7 atm (110 ± 10 psi}.
3051 - 1 Revision 0
November 1992
4.1 Microwave apparatus requirements.
4.1.1 The microwave unit provides programmable power with a
minimum of 574 Wand can be programmed to within ± 10 Wof the required
power.
4.1.2 The microwave unit cavity is corrosion resistant as well as
ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires Teflon PFA digestion vessels (120 ml
capacity) capable of withstanding pressures up to 7.5 ± 0.7 atm (110 ± 10
psi) and capable of controlled pressure relief at pressures exceeding 7.5
± 0.7 atm (110 ± 10 psi).
4.1.5 A rotating turntable is employed to insure homogeneous

distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum ~f 3 rpm.
4 .1. 6 Those 1aboratori es now using or con temp lat i ng the use of
kitchen type microwave ovens for this method should be aware of several
significant safety issues. First, when an acid such as nitric is used to
assist sample digestion in microwave units in open vessels, or sealed
vessels equipped with venting features, there is the potential for the
acid gases released to corrode the safety devices that prevent the
microwave magnetron from shutting off when the door is opened. This can
result in operator exposure to microwave energy. Use of a unit with
corrosion resistant safety devices prevents this from occurring.
The second safety concern relates to the use of sealed containers without
pressure relief valves in the unit. Temperature is the important variable
controlling the reaction. Pressure is needed to attain elevated tempera-
tures but must be safely contained. However, many digestion vessels con-
structed from certain Teflons may crack, burst, or explode in the unit
under certain pressures. Only unlined PFA Teflon containers with pressure
relief mechanisms are considered acceptable at present.
Users are therefore advised not to use kitchen type microwave ovens or to
use sealed containers without pressure relief valves for microwave acid
digestions by this method. Use of laboratory-grade microwave equipment is
required to prevent safety hazards. For further details consult reference
2.
4.2 Polymeric volumetric ware in plastic (Teflon or polyethylene)
50 or 100 ml capacity.
3051 - 2 Revision 0
November 1992
4.3 Whatman No. 41 filter paper (or equivalent).
4.4 Disposable polypropylene filter funnel.
4.5 Analytical balance, 300 g capacity, and minimum ± 0.001 g.
5.0 REAGENTS
5.1 All acids should be sub-boiling distilled where possible to minimize
the blank levels due to meta 11 ic contamination. Other grades may be used,
provided it is first ascertained that the reagent is of sufficient purity to
permit its use without lessening the accuracy of the determination.
5.1.l Concentrated nitric acid, HN0 3 • Acid should be analyzed to
determine levels of impurity.
5. 2 Reagent Water. Reagent water sha 11 be interference free. A11
references to water in the method refer to reagent water unless otherwise
specified (Ref. 3).

6.2 All sample containers must be prewashed with detergents, acids and
water. Plastic and glass containers are both suitable. See Chapter Three, Step
3.1.3 of this manual, for further information.
6.3 Samples must be refrigerated upon receipt and analyzed as soon as
possible.
7. 0 PROCEDURE
7.1 Calibration of Microwave Equipment
7.1.l Measurement of the available power for heating is evaluated
so that absolute power in watts may be transferred from one microwave unit
to another. For cavity type microwave equipment, this is accomplished by
measuring the temperature rise in 1 kg of water exposed to microwave
radiation for a fixed period of time. The analyst can relate power in
watts to the partial power setting of the unit. The calibration format
required for laboratory microwave units depends on the type of electronic
system used by the manufacturer to provide partial microwave power. Few
units have an accurate and precise linear relationship between percent
power settings and absorbed power. Where linear circuits have been
3051 - 3 Revision 0
November 1992
utilized, the calibration curve can be determined by a three-point
calibration method (7.1.3), otherwise, the analyst must use the multiple
point calibration method (7.1.2).
7.1.2 The multiple point calibration involves the measurement of
absorbed power over a large range of power settings. Typically, for a 600
Wunit, the following power settings are measured; 100, 99, 98, 97, 95,
90, 80, 70, 60, 50, and 40% using the procedure described in section
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the unit's electronics are known to have nonlinear
deviations in any region of proportional power control, it will be
necessary to make a set of measurements that bracket the power to be used.
The final calibration point should be at the partial power setting that
will be used in the test. This setting should be checked periodically to
evaluate the integrity of the calibration. If a significant change is
detected (±10 W), then the entire calibration should be reevaluated.
7.1.3 The three-point calibration involves the measurement of
absorbed power at three different power settings. Measure the power at
1003 and 503 using athe procedure described in section 7.1.4. From the
2-point line calculate the power setting corresponding to the required
power in watts specified in the' procedure. Measure the absorbed power at
that partial power setting. If the measured absorbed power does not
correspond to the specified power within ±10 W, use the multiple point
calibration in 7.1.2. This point should also be used to periodically
verify the integrity of the calibration.
7.1.4 Equilibrate a large volume of water to room temperature
(23 ± 2°C). One kg of reagent water is weighed (1,000.0 g ± 0.1 g) into
a Teflon beaker or a beaker made of some other material that does not
significantly absorb microwave energy (glass absorbs microwave energy and
is not recommended). The initial temperature of the water should be 23 ±
2 •c measured to± 0.05 •c. The covered beaker is circulated continuously
(in the normal sample path) through the microwave field for 2 minutes at
the desired partial power setting with the unit's exhaust fan on maximum
(as it will be during normal operation). The beaker is removed and the
water vigorously stirred. Use a magnetic stirring bar inserted
immediately after microwave irradiation and record the maximum temperature
within the first 30 seconds to ± 0.05 •c. Use a new sample for each
additional measurement. If the water is reused both the water and the
beaker must have returned to 23 ± 2°C. Three measurements at each power
setting should be made.
3051 - 4 Revision 0
November 1992
The absorbed power is determined by the following relationship
P = (K) (Cp) (m) (l\T)
Eq. 1
t
P =the apparent power absorbed by the sample in watts (W).

(W=joul e·sec· 1 )
K = the conversion factor for thermochemi ca 1 ca 1ori es·sec· 1 to watts
(=4.184)
Cp = the heat capacity, thermal capacity, or specific heat
(cal·g· 1 ··c-1 ), of water. m = the mass of the water sample in grams (g).
l\T =the final temperature minus the initial tempera ture (°C), and
t =the time in seconds (s).
Using the experimental conditions of 2 minutes and 1 kg of distilled water

(heat capacity at 25 °C is 0.9997 cal·g· 1·°C- 1 ) the calibration equation
simplifies to:
Eq. 2 P = (l\T) (34.85)
NOTE: Stable line voltage is necessary for accurate and reproducible
calibration and operation. The line voltage should be within
manufacturer's specification, and during measurement and operation should
not vary by more than ±2 V. A constant power supply may be necessary for
microwave use if the source of the line voltage is unstable.
Electronic components in most microwave units are matched to
the units' function and output. When any part of the high v o 1 t a g e
circuit, power source, or control components in the unit have been
serviced or replaced, it will be necessary to recheck the units'
calibration. If the power output has changed significantly (±10 W), then
the entire calibration should be reevaluated.
7 .2 All digestion vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water. When switching between high concen-tration
samples and low concentration samples, all digestion vessels should be cleaned
by leaching with hot (1:1) hydrochloric acid for a minimum of two hours followed
with hot (1:1) nitric acid for a minimum of two hours and rinsed with reagent
water and dried in a clean environment. This cleaning procedure should also be
used whenever the prior use of the digestion vessels is unknown or cross
contamination from vessels is suspected. Polymeric volumetric ware and storage
3051 - 5 Revision 0
November 1992
containers should be cleaned by leaching with more dilute acids appropriate for
the specific plastics used and then rinsed with reagent water and dried in a
clean environment.
7.3 Sample Digestion
7.3.1 Weigh the Teflon PFA digestion vessel, valve and cap
assembly to 0.001 g prior to use.
7.3.2 Weigh a well-mixed sample to the nearest 0.001 g into the
Teflon PFA sample vessel equipped with a single-ported cap and a pressure
relief valve. For soils, sediments, and sludges use no more than 0.500 g.
For oils use no more than 0.250 g.
7.3.3 Add 10 ± 0.1 ml concentrated nitric acid in a fume hood.
If a vigorous reaction occurs, allow the reaction to stop before capping
the vessel. Cap the vessel and torque the cap to 12 ft- lb (16 N-m)
according to the unit manufacturer's directions. The sample vessel may be
connected to an overflow vessel using Teflon PFA connecting tubes. Weigh
the vessels to the nearest 0.001 g. Place the vessels in the microwave
carousel. Connect the overflow vessels to the center well of the unit.
CAUTION: When digesting sample~ containing volatile or easily oxidized
organic compounds, initially weigh no more than 0.10 g and observe the
reaction before capping the vessel. If a vigorous reaction occurs, allow
the reaction to cease before capping the vessel. If no appreciable
reaction occurs, a sample weight up to 0.25 g can be used.
7.3.4 Place the vessels evenly distributed in the turntable of
the microwave unit using groups of 2 sample vessels or 6 sample vessels.
Any vessels containing 10 ml of nitric acid for analytical blank purposes
are counted as sample vessels. When fewer than the recommended number of
samples are to be digested, i.e., 3 samples plus 1 blank, the remaining
vessels should be filled with 10 ml of nitric acid to achieve the full
complement of vessels. This provides an energy balance since the
microwave power absorbed is proportional to the total mass in the cavity
(Ref. 4). Irradiate each group of 2 sample vessels at 344 W for 10
minutes and each group of 6 sample vessels at 574 Wfor 10 minutes. The
temperature of each sample should rise to 175 ·c in less than 5.5 minutes
and remain between 170-180 ·c for the balance of the 10 minute irradiation
period. The pressure should peak at less than 6 atm for most soil,
sludge, and sediment samples (Ref. 5). The pressure will exceed these
limits in the case of high concentrations of carbonate or organic
compounds. In these cases the pressure will be 1imited by the relief
pressure of the vessel to 7.5 ± 0.7 atm (110 ± 10 psi).
7. 3. 4.1 Newer microwave uni ts may be capable of higher
power (W) that permits digestion of a larger number of samples per
batch. If the analyst wishes to digest other that two or six
samples at a time, the analyst may use different values of power as
3051 - 6 Revision 0
November 1992
long as they result in the same time and temperature conditions
defined in 7.3.4. That is, any sequence of power that brings the
samples to 175°C in 5.5 minutes and permits a slow rise to 175 -
180°C during the remaining 4.5 minutes (Ref. 5).
Issues of safety, structural integrity (both temperature and
pressure limitations}, heat loss, chemical compatibility, microwave
absorption of vessel material, and energy transport will be
considerations made in choosing alternative vessels. If all of the
considerations are met and the appropriate power settings provided
to reproduce the reaction conditions defined in 7.3.4, then these
alternative vessels may be used (Ref. 1,2}.
7.3.5 At the end of the microwave program, allow the vessels to
cool for a minimum of 5 minutes before removing them from the microwave
unit. When the vessels have cooled to room temperature, weigh and record
the weight of each vessel assembly. If the weight of acid plus sample
has decreased by more than 10 percent from the original we i g h t ,
discard the sample. Determine the reason for the weight loss. These are
typically attributed to loss of vessel seal integrity, use of a digestion
time longer than 10 minutes, too large a sample, or improper heating
conditions. Once the source of the loss has been corrected, prepare
a new sample or set of samples for digestion beginning at 7.3.1.
7.3.6 Complete the preparation of the sample by carefully uncapping
and venting each vessel in a fume hood. Transfer the sample to an acid-
cleaned polyethylene bottle. If the digested sample contains particulates
which may clog nebulizers or interfere with injection of the sample into
the instrument, the sample may be centrifuged, allowed to settle, or
filtered.
7.3.6.1 Centrifugation: Centrifugation at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.3.6.2 Settling: Allow the sample to stand until the
supernatant is cl ear. Allowing a sample to stand overnight wil 1
usually accomplish this. If it does not, centrifuge or filter the
sample.
7.3.6.3 Filtering: The filtering apparatus must be
thoroughly cleaned and prerinsed with dilute nitric acid. Filter
the sample through quantitative filter paper into a second
acid-cleaned container.
7.3.7 Dilute the digest to a known volume ensuring that the samples
and standards are matrix matched. The digest is now ready for analysis
for elements of interest using the appropriate SW-846 method.
3051 - 7 Revision 0
November 1992
7. 4 Ca lcul at ions: The concentrations determined are to be reported on the
basis of the actual weight of the original sample.
8.0 QUALITY CONTROL

8.1 All quality control data must be maintained and available for
reference or inspection for a period of three years. This method is restricted
to use by, or under supervision of, experienced analysts. Refer to the
appropriate section of Chapter One for additional quality control guidance.
8.2 Replicate samples should be processed on a routine basis. A replicate
sample is a sample brought through the whole sample preparation and analytical
process. A replicate sample should be processed with each analytical batch or
every 20 samples, whichever is the greater number. A replicate sample should be
prepared for each matrix type (i.e., soil, sludge, etc.).
8.3 Spiked samples or standard reference materials should be included with
each group of samples processed or every 20 samples, whichever is the greater
number. A spiked sample should also be included whenever a new sample matrix is
being analyzed.

9 .1 Pree is ion: The prec 1s1 on of Method 3051, as determined by the
statistical examination of interlaboratory test results is as follows:
9.2 Repeatability: If successive results are obtained by the same analyst
with the same apparatus under constant operating conditions on identical test
material, then the difference between these successive results will not, with 95%
probability, exceed the repeatability value. For example, in the case of lead,
an average of only 1 case in 20 would exceed
0.206 x
in the long run, where xis one result in µg/g (Ref. 6).
9.3 Reproducibility: If two successive measurements are made independently
by each of two different analysts working in different laboratories on identical
test material, then the difference between the average result for each analyst
will not, with 95% probability, exceed the reproducibility value. For example,
in the case of lead, an average of only 1 case in 20 would exceed
0.303 x
in the long run, where x is the average of two successive measurements in µg/g
(Ref. 2).
3051 - 8 Revision 0
November l 9•J2
As can be seen in Table 1, repeatability and reproducibility differ between
elements, and usually depend on that element's concentration. Table 2 provides
an example of how users of the method can determine expected values for
repeatability and reproducibility; nominal values of lead have been used for this
model {Ref. 6}.
9.4 Bias: In the case of SRM 1085 - Wear Metals in Oil, the bias of this
test method is different for each element. An estimate of bias, as shown in
Table 3, is:
Bias = Amount found - Amount expected.
However, the ·bias estimate inherits both the uncertainty in the
measurements made using Method 3051 and the uncertainty on the certificate, so
whether the bias is real or only due to measurement error must also be con-
sidered. The concentrations found for Al, Cr, and Cu using Method 3051 fall
within their certified ranges on SRM 1085, and 95% confidence intervals for Fe
and Ni overlap with their respective certified ranges; therefore, the observed
biases for these elements are probably due to chance and should be considered
insignificant. Biases should not be estimated at all for Ag and Pb because these
elements were not certified. Therefore, the only two elements considered in this
table for which the bias estimates are significant are Mg and Mo.
10.0 REFERENCES
1. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods. 3rd
ed; U.S. Environmental Protection Agency, Office of Sol id Waste and
Emergency Response. U.S. Government Printing Office: Washington, DC,
1986; SW-846.
2. Kingston, H. M. and L.B. Jassie, "Safety Guidelines for Microwave Systems
in the Analytical Laboratory". In Introduction to Microwave Acid
Decomposition: Theory and Practice; Kingston, H. M. and Jassie, L. B.,
eds.; ACS Professional Reference Book Series; American Chemical Society:
Washington, DC, 1988.
for Reagent Water ; ASTM, Philadelphia, PA, 1985, 01193-77.
4. Introduction to Microwave Sample Preparation: Theory and Practice,
Kingston, H. M. and Jassie, L. B., Eds.; ACS Professional Reference Book
Series; American Chemical Society: Washington, DC, 1988.
3051 - 9 Revision 0
November 1992
5. Kingston, H. M. EPA IAG #DWl-393254-01-0 January I-March 31, 1988,
quarterly Report.
6. Binstock, D. A., Yeager, W. M., Grohse, P. M. and Gaskill, A. Validation
of a Method for Determining Elements in Solid Waste bv Microwave Diges-
tion, Research Triangle Institute Technical Report Draft, RTI Project
Number 321U-3579-24, November, 1989, prepared for the Office of Sol id
Waste, U.S. Environmental Protection Agency, Washington, DC 20460.
3051 - 10 Revision 0
November 1992
TABLE 1.
EQUATIONS RELATING REPEATABILITY AND REPRODUCIBILITY TO MEAN
CONCENTRATION OF DUPLICATE DETERMINATION WITH 95 PERCENT CONFIDENCE
Element Repeatability Reproducibility
Ag 0 .195Xa 0.314X
Al 0.232X 0.444X
B 12. 9b 22 .6b
Ba 0.238X 0.421X
Be 0.082b 0.082b
Ca 0.356X 1. 27X
Cd 0.385X 0.571X
Co 0.291X 0.529X
Cr 0.187X 0. l 95X
Cu 0.212X 0.322X
Fe 0.257X 0.348X
Mg 0.238X 0.399X
Mn 1. 96Xl/2c 4.02Xl/2
Mo 0.701X 0.857X
Ni 0.212X 0.390X
Pb 0.206X 0.303X
Sr 0.283X 0.368X
v 1. 03Xl/2 2.23Xl/2
Zn 3.82Xl/2 7.69Xl/2
aLog transformed variable based on one-way analysis of variance.
bRepeatability and reproducibility were independent of concentratio .
csquare root transformed variable based on one-way analysis of variance.
TABLE 2.
REPEATABILITY AND REPRODUCIBILITY FOR LEAD
BY METHOD 3051
Average Value Repeatability Reproducibility
50 10.3 15.2
100 20.6 30.3
200 41. 2 60.6
300 61.8 90.9
400 82.4 121
500 103 152
all results are in mg/Kg
November 1992
TABLE 3.
RECOVERY AND BIAS DATA FOR SRM 1085 - WEAR METALS IN OIL
Amount Amount
Expected Found* Absolute Relative Significant
(Certified (95% Conf Bias Bias (due to more
Element Range) Interval) (µg/g) (Percent) than chance)
Ag (291)** 234±16
Al 296±4 295±12 -1 0 No
Cr 298±5 293±10 -5 -2 No
Cu 295±10 289±9 -6 -2 No
Fe 300±4 311±14 +11 +4 No
Mg 297±3 270±11 -27 -9 Yes
Mo 292±11 238±11 -54 -18 Yes
Ni 303±7 293±9 -10 -3 No
Pb (305)** 279±8
all values in mg/Kg
*Results taken from table 4-7, Ref. 2.
**Value not certified, so should not be used in bias detection and
estimation.
November 199
METHOD 3051
MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS
SLUDGES, SOILS, AND OILS
Start
7 1 Call.brat•
lha microwave
equipmant
7 2 Acid wa•h 7.3 l Weigh

and H,O rin•• al>.quot into
all diga•tion th• d>.geation
vessels and veaael
glassware
1 3.2 Add
concenlraled
HNO,, cap after
reactl.on
a lopped
1 3 3 Place 6
•ample v••••l•
l.n oven, heat
accord>.ng lo
power program
1 3.4 Allow
aampl•• lo Delarmina
cool to room r•a•on !or
lamperatur• lo••••
Yea
7 3 6 Place 7361-7363
1 3 5 WeJ.gh •ample in Centrifuge,
each veasel ac>.d·claaned •attle, and
a•••mbly polyelhyhne filter sample
bo l l l e
No
7 3 7 u.. tha
appropriate
SW-846 melhod
to analyze
1 4 Calculate
concentration•
ba•ed on
original aample
.. .,.ghl
Stop
November 1992
METHOD 3510
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION

1.1 This method describes a procedure for i sol at i ng organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described in Step 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water-soluble organics in preparation for a
variety of chromatographic procedures.
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separatory
funnel. The extract is dried, concentrated, and, as necessary, exchanged into
a solvent compatible with the cleanup or determinative step to be used.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.1 Separatory funnel - 2-liter, with Teflon stopcock.
4.2 Drying column - 20-mm i.d. Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without frits
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed
by 50 ml of elution solvent prior to packing the column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10-ml, graduated (Kontes K-570050-1025 or
equivalent). Ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500-ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4. 3. 3 Snyder column - Three-ball macro (Kontes K-503000-0121 or
equivalent).
3510 - 1 Revision 1
December 1987
4.3.4 Snyder column - Two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The bath should be used in a hood.
4.6 Vials - Glass, 2-ml capacity with Teflon lined screw-cap.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Erlenmeyer flask - 250-ml.
4.9 Syringe - 5-ml.
4.10 Graduated cylinder - I-liter.
5.0 REAGENTS
determination.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in water
and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray.
5.5 Sulfuric acid solution (1:1), H2S04. Slowly add 50 ml of H2S04 (sp.
gr. 1.84) to 50 ml of water.
5.6 Extraction/exchange solvent - Methylene chloride, hexane,
2-propanol, cyclohexane, acetonitrile (pesticide quality or equivalent).
6.1 See the introductory material to this chapter, Organic Analytes,
Step 4 .1.
7. 0 PROCEDURE
7.1 Using a 1-1i ter graduated cylinder, measure 1 1i ter ( nomi na 1) of
sample and transfer it to the separatory funnel. If high concentrations are
3510 - 2 Revision 1
December 1987
anticipated, a smaller volume may be used and then diluted with water to
1 liter. Add 1.0 ml of the surrogate standards to all samples, spikes, and
blanks (see Method 3500 for details on the surrogate standard solution and the
matrix spike solution). For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng/ul of each base/neutral
analyte and 200 ng/ul of each acid analyte in the extract to be analyzed
(assuming a 1 ul injection). If Method 3640, Gel-Permeation Cleanup, is to be
used, add twice the volume of surrogates and matrix spiking compounds since
half the extract is lost due to loading of the GPC column.
7. 2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.3 Add 60 ml of methylene chloride to the separatory funnel.
7.4 Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly; therefore,
initial venting should be done immediately after the separatory funnel
has been sealed and shaken once.
7. 5 All ow the organic layer to separate from the water phase for a
minimum of 10 minutes. If the emulsion interface between layers is more
than one-third the size of the solvent layer, the analyst must employ
mechanical techniques to complete the phase separation. The optimum
technique depends upon the sample and may include stirring, filtration of
the emulsion through glass wool, centrifugation, or other physical methods.
Collect the solvent extract in an Erlenmeyer flask. If the emulsion cannot
be broken (recovery of < 80% of the methylene chloride, corrected for the
water solubility of methylene chloride), transfer the sample, solvent, and
emulsion into the extraction chamber of a continuous extractor and proceed
as described in Method 3520.
7.6 Repeat the extraction two more times using fresh portions of
solvent (Steps 7.3 through 7.5). Combine the three solvent extracts.
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1. Serially
extract three times with 60 ml of methylene chloride, as outlined in Steps
7.3 through 7.5. Collect and combine the extracts and label the combined
extract appropriately.
7.8 If performing GC/MS analysis (Method 8250 or 8270), the acid and
base/neutral extracts may be combined prior to concentration. However, in
some situations, separate concentration and analysis of the acid and
base/neutral extracts may be preferable (e.g. if for regulatory purposes
the presence or absence of specific acid or base/neutral compounds at low
concentrations must be determined, separate extract analyses may be
warranted).
3510 - 3 Revision 1
December 1987
7.9 Assemble a Kuderna-Danish (K-D} concentrator by attaching a 10-ml
concentrator tube to a 500-ml evaporation flask.
7.10 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the Erlenmeyer fl ask, which contained the sol vent
extract, with 20-30 ml of methylene chloride and add it to the column to
complete the quantitative transfer.
7.11 Add one or two clean boiling chips to the flask and attach a three
ball Snyder column. Prewet the Synder column by adding about 1 ml of
methylene chloride to the top of the column. Place the K-D apparatus on a hot
water bath (80-90°C} so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 10-20 minutes. At
the proper rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid reaches
1 ml, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes.
7.12 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent, a new
boiling chip, and reattach the Snyder column. Concentrate the extract, as
described in Step 7.11, raising the temperature of the water bath, if
necessary, to maintain proper distillation.
7.13 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange
solvent. If sulfur crystals are a problem, proceed to Method 3660 for
cleanup. The extract may be further concentrated by using the technique
outlined in Step 7.14 or adjusted to 10.0 ml with the solvent last used.
7.14 If further concentration is indicated in Table 1, add another clean
boiling chip to the concentrator tube and attach a two ball mi era-Snyder
column. Prewet the column by adding 0.5 ml of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot water bath
so that the concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as required,
to comp 1ete the concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the chambers
will not flood. When the apparent volume of liquid reaches 0.5 ml, remove the
K-D apparatus from the water bath and allow it to drain and cool for at least
10 minutes. Remove the Synder column and rinse the flask and its lower joints
into the concentrator tube with 0. 2 ml of extraction sol vent. Adjust the
final volume to 1.0-2.0 ml, as indicated in Table 1, with solvent.
7.15 The extract obtained (from either Step 7.13 or 7.14) may now be
analyzed for analyte content using a variety of organic techniques. If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored
l anger than 2 days, it should be transferred to a vi al with a Te fl on 1i ned
screw-cap and labeled appropriately.
3510 - 4 Revision 1
December 1987
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
the Analysis of Pollutants Under the Clean Water Act; Final Rule and
Interim Final Rule and Proposed Rule," October 26, 1984.
3510 - 5 Revision 1
December 1987
TABLE 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Exchange Exchange Volume final

solvent solvent of extract extract
Initial Secondary required required required volume
Determinative extraction extraction for for for for
method pH pH analysis cleanup cleanup (ml) analysis (ml)
w 8040 <2 none 2-propanol hexane 1.0 I. 0, 10. oa

c.n 8060
...... as received none hexane hexane 2.0· 10.0
0
8080 5-9 none hexane hexane 10.0 10.0
O'I
8100 as received none none cyclohexane 2.0 1.0
8120 as received none hexane hexane 2.0 1.0
8250b > 11 <2 none - - 1.0
8270b > 11 <2 none - - 1.0
8310 as received none acetonitril e - - 1.0
aphenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optional derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD.
o:xi bThe specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance
~ ~
(1) ~.
on the cleanup procedures available if required.
3 VI
O" ~.
(1) 0
~ :J
............
\0
co
"
M!TMOO 3510
S~PAA&TOAY ~UNNEL LIOUIO-LIOUIO !XTR&CTION
St•rt
7. l AOCI 7.8
1---~•"rroo•t• co ... 01ric
•t•nO•rCI• to D••c/ricutr•l
• 11 aa1110 l••. eat.ract.s
•Dlke•. •nCI or 1or to
Dl•l'lk• c;onceritret tori
7.2 7.9
C:f\ec1c 1nC1 &a•c•DlC K-0

aa,u•t oM COl'ICentrator
7.3-7.• 7. lO
Ory ana c:oll•c:t

••tr•ct
7. ts
C:onc•,,tr•tc
eatrac:t u•ll'IO
K-0 •PO•r•tus
1.1 7. , .
C:o ll•ct U•c K-0
al'ICI co-ln• aoper•tY•:
••tract• ena ACljuat tll'lel
leoe1 WOlYlllC
3510 - 7 Revision 1
December 1987
METHOD 3520
CONTINUOUS LIQUID-LIQUID EXTRACTION

1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method al so describes concentration techniques
suitable for preparing the extract for the appropriate determinative steps
described in Step 4.3 of Chapter Four.
water-insoluble and slightly soluble organics in preparation for a variety of
chromatographic procedures.
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate
the effectiveness of any such automatic extraction device before employing it
in sample extraction.
2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH
(see Table 1), and extracted with organic solvent for 18-24 hours. The
extract is dried, concentrated, and, as necessary, exchanged into a solvent
compatible with the determinative step being employed.
3.0 INTERFERENCES
4.1 Continuous liquid-liquid extractor - Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Hershberg-Wolf
Extractor -- Ace Glass Company, Vineland, New Jersey, P/N 6841-10, or
equivalent).
4.2 Drying column - 20 mm i.d. Pyrex chromatographic column with Pyrex
may be purchased. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone followed
3520 - 1 Revision 1
December 1987
extracts.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.6 Vials - 2-ml, glass with Teflon lined screw-cap.
4.8 Heating mantle - Rheostat controlled.
4.9 Syringe - 5-ml.
5.0 REAGENTS
determination.
5.2 ASTM Type II Water (ASTM Dll93-77 (1983)). All references to water
5.3 Sodium hydroxide solution (lON), NaOH. Dissolve 40 g NaOH in water
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray.
5.5 Sulfuric acid solution (1:1), H2S04. Slowly add 50 ml of H2S04 (sp.
gr. 1.84) to 50 ml of water.
5.6 Extraction/exchange solvent - Methylene chloride, hexane,
2-propanol, cyclohexane, acetonitrile (pesticide quality or equivalent).
3520 - 2 Revision 1
December 1987
6 .1 See the introductory material to this chapter, Organic Anal ytes,
Step 4 .1.
7.0 PROCEDURE
7.1 Using a graduated cylinder, measure out 1 liter (nominal) of sample
and transfer it to the continuous extractor. If high concentrations are
anticipated, a smaller volume may be used and then diluted with water to
1 liter. Check the pH of the sample with wide-range pH paper and adjust the
pH, if necessary, to the pH indicated in Table 1. Pipet 1.0 ml of the
surrogate standard spiking solution into each sample into the extractor and
mix well. (See Method 3500 for details on the surrogate standard solution and
the matrix spike solution.) For the sample in each analytical batch selected
for spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount of the surrogates and matrix spiking compounds added to
the sample should result in a final concentration of 100 ng/ul of each
base/neutral analyte and 200 ng/ul of each acid analyte in the extract to be
analyzed (assuming a 1 ul injection). If Method 3640, Gel-Permeation Cleanup,
is to be used, add twice the volume of surrogates and matrix spiking compounds
since half the extract is lost due to loading of the GPC column.
7.2 Add 300-500 ml of methylene chloride to the distilling flask. Add
several boiling chips to the flask.
7.3 Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and
concentrated as described in Steps 7.7 through 7.11.
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to< 2
with sulfuric acid (1:1). Attach a clean distilling flask containing 500 ml
of methylene chloride to the continuous extractor. Extract for 18-24 hours,
allow to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8250 or 8270), the acid and
base/neutral extracts may be combined prior to concentration. However, in
some situations, separate concentration and analysis of the acid and
base/neutral extracts may be preferable (e.g. if for regulatory purposes the
presence or absence of specific acid or base/neutral compounds at low
concentrations must be determined, separate extract analyses may be
warranted).
7. 7 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL
7 .8 Dry the extract by passing it through a drying column containing
concentrator. Rinse the flask which contained the solvent extract with
3520 - 3 Revision 1
December 1987
20-30 ml of methylene chloride and add it to the column to complete the
quantitative transfer.
ba 11 Snyder column. Prewet the Snyder column by adding about 1 ml of
water bath (80-90°C) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete the concentration in 10-20 minutes. At
but the chambers will not flood. When the apparent volume of liquid reaches 1
ml, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joints into the concentrator tube with 1-2 ml of extraction
solvent.
momentarily remove the Snyder column, add 50 ml of the exchange solvent, a new
boiling chip, and reattach the Snyder column. Concentrate the extract, as
described in Step 7. 9, raising the temperature of the water bath, if
7.12 Add another one or two clean boiling chips to the concentrator tube
and attach a two ball micro-Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column. Place the
K-D apparatus in a hot water bath so that the concentrator tube is partially
immersed in the hot water. Adjust the vertical position of the apparatus and
the water temperature, as required, to complete the concentration in
5-10 minutes. At the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water bath and
allow it to drain and cool for at least 10 minutes. Remove the Synder column,
rinse the flask and its lower joints into the concentrator tube with 0.2 ml of
methylene chloride or exchange solvent, and adjust the final volume to 1.0 to
2.0 ml, as indicated in Table 1, with solvent.
7.13 The extracts obtained may now be analyzed for analyte content using
a variety of organic techniques {see Step 4.3 of this chapter). If analysis
of the extract will not be performed immediately, stopper the concentrator
tube and store refrigerated. If the extract will be stored longer than 2
days, it should be transferred to a vial with a Teflon lined screw-cap and
labeled appropriately.
3520 - 4 Revision 1
December 1987
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spike, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
Method 3500 for extraction and sample-preparation procedures.
10.0 REFERENCES
2. Rohrbough, W. G. ; et a1 . Reagent Chemi ca 1s, American Chemi ca 1 Soc i etv
3520 - 5 Revision 1
December 1987
TABLE 1.
Exchange Exchange Volume Final
method pH pH analysis cleanup cleanup (mL) analysis (mL)
8040 < 2 none 2-propanol hexane 1. 0 1. 0. 10.Qa

8090 5-9 none hexane hexane 2.0 1. 0
8100 as received none none cyclohexane 2.0 1. 0
825ob > 11 < 2 none 1. 0
8270b > 11 < 2 none 1. 0
8310 as received none acetonitrile 1. 0
aPhenols may be analyzed, by Method 8040, using a 1. 0 mL 2-propanol extract by GC/FID. Method 8040 also
contains an optional derivatization procedure for phenols which results in a 10 mL hexane extract to be
analyzed by GC/ECD.
brhe specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on
the cleanup procedures available if required.
3520 - 6 Revision 1
December 1987
METHOD 3520
7. 1 7.7 7.13
Adel
•PPr"OPr"l•te
•ur"r"OG•te •nel Aaae,.ble K-0 An•lyze u•lng
lll•tr"lX •Olklng concentr"•to,. orgenlc
•olutlon• tecnnlque•
7.2 7.1
Adel Ory
••tnylene extr•ct:
cnlor"1CI• to collect e1r1ee1
CIUtlll1ng ••tr"ect sn K-0
fl••k concentr"etor"
7.3 •.9
Adel
r"e•gent w•ter" Concentr"ete
to extr"•ctor; ua1ng Snyder"
extr"•ct for colu111n •nd K-D
Sl-24 l"lr"& •ODer"etus
7.5 ACIJu•t 7 .10

pH of Add
•Queou• Pli•ae: ••chen1•
•Xtr"•Ct for" •olvent:
11-2• ,,,.. wltl'\ concentrete
cl••n f le•k extrect
7.8 Comln• 7.12 l'"urtl"ler

~~~~.r~-:::: eclel encs concen-
] l>•••/neutr"el tre te extrect
extrect• lf neceaeery;
Pr"lOr" to eCIJU•t fln•l
concentretlon volu••
3520 - 7 Revision 1
December 1987
METHOD 3540
SOXHLET EXTRACTION

1.1 Method 3540 is a procedure for extracting nonvolatile and semi -
volatile organic compounds from solids such as soils, sludges, and wastes.
The Soxhlet extraction process ensures intimate contact of the sample matrix
with the extraction solvent.
water-insoluble and slightly water-soluble organics in preparation for a
variety of chromatographic procedures.
2.1 The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using
an appropriate solvent in a Soxhlet extractor. The extract is then dried,
concentrated, and, as necessary, exchanged into a solvent compatible with the
cleanup or determinative step being employed.
3.0 INTERFERENCES
4.1 Soxhlet extractor - 40-mm i.d., with 500-ml round-bottom flask.
4.2 Drying column - 20-mm i.d. Pyrex chromatographic column with Pyrex
may be purchased. Use a sma 11 pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 ml of acetone fo 11 owed
extracts.
4.3.3 Snyder column - Three ba 11 macro (Kontes K-503000-0121 or
equivalent).
3540 - 1 Revision 1
December 1987
equivalent).
4.6 Vials - Glass, 2-ml capacity, with Teflon lined screw-cap.
4.7 Glass or paper thimble or glass wool - Contaminant free.
4.9 Syringe - 5-ml.
4.10 Apparatus for determining percent moisture
4.10.1 Oven - Drying.
4.10.2 Desiccator.
4.10.3 Crucibles - Porcelain.
4.11 Apparatus for grinding - If the sample will not pass through a 1-mm
standard sieve or cannot be extruded through a 1-mm opening, it should be
processed into a homogeneous sample that meets these requirements. Fi sher
Mortar Model 155 Grinder, Fisher Scientific Co., Catalogue Number 8-323, or an
equivalent brand and model, is recommended for sample processing. This
grinder should handle most solid samples, except gummy, fibrous, or oily
materials.
5.0 REAGENTS
i nd i cat e d , i t i s i ntended that a 11 reagents sh a 11 conform to the
spec i fi cations of the Committee on Analytical Reagents of the American
determination.
5.2 ASTM Type II Water (ASTM D1193-77 (1983)). All references to water in
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by washing with
methylene chloride followed by heating at 400°C for 4 hours in a shallow tray.
3540 - 2 Revision 1
December 1987
5.4 Extraction solvents
5.4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems:
5.4.1.1 Toluene/Methanol ((10:1) (v/v)), C5H5CH3/CH30H.
Pesticide quality or equivalent.
5. 4. 1. 2 Acetone/Hexane ( ( 1: 1) ( v/v)), CH3COCH3/CH3 (CH2) 4CH3.
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH2Cl2. Pesticide quality or
equivalent.
5.5 Exchange solvents - Hexane, 2-propanol, cyclohexane, acetonitrile
(pesticide quality or equivalent).
6.1 See the introductory material to this chapter, Organic Analytes, Step
4.1.
7. 0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - Decant and discard any water layer on
a sediment sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7 .1.2 Waste samples - Samples consisting of multi phases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1-mm sieve or can
be extruded through a 1-mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.2 Determination of percent moisture - In certain cases, sample results
are desired based on a dry-weight basis. When such data is desired, a portion
of sample for moisture determination should be weighed out at the same time as
the portion used for analytical determination.
7.2.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a ta red crucible. Determine the percent
moisture by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
3 moisture = g of sample - g of dry sample x 100

g of sample
3540 - 3 Revision 1
December 1987
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely
for the duration of the extraction period. A glass wool plug above and below
the sample in the Soxhlet extractor is an acceptable alternative for the
thimble. Add 1.0 ml of the surrogate standard spiking solution onto the
sample (see Method 3500 for details on the surrogate standard and matrix
spiking solutions.) For the sample in each analytical batch selected for
should result in a final concentration of 100 ng/ul of each base/neutral
analyte and 200 ng/ul of each acid analyte in the extract to be analyzed
(assuming a 1 ul injection). If Method 3640, Gel-permeation cleanup, is to be
used, add twice the volume of surrogates and matrix spiking compounds since
half the extract is lost due to loading of the GPC column.
7.4 Place 300 ml of the extraction solvent (Step 5.3) into a 500-ml
round-bottom flask containing one or two clean boiling chips. Attach the
flask to the extractor and extract the sample for 16-24 hours at 4-6
cycles/hr.
7.5 Allow the extract to cool after the extraction is complete.
7 .6 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-ml
concentrator. Wash the extractor flask and sodium sulfate column with 100 to
125 ml of extraction solvent to complete the quantitative transfer.
7. 8 Add one or two clean boiling chips to the fl ask and attach a three
ball Snyder column. Prewet the Snyder column by adding about 1 ml of
water bath (15-20°C above the boiling point of the solvent) so that the
concentrator tube is partially immersed in the hot water and the entire lower
rounded surface of the fl ask is bathed with hot vapor. Adjust the vertical
position of the apparatus and the water temperature, as required, to complete
the concentration in 10-20 minutes. At the proper rate of distillation the
balls of the column will actively chatter, but the chambers will not flood.
When the apparent volume of liquid reaches 1 ml, remove the K-D apparatus from
the water bath and allow it to drain and cool for at least 10 minutes.
momentarily remove the Snyder column, add 50 ml. of the exchange solvent and a
new boiling chip, and reattach the Snyder column. Concentrate the extract as
described in Step 7.6, raising the temperature of the water bath, if
3540 - 4 Revision 1
December 1987
7.11 If further concentration is indicated in Table 1, add another one or
two clean boiling chips to the concentrator tube and attach a two ball micro-
Snyder column. Prewet the column by adding 0.5 ml of methylene chloride or
exchange solvent to the top of the column. Place the K-D apparatus in a hot
water bath so that the concentrator tube is partially immersed in the hot
water. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete the concentration in 5-10 minutes. At
but the chambers will not flood. When the apparent volume of liquid reaches
0.5 ml, remove the K-D apparatus from the water bath and allow it to drain and
cool for at least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joints into the concentrator tube with 0.2 ml of solvent.
Adjust the final volume to 1.0-2.0 ml, as indicated in Table 1, with solvent.
7.12 The extracts obtained may now be analyzed for analyte content using
a variety of organic techniques (see Step 4.3 of this Chapter). If analysis
of the extract wi 11 not be performed immediately, stopper the concentrator
tube and store refrigerated. If the extract will be stored 1onger than 2
days, it should be transferred to a vial with Teflon lined screw-cap and
labeled appropriately.
8.0 QUALITY CONTROL
8 .1 Any reagent bl an ks or matrix spike samples should be subjected to
10.0 REFERENCES
2. Rohrbaugh, W. G. ; et al . Reagent Chemi ca 1s, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC,
1986.
for Reagent Water"; ASTM: Philadelphia, PA, 1985; 01193-77.
3540 - 5 Revision 1
December 1987
TABLE 1.

required required required volume
Determinative Extraction for for for for
method pH analysis cleanup cleanup (ml) analysis (ml)
w so4oa as received 2-propanol hexane 1.0 i.o, Io.ob

U'I
~
8060 as received hexane hexane 2.0 10.0
0 8080 as received hexane hexane 10.0 10.0
0\ 8100 as received none cyclohexane 2.0 1.0
s2soa,c as received none - - 1.0
821oa,c as received none - - 1.0
8310 as received acetonitrile - - 1.0
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
concentration of the extract to 10.0 ml.
c:::ic b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method
(I)
O<
(I)
8040 also contains an optional derivatization procedure for phenols which results in a 10 ml
(I) .....
3 V> hexane extract to be analyzed by GC/ECD.
0- .....
(I)0
-- c The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for
~ :::s
guidance on the cleanup procedures available if required.
'°
00
.......
METHOD 35'0
SOXHLET fXTAACTION
Ster-t
7.1 7.6 •. l!I
use ">------11.t"--;;:A;:e::c";o nc • n t,. at. e

•oor-opr-1•te Asse,,.ble K-0 ustng Snyaer
••"'Pl• l'lenaltng concentr-•tor colu"'n enc K-0
tecl'ln1Que •ppar-atus
7.2 7.7 •.7
Oeter-1111ne 0,.y end collect AC)USt Sa,,.ple

oer-c•nt ••trect tn K-0 volume
11101 s tur-e concentr-ator-
7.3 4.6 5. 1
Aad
eppr-ope1ate Concent,.•te
surrog•tl! and ustng Snyder- An a 1 y z • us 1 n g
aetr-1• SP1ktng colu•n ana K-0 O'"Q•M1c
st ender-as •ooer-etus techn1Ques
1.4 Plece
----111ethy lene
chlor-1oe:
ecetone tn
t l•sk; ••tr-act
tor- 16-2• nr-s
7.5
Cool ••tr-ect
3540 - 7 Revhion 1
December 1987
METHOD 3600
CLEANUP

1.1 General
1.1.l Injection of extracts into a gas or liquid chromatograph can
cause extraneous peaks, deterioration of peak re solution and column
efficiency, and loss of detector sensitivity and can greatly shorten the
lifetime of expensive columns. The following techniques have been
applied to extract purification: partitioning between immiscible
sol vents; adsorption chromatography; gel permeation chromatography;
chemical destruction of interfering substances with acid, alkali, or
oxidizing agents; and distillation. These techniques may be used
individually or in various combinations, depending on the extent and
nature of the co-extractives.
1.1.2 It is an unusual situation (e.g. with some water samples)
when extracts can be directly determined without further treatment. Soil
and waste extracts often require a combination of cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC), to eliminate the
high boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
1. 2 Specific
1.2.1 Adsorption column chromatography - Alumina (Methods 3610 and
3611), Florisil (Method 3620), and silica gel (Method 3630) are useful
for separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity.
1.2.2 Acid-base partitioning - Useful for separating acidic or
basic organics from neutral organics. It has been applied to analytes
such as the chlorophenoxy herbicides and phenols.
1.2.3 Gel permeation chromatography (GPC) - The most universal
cleanup technique for a broad range of semivolatile organics and
pesticides. It is capable of separating high molecular-weight material
from the sample analytes. It has been used successfully for all the
semivolatile base, neutral, and acid compounds associated with the EPA
Priority Pollutant and the Super fund Hazardous Substance Lists. GPC is
usually not applicable for eliminating extraneous peaks on a chromatogram
which interfere with the analytes of interest.
1.2.4 Sulfur cleanup - Useful in eliminating sulfur from sample
extracts, which may cause chromatographic interference with analytes of
interest.
3600 - 1 Revision 1
December 1987
1.2.5 Table 1 indicates the recommended cleanup techniques for the
indicated groups of compounds. This information can a1so be used as
guidance for compounds that are not listed. Compounds that are
chemically similar to these groups of compounds should follow a similar
elution pattern.
2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES
3.1 Analytical interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free of interferences, under
the conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be
necessary for reagent purification.
4. 1 Refer to the specific cleanup method for apparatus and materials
needed.
5. 0 REAGENTS
5.1 Refer to the specific cleanup method for the reagents needed.
Step 4. I.
7.0 PROCEDURE
7.1 Prior to using the cleanup procedures, samples should undergo
solvent extraction. Chapter Two, Step 2.3.3, may be used as a guide for
choosing the appropriate extraction procedure based on the physical
composition of the waste and on the analytes of interest in the matrix (see
also Method 3500 for a general description of the extraction technique). For
some organic liquids, extraction prior to cleanup may not be necessary.
7.2 In most cases, the extracted sample is then analyzed by one of the
determinative methods available in Step 4.3 of this chapter. If the analytes
of interest are not able to be determined due to interferences, cleanup is
performed.
7 .3 Many of the determinative methods specify cleanup methods that
should be used when determining particular analytes (e.g. Method 8060, gas
chromatography of phtha late esters, recommends using either Method 3610
3600 - 2 Revision 1
December 1987
(Alumina column cleanup) or Method 3620 (Florisil column cleanup) if
interferences prevent analysis) . However, the experience of the analyst may
prove invaluable in determining which cleanup methods are needed. As
indicated in Section 1.0 of this method, many matrices may require a
com bi nation of cleanup procedures in order to ensure proper ana lyt i cal
determinations.
7.4 Guidance for cleanup is specified in each of the methods that
f o11 ow. The amount of extract cleanup required prior to the final
determination depends on the selectivity of both the extraction procedure and
the determinative method and the required detection limit.
7.5 Following cleanup, the sample is concentrated to whatever volume is
required in the determinative method. Analysis follows as specified in the
determinative procedure (Step 4.3 of this Chapter).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered by the cleanup technique before the cleanup is
applied to actual samples.
8.2 For sample extracts that are cleaned up, the associated quality
control samples (e.g. spikes, blanks, replicates, and duplicates) must also be
processed through the same cleanup procedure.
8.3 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup al so be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
interest and to verify the absence of interferences from reagents.
9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES
10.1 Refer to the specific cleanup method.
3600 - 3 Revision 1
December 1987
TABLE 1.
RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Determinativea Cleanup
Analyte Group Method Method Option
Phenols 8040 3630b, 3640, 3650, 8040C

Phthalate esters 8060 3610, 3620, 3640
Nitrosami nes 8070 3610, 3620, 3640
Organochlorine pesticides & PCBs 8080 3620, 3640, 3660
Nitroaromatics and cyclic ketones 8090 3620, 3640
Polynuclear aromatic hydrocarbons 8100 3611, 3630' 3640
Chlorinated hydrocarbons 8120 3620, 3640
Organophosphorous pesticides 8140 3620
Chlorinated herbicides 8150 815od
Priority pollutant semivolatiles 8250, 8270 3640, 3650, 3660
Petroleum waste 8250, 8270 3611, 3650
a The GC/MS Methods, 8250 and 8270, are al so appropriate determinative

methods for all analyte groups, unless lower detection limits are
required.
b Cleanup applicable to derivatized phenols.
c Method 8040 includes a derivatization technique followed by GC/ECD
analysis, if interferences are encountered using GC/FID.
d Method 8150 incorporates an acid-base cleanup step as an integral part of
the method.
3600 - 4 Revision 1
December 1987
METHOO 3600
CLEANUP
7. 1
Co solvent
••tr•ct1on
7.2
Analy~•
an•lyte by
a C1eter111Snatlve
.. e tho Cl rr-0111
Sec .... J
7 .3 Use
cleenuo
11ethOCI
sciec1r1ea for
th• Cleter1111n-
at 1ve 11ethoo
7.S
Stoo
Concentrete
ae111cil• to
reQulrea •oll,, .. •
3600 - 5 Revision I
December 1987
METHOD 3650
ACID-BASE PARTITION CLEANUP

1.1 Method 3650 was formerly Method 3530 in the second edition of this
manual.
1.2 This is a liquid-liquid partitioning cleanup method to separate acid
analytes, e.g. organic acids and phenols, from base/neutral analytes, e.g.
amines, aromatic hydrocarbons, and halogenated organic compounds, using pH
adjustment. It may be used for cleanup of petroleum waste prior to alumina
cleanup. Specific examples of compounds that are separated by this method are
in Table I.
2.1 The solvent extract from a prior solvent extraction method is shaken
with water that is strongly basic. The acid analytes partition into the
aqueous layer, whereas, the basic and neutral compounds stay in the organic
solvent. The base/neutral fraction is concentrated and is then ready for
further cleanup, if necessary, or analysis. The aqueous layer is acidified and
extracted with an organic solvent. This extract is concentrated and is then
ready for analysis of the acid analytes.
3.0 INTERFERENCES
3.1 More extensive procedures than those outlined in this method may be
3.2 A method blank must be run for the compounds of interest prior to use
of the method. The interferences must be below the method detection limit
before this method is applied to actual samples.
4.1 Drying column - 20 mm i.d. Pyrex chromatographic column with Pyrex
NOTE: Fritted glass discs are difficult to clean after highly
contaminated extracts have been passed through them. Columns
without frits are recommended. Use a small pad of Pyrex glass wool
to retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 ml of elution solvent (Table 1) prior to
packing the column with adsorbent.
4.2 Kuderna-Danish (K-D) apparatus (Kontes K-570025-0500)
4. 2. I Concentrator tube - 10-ml graduated (Kontes K570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of the
extracts.
3650 - I Revision I
December 1987
4.2.2 Evaporation flask - 500-ml (K-570001-0500 or equivalent).
Attach to concentrator tube with springs.
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K569001-0219 or
equivalent).
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Vials - Glass, 2-ml capacity with Teflon lined screw-cap.
4.4 Water bath - Heated, concentric ring cover, temperature control of
± 2°C. Use this bath in a hood.

5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise indicated, it is intended that all inorganic reagents shall conform
to the specifications of the Committee on Analytical Reagents of the American
determination.
5.3 Methylene chloride, CH2Cl2. Pesticide quality or equivalent.
5.4 Sodium hydroxide (ION), NaOH. Dissolve 40 g of sodium hydroxide in
100 ml of water.
5.5 Sulfuric acid (1:1 v/v in water), H2S04. Slowly add 50 ml H2S04 to
50 ml of water.
5.6 Sodium sulfate, Na2S04. Granular, anhydrous, purify by rinsing with
acetone followed by the elution solvent and then drying at 200°C for 4 hours.
5.7 Acetone, CH3COCH3. Pesticide quality or equivalent.
5.8 Methanol, CH30H. Pesticide quality or equivalent.
5.9 Ethyl ether, C2H50C2H5. Pesticide quality or equivalent.
3650 - 2 Revision 1
December 1987
Step 4 .1.
7.0 PROCEDURE
7.1 Place 10 ml of the solvent extract from a prior extraction procedure
into a 125-ml separatory funnel.
7.3 Slowly add 20 ml of prechilled water which has been previously
adjusted to a pH of 12-13 with ION sodium hydroxide.
7 .4 Seal and shake the separatory funnel for at least 2 minutes with
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once.
7. 5 A11 ow the organic layer to separate from the aqueous phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends
upon the sample, and may include stirring, filtration of the emulsion through
glass wool, centrifugation, or other physical methods.
7. 6 Separate the aqueous phase and transfer it to a 125-ml Erlenmeyer
flask. Repeat the extraction two more times using fresh 20 ml aliquots of
dilute sodium hydroxide (pH 12-13). Combine the aqueous extracts.
7.7 Water soluble organic acids and phenols will be primarily in the
aqueous phase. Base/neutral analytes will be in the methylene chloride. If the
analytes are only in the aqueous phase, discard the methylene chloride and
proceed to Step 7.8. If the analytes are only in the methylene chloride,
discard the aqueous phase and proceed to Step 7.10.
7.8 Externally cool the 125-ml Erlenmeyer flask with ice while adjusting
the aqueous phase to a pH of 1-2 with sulfuric acid (1:1). Transfer the cool
aqueous phase to a clean 125-ml separatory funnel. Add 20 ml of methylene
chloride to the separatory funnel and shake for at least 2 minutes. Allow the
methylene chloride to separate from the aqueous phase and collect the
methylene chloride in an Erlenmeyer flask.
7.9 Add 20-ml of methylene chloride to the separatory funnel and extract
at pH 1-2 a second ti me. Perform a third extraction in the same manner
combining the extracts in the Erlenmeyer flask.
7 .10 Assemble a Kuderna-Dani sh (K-D) concentrator by attaching a 10-ml
3650 - 3 Revision 1
December 1987
7.11 Dry both acid and base/neutral fractions by passing them through a
drying column containing about 10 cm of anhydrous sodium sulfate. Collect the
dried fractions in K-D concentrators. Rinse the Erlenmeyer fl asks which
contained the sol vents and the columns with 20 ml of methylene chloride to
7.12 Concentrate both acid and base/neutral fractions as follows: Add
one or two boiling chips to the flask and attach a three ball macro-Snyder
column. Prewet the Snyder column by adding about 1 ml of methylene chloride to
the top of the column. Place the K-D apparatus on a hot water bath {80-90°C)
so that the concentrator tube is partially immersed in the warm water. Adjust
the vertical position of the apparatus and the water temperature as required
to complete the concentration in 15-20 minutes. At the proper rate of
distillation, the balls of the column will actively chatter but the chambers
wi 11 not flood. When the volume of liquid reaches 1 ml, remove the K-D
apparatus from the water bath and allow it to cool. Remove the Snyder column
and rinse the fl ask and its lower joints into the concentrator tube with
1-2 ml of methylene chloride.
7 .13 Add another one or two boiling chips to the concentrator tube and
attach a two ball micro-Snyder column. Prewet the column by adding 0.5 ml of
methylene chloride to the top of the column. Place the K-D apparatus in a hot
water bath {80-90°C) so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 5-10 minutes. At the
proper rate of distillation the balls of the column will actively chatter but
the chambers will not flood. When the volume of the liquid reaches 0. 5 ml,
remove the K-D apparatus and allow it to cool. Remove the Snyder column and
rinse the flask and its lower joints into the concentrator tube with 0.2 ml of
methylene chloride. Adjust the final volume to 1 ml with methylene chloride.
7.14 The acid fraction is now ready for analysis. If the base/neutral
fraction requires further cleanup by the alumina column cleanup for petroleum
waste (Method 3611), the solvent may have to be changed to hexane. To the 1 ml
base/neutral fraction, 5 ml of hexane should be added, and this mixture
concentrated to 1 ml using the micro K-D apparatus {repeat 2 more times). If
no further cleanup of the base/neutral extract is required, it is also ready
for analysis.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for general quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before applying this method to actual samples.
8.3 For samples that are cleaned using this method, the associated
quality control samples must be processed through this cleanup method.
3650 - 4 Revision 1
December 1987
10.0 REFERENCES
1. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, 3rd
ed.; U.S. Environmental Protection Agency. Office of Solid Waste and
Emergency Response. U.S. Government Printing Office: Washington, DC, 1987;
SW-846; 955-001-00000-1.
2. Test Methods: Methods for Organic Chemical Analysis of Municipal and
Industrial Wastewater; U.S. Environmental Protection Agency. Office of
Research and Development. Environmental Monitoring and Support Laboratory.
ORD Publication Offices of Center for Environmental Research Information:
Cincinnati, OH, 1982; EPA-600/4-82-057.
for Reagent Water"; ATSM: Philadelphia, PA, 1985; Dll93-77.
3650 - 5 Revision 1
December 1987
TABLE 1.
ANALYTES WHICH CAN BE PARTITIONED BY METHOD 3650
Chemical Abstracts Service

Compound Registry Number Fraction
Benz(a)anthracene 56-55-3 Base-neutral

Benzo(a)pyrene 50-32-8 Base-neutral
Benzo(b)fluoranthene 205-99-2 Base-neutral
Chlordane 57-74-9 Base-neutral
Chlorinated dibenzodioxins Base-neutral
2-Chlorophenol 95-57-8 Acid
Chrysene 218-01-9 Base-neutral
Creosote 8001-58-9 Base-neut ra 1
and Acid
Cresol(s) Acid
Cresylic acid(s) Acid
Dichlorobenzene(s) Base-neutral
Dichlorophenoxyacetic acid 94-75-7 Acid
2,4-Dimethylphenol 105-67-9 Acid
Di nitrobenzene 25154-54-5 Base-neutral
4,6-Dinitro-o-cresol 534-52-1 Acid
2,4-Dinitrotoluene 121-14-2 Base-neut ra 1
Heptachlor 76-44-8 Base-neutral
Hexachlorobenzene 118-74-1 Base-neutral
Hexachlorobutadiene 87-68-3 Base-neutral
Hexachloroethane 67-72-1 Base-neutral
Hexachlorocyclopentadiene 77-47-4 Base-neutral
Naphthalene 91-20-3 Base-neutral
Nitrobenzene 98-95-3 Base-neutral
4-Nitrophenol 100-02-7 Acid
Pentachlorophenol 87-86-5 Acid
Phenol 108-95-2 Acid
Phorate 298-02-2 Base-neutral
2-Picoline 109-06-8 Base-neutral
Pyridine 110-86-1 Base-neutral
Tetrachlorobenzene(s) Base-neutral
Tetrachlorophenol(s) Acid
Toxaphene 8001-35-2 Base-neutral
Trichlorophenol(s) Acid
2,4,5-TP (Silvex) 93-72-1 Acid
3650 - 6 Revision 1
December 1987
METHOD 3650
ACID-BASE PARTITION CLEANUP
Star\
T.1 Place extract T.6 Coapl1t1 ph•••

or or1aaic liqaid 11par1tio11 vitb T.10 A11eabl1 1-D
vutl iato HCll&aical apparatu
11paratory faaa1l tlcllaiqau
T.e Traaahr T.11 Dry extract•·

aqa1oa1 pha11 to collect 1xtrect1 in
T.2 Add a1thyl1a1 flult: reput 1-D
chloride 1xtractioa tvic1: coac111trator:ri111
coabiu aquou flull with
extract• a1tbyl111 chloride
T.12 Add boili111

cbipl to flull:
attach eacro-colaaa:
T.3 Add pr1cbill1d T.T Di1card aqa1oa1 7.T Di1card or1a11ic place 1-D apparata1
dilate 1odiH phaH pha11 011 bot vat1r bath·
hydroxide coaceatrate· r1aov1
apparata1 fro• water
bath: drain and cool.
reaon colna
T.a Adja1t pH with T.13 Add boiliDI

1alfaric acii: tra111- chip• to coac11trator
f1r aqa1011 pba11 to tab•: attach aicro-
T.4 Seal and 1hab1 cl••• ••rr•torJ faa- colaaa: place 1-D ap-
11paratory faaa1l a1l: ad a1tbyl1111 parat11 oa bot vat1r
chloride: 1balt1: al- bath: coac11trat1:
low pba11 11paratioa: r1aov1 apparat11 fro1
collect eolveat ph••• water llatb: drain and
ill flult cool: reaove colaan
T.6 Allow T.9 P1rfora 2 aore

11parat1oa ot ntractioaa: T.13 Ad1••t final
organic layer fro• coabiu all vol••• w th 1olv1at
aquou plu.11 extract•
3650 - 7 Revision I
December 1987
METHOD 3650
(Continued)
7.14 Add k•xaae to

bau/antral
extract.coaceatrat•
uh1 aicro-1-D
apparatae: cloaaap
( lletkod 3811)
3650 - 8 Revision 1
December 1987
METHOD 5030
PURGE-AND-TRAP

1.1 This method describes sample preparation and extraction for the
analysis of volatile organics by a purge-and-trap procedure. The gas
chromatographic determinative steps are found in Methods 8010, 8015, 8021, and
8030. Although applicable to Method 8240, the purge-and-trap procedure is
already incorporated into Method 8240.
1.2 Method 5030 can be used for most volatile organic compounds that have
boiling points below 200°C and are insoluble or slightly soluble in water.
Volatile water-soluble compounds can be included in this analytical technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times
higher because of poor purging efficiency. The method is al so limited to
compounds that elute as sharp peaks from a GC column packed with graphitized
carbon lightly coated with a carbowax. Such compounds include low-molecular-
weight halogenated hydrocarbons, aromatics, ketones, nitriles, acetates,
acrylates, ethers, and sulfides.
1.3 Water samples can be analyzed directly for volatile organic compounds
by purge-and-trap extraction and gas chromatography. Higher concentrations of
these analytes in water can be determined by direct injection of the sample
into the chromatographic system.
1.4 This method also describes the preparation of water-miscible liquids,
solids, wastes, and soil/sediments for analysis by the purge-and-trap
procedure.
2.1 The purge-and-trap process - An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are adsorbed. After
purging is completed, the sorbent column is heated and backflushed with inert
gas to desorb the components onto a gas chromatographic column.
2.2 If the above sample introduction techniques are not applicable, a
portion of the sample is dispersed in methanol to dissolve the volatile
organic constituents. A portion of the methanolic solution is combined with
water in a specially designed purging chamber. It is then analyzed by purge-
and-trap GC following the normal water method.
3.0 INTERFERENCES
3.1 Impurities in the purge gas and from organic compounds out-gassing
from the plumbing ahead of the trap account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
5030 - 1 Revision 1
December 1987
contamination under the conditions of the analysis by running laboratory
reagent blanks. The use of non-TFE plastic coating, non-TFE thread sealants,
or fl ow contra 11 ers with rubber components in the purging device should be
avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A field reagent blank prepared
from reagent water and carried through sampling and handling protocols serves
as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-level and low-
level samples are analyzed sequentially. Whenever an unusually concentrated
sample is analyzed, it should be followed by an analysis of reagent water to
check for cross-contamination. The trap and other parts of the system are
subject to contamination; therefore, frequent bake-out and purging of the
entire system may be required.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
4.1 Microsyringes - 10-uL, 25-uL, 100-uL, 250-uL, 500-uL, and 1,000 uL:
These syringes should be equipped with a 20-gauge (0.006-in i.d.) needle
having a length sufficient to extend from the sample inlet to within 1 cm of
the glass frit in the purging device. The needle length will depend upon the
dimensions of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe - 5-mL, gas-tight with shutoff valve.
4.4 Balance - Analytical, capable of accurately weighing 0.0001 g, and a
top-loading balance capable of weighing 0.1 g.
4.5 Glass scintillation vials - 20-mL, with Teflon lined screw-caps or
glass culture tubes with Teflon lined screw-caps.
4.6 Volumetric flasks - 10-mL and 100-mL, class A with ground-glass
stoppers.
4.7 Vials - 2-mL, for GC autosampler.
4.8 Spatula - Stainless steel.
4.9 Disposable pipets - Pasteur.
4.10 Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
5030 - 2 Revision 1
December 1987
4.10.l The recommended purging chamber is designed to accept 5-ml
samples with a water column at least 3 cm deep. The gaseous head space
between the water column and the trap must have a total volume of less
than 15 ml. The purge gas must pass through the water column as finely
divided bubbles with a diameter of less than 3-mm at the origin. The
purge gas must be introduced no more than 5 mm from the base of the water
column. The sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be used, provided equivalent
performance is demonstrated.
4.10.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal . It is
recommended that 1.0 cm of methyl silicone-coated packing be inserted at
the inlet to extend the life of the trap (see Figures 2 and 3). If it is
not necessary to analyze for dichlorodifluoromethane or other
fluorocarbons of similar volatility, the charcoal can be eliminated and
the polymer increased to fill 2/3 of the trap. If only compounds boiling
above 35°C are to be analyzed, both the silica gel and charcoal can be
eliminated and the polymer increased to fill the entire trap. Before
initial use, the trap should be conditioned overnight at 180°C by
backflushing with an inert gas flow of at least 20 ml/min. Vent the trap
effluent to the hood, not to the analytical column. Prior to daily use,
the trap should be conditioned for 10 minutes at 180°C with backflushing.
The trap may be vented to the analytical column during daily conditioning;
however, the column must be run through the temperature program prior to
analysis of samples.
4.10.3 The desorber should be capable of rapidly heating the trap to
180°C for desorption. The polymer section of the trap should not be
heated higher than 180°C, and the remaining sections should not exceed
220°C during bake-out mode. The desorber design illustrated in Figures 2
and 3 meet these criteria.
4.10.4 The purge-and-trap device may be assembled as a separate unit
or may be coupled to a gas chromatograph, as shown in Figures 4 and 5.
4.10.5 Trap Packing Materials
4.10.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.10.5.2 Methyl silicone packing - OV-1 (3%) on Chromosorb-W,
60/80 mesh or equivalent.
4.10.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.10.5.4 Coconut charcoal - Prepare from Barnebey Cheney, CA-
580-26 lot #M-2649, by crushing through 26 mesh screen.
5030 - 3 Revision 1
December 1987
4.11 Heater or heated oil bath - Capable of maintaining the purging
chamber to within 1°C over a temperature range from ambient to l00°C.
5.0 REAGENTS
determination.
5.2 ASTM Type II Water (ASTM 01193-77 (1983)). All references to water in
5.3 Methanol, CH30H. Pesticide quality or equivalent. Store away from
other solvents.
5.4 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of compounds
of interest.
5.4.1 Tetraglyme (tetraethylene glycol dimethylether, Aldrich #17,
240-5 or equivalent), C8H1805. Purify by treatment at reduced pressure in
a rotary evaporator. The tetraglyme should have a peroxide content of
less than 5 ppm as indicated by EM Quant Test Strips (available from
Scientific Products Co., Catalog No. Pll26-8 or equivalent).
CAUTION: Glycol ethers are suspected carcinogens. All solvent handling
should be done in a hood while using proper protective equipment to
minimize exposure to liquid and vapor.
Peroxides may be removed by passing the tetraglyme through a column of
activated alumina. The tetraglyme is placed in a round bottom flask
equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed in a water bath at 90-100°C and vacuum
is maintained at < 10 mm Hg for at least two hours using a two-stage
mechanical pump. The vacuum system is equipped with an all-glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 0.1 mg/ml of 2,6-di-tert-butyl-4-methyl-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw-cap bottle in an area that is not contaminated by solvent vapors.
5.4.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, a water/tetraglyme blank must be
analyzed.
5.5 Polyethylene glycol, H(OCH2CH2)nOH. Free of interferences at the
detection limit of the analytes.
5030 - 4 Revision 1
December 1987
6.1 Refer to the introductory material to this Chapter, Organic Analytes,
Step 4.1.
7. 0 PROCEDURE
7.1 Initial calibration - Prior to using this introduction technique for
any GC method, the system must be calibrated. General calibration procedures
are discussed in Method 8000, Step 7.4, while the specific determinative
methods and Method 3500 give details on preparation of standards.
7.1.1 Assemble a purge-and-trap device that meets the specification
in Step 4.10. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 ml/min. Prior to use, condition the
trap daily for 10 minutes while backflushing at 180°C with the column at
220°C.
7.1.2 Connect the purge-and-trap device to a gas chromatograph.
7.1.3 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device. (Use freshly prepared stock solutions
when preparing the calibration standards for the initial calibration.) Add
5.0 ml of water to the purging device. The water is added to the purging
device using a 5-ml glass syringe fitted with a 15-cm 20-gauge needle.
The needle is inserted through the sample inlet shown in Figure 1. The
internal diameter of the 14-gauge needle that forms the sample inlet will
permit insertion of the 20-gauge needle. Next, using a 10-ul or 25-ul
microsyringe equipped with a long needle (Step 4.1}, take a volume of the
secondary dilution solution containing appropriate concentrations of the
calibration standards. Add the aliquot of calibration solution directly
to the reagent water in the purging device by inserting the needle through
the sample inlet. When discharging the contents of the micro-syringe, be
sure that the end of the syringe needle is well beneath the surface of the
reagent water. Similarly, add 10 ul of the internal standard solution.
Close the 2-way syringe valve at the sample inlet.
7.1.4 Carry out the purge-and-trap analysis procedure using the
specific conditions given in Table 1.
7.1.5 Calculate response factors or calibration factors for each
analyte of interest using the procedure described in Method 8000, Step
7.4.
7.1.6 The average RF must be calculated for each compound. A system
performance check should be made before this calibration curve is used.
If the purge-and-trap procedure is used with Method 8010, the following
five compounds are checked for a minimum average response factor:
chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-tetrachloroethane;
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have RFs
5030 - 5 Revision 1
December 1987
of 0.4-0.6 and are used to check compound instability and check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
1. Chloromethane - This compound is the most likely compound to
be lost if the purge flow is too fast.
2. Bromoform - This compound is one of the compounds most
likely to be purged very poorly if the purge flow is too slow. Cold
spots and/or active sites in the transfer lines may adversely affect
response.
3. Tetrach l oroethane and 1, 1-di ch l oroethane - These compounds
are degraded by contaminated transfer lines in purge-and-trap
systems and/or active sites in trapping materials.
7.2 On-going calibration - Refer to Method 8000, Steps 7.4.2.3 and
7.4.3.4 for details on continuing calibration.
7.3 Sample preparation
7.3.l Water samples
7.3.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and wi 11 prevent contamination of the purge-and-trap
system. Two screening techniques that can be utilized are: the use
of an automated headspace sampler (modified Method 3810), interfaced
to a gas chromatograph ( GC), equipped with a photo i oni zat ion
detector (PIO), in series with an electrolytic conductivity detector
(ECO}; and extraction of the sample with hexadecane (Method 3820) and
analysis of the extract on a GC with a FID and/or an ECO.
7.3.1.2 All samples and standard solutions must be allowed to
warm to ambient temperature before analysis.
7.3.1.3 Assemble the purge-and-trap device. The operating
conditions for the GC are given in Section 7.0 of the specific
determinative method to be employed.
7.3.1.4 Daily GC calibration criteria must be met (Method 8000,
Step 7.4) before analyzing samples.
7.3.1.5 Adjust the purge gas flow rate (nitrogen or helium) to
that shown in Table 1, on the purge-and-trap device. Optimize the
flow rate to provide the best response for chloromethane and
bromoform, if these compounds are analytes. Excessive flow rate
reduces chloromethane response, whereas insufficient flow reduces
bromoform response.
7.3.1.6 Remove the plunger from a 5-ml syringe and attach a
closed syringe valve. Open the sample or standard bottle, which has
been allowed to come to ambient temperature, and carefully pour the
5030 - 6 Revision 1
December 1987
sample into the syringe barrel to just short of overflowing. Replace
the-~yringe plunger and compress the sample. Open the syringe valve
and vent any residual air while adjusting the sample volume to
5.0 ml. This process of taking an aliquot destroys the validity of
the liquid sample for future analysis; therefore, if there is only
one VOA vial, the analyst should fill a second syringe at this time
to protect against possible loss of sample integrity. This second
sample is maintained only until such time when the analyst has
determined that the first sample has been analyzed properly. Filling
one 20-ml syringe would allow the use of only one syringe. If a
second analysis is needed from a syringe, it must be analyzed within
24 hours. Care must be taken to prevent air from leaking into the
syringe.
7.3.1.7 The following procedure is appropriate for diluting
purgeable samples. All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.
7.3.1.7.1 Dilutions may be made in volumetric flasks
(10-ml to 100-ml). Select the volumetric flask that will allow
for the necessary dilution. Intermediate dilutions may be
necessary for extremely large dilutions.
7.3.1.7.2 Calculate the approximate volume of water to be
added to the volumetric flask selected and add slightly less
than this quantity of water to the flask.
7.3.1.7.3 Inject the proper aliquot of samples from the
syringe prepared in Step 7.3.1.5 into the flask. Aliquots of
less than I-ml are not recommended. Oil ute the sample to the
mark with reagent water. Cap the flask, invert, and shake three
times. Repeat the above procedure for additional dilutions.
7.3.1.7.4 Fill a 5-ml syringe with the diluted sample as
in Step 7. 3. I. 5.
7.3.1.8 Add 10.0 ul of surrogate spiking solution (found in
each determinative method, Section 5.0) and, if applicable, 10 ul of
internal standard spiking solution through the valve bore of the
syringe; then close the valve. The surrogate and internal standards
may be mixed and added as a single spiking solution. Matrix spiking
solutions, if indicated, should be added (10 ul) to the sample at
this time.
7.3.1.9 Attach the syringe-syringe valve assembly to the
syringe va 1ve on the purging device. Open the syringe va 1ves and
inject the sample into the purging chamber.
7.3.1.10 Close both valves and purge the sample for the time and
at the temperature specified ~n Table I.
7.3.1.11 At the conclusion of the purge time, attach the trap to
the chromatograph, adjust the device to the desorb mode, and begin
5030 - 7 Revision I
December 1987
the gas chromatographic temperature program and GC data acquisition.
Concurrently, introduce the trapped materials to the gas
chromatographic column by rapidly heating the trap to 180°C while
backflushing the trap with inert gas between 20 and 60 ml/min for the
time specified in Table 1.
7.3.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5-ml flushes of water (or methanol followed by water)
to avoid carryover of pollutant compounds into subsequent analyses.
7.3.1.13 After desorbing the sample, recondition the trap by
returning the purge-and-trap device to the purge mode. Wait 15
seconds; then close the syringe valve on the purging device to begin
gas flow through the trap. The trap temperature should be maintained
at 180°C for Methods 8010 and 8020, and 210°C for Methods 8015 and
8030. Trap temperatures up to 220°C may be employed; however, the
higher temperature will shorten the useful life of the trap. After
approximately 7 minutes, turn off the trap heater and open the
syringe valve to stop the gas flow through the trap. When cool, the
trap is ready for the next sample.
7.3.1.14 If the initial analysis of a sample or a dilution of
the sample has a concentration of analytes that exceeds the initial
calibration range, the sample must be reanalyzed at a higher
dilution. When a sample is analyzed that has saturated response from
a compound, this analysis must be followed by a blank water analysis.
If the blank analysis is not free of interferences, the system must
be decontaminated. Sample analysis may not resume until a blank can
be analyzed that is free of interferences.
7.3.1.15 All dilutions should keep the response of the major
constituents (previously saturated peaks) in the upper half of the
linear range of the curve. Proceed to Method 8000 and the specific
determinative method for details on calculating analyte response.
7.3.2 Water-miscible liquids
7.3.2.1 Water-miscible liquids are analyzed as water samples
after first diluting them at least 50-fold with water.
7.3.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample to a 100-ml volumetric flask and
diluting to volume with water. Transfer immediately to a 5-ml gas-
tight syringe.
7.3.2.3 Alternatively, prepare dilutions directly in a 5-ml
syringe filled with water by adding at least 20 ul, but not more than
100-ul of liquid sample. The sample is ready for addition of
surrogate and, if applicable, internal and matrix spiking standards.
5030 - 8 Revision 1
December 1987
7.3.3 Sediment/soil and waste samples - It is highly recommendt.
that all samples of this type be screened prior to the purge-and-trap GC
analysis. These samples may contain percent quantities of purgeable
organics that wi 11 contaminate the purge-and-trap system, and require
extensive cleanup and instrument downtime. See Step 7. 3 .1.1 for
recommended screening techniques. Use the screening data to determine
whether to use the low-level method (0.005-1 mg/kg) or the high-level
method (> 1 mg/kg).
7.3.3.1 Low-level method - This is designed for samples
containing individual purgeable compounds of < 1 mg/kg. It is
limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-level method is based on
purging a heated sediment/soil sample mixed with water containing the
surrogate and, if applicable, internal and matrix spiking standards.
Analyze all reagent blanks and standards under the same conditions as
the samples.
7.3.3.1.l Use a 5-g sample if the expected concentration
is < 0.1 mg/kg or a 1-g sample for expected concentrations
between 0.1 and 1 mg/kg.
7.3.3.1.2 The GC system should be set up as in Section
7.0 of the specific determinative method. This should be done
prior to the preparation of the sample to avoid loss of
volatiles from standards and samples. A heated purge
calibration curve must be prepared and used for the quantitation
of all samples analyzed with the low-level method. Follow the
initial and daily calibration instructions, except for the
addition of a 40°C purge temperature for Methods 8010 and 8020.
7.3.3.1.3 Remove the plunger from a 5-ml Luerlock type
syringe equipped with a syringe valve and fill until overflowing
with reagent water. Replace the plunger and compress the water
to vent trapped air. Adjust the volume to 5.0 ml. Add 10 ul
each of surrogate spiking solution and internal standard
solution to the syringe through the valve. (Surrogate spiking
solution and internal standard solution may be mixed together.)
Matrix spiking solutions, if indicated, should be added (IO ul)
to the sample at this time.
7.3.3.1.4 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard any
supernatant liquids. Mix the contents of the sample container
with a narrow metal spatula. Weigh the amount determined in
Step 7. 3. 3 .1.1 into a tared purge device. Note and record the
actual weight to the nearest 0.1 g.
7.3.3.1.5 In certain cases, sample results are desired
based on a dry-weight basis. When such data is desired, a
portion of sample for moisture determination should be weighed
out at the same ti me as the portion used for anal yt i cal
determination. Immediately after weighing the sample for
5030 - 9 Revision 1
December 1987
extraction, weigh 5-10 g of the sample into a tared crucible.
Determine the percent moisture by drying overnight at 105°C.
Allow to cool in a desiccator before weighing:
% moisture =
g of sample - g of dry sample x 100
g of sample
7.3.3.1.6 Add the spiked water to the purge device, which
contains the weighed amount of sample, and connect the device to
the purge-and-trap system.
NOTE: Prior to the attachment of the purge device, Steps 7.3.3.1.4 and
7.3.3.1.6 must be performed rapidly and without interruption to avoid
loss of volatile organics. These steps must be performed in a
laboratory free of solvent fumes.
7.3.3.1.7 Heat the sample to 40°C ± 1°C {Methods 8010 and
8020) or to 85°C ± 2°C {Methods 8015 and 8030) and purge the
sample for the time shown in Table 1.
7.3.3.1.8 Proceed with the analysis as outlined in Steps
7.3.1.11-7.3.1.15. Use 5 ml of the same water as in the reagent
blank. If saturated peaks occurred or would occur if a 1-g
sample were analyzed, the high-level method must be followed.
7.3.3.2 High-level method - The method is based on extracting
the sediment/soil with methanol. A waste sample is either extracted
or diluted, depending on its solubility in methanol. Wastes {i.e.
petroleum and coke wastes) that are insoluble in methanol are diluted
with reagent tetraglyme or possibly polyethylene glycol (PEG). An
aliquot of the extract is added to water containing surrogate and, if
applicable, internal and matrix spiking standards. This is purged at
the temperatures indicated in Table 1. All samples with an expected
concentration of> 1.0 mg/kg should be analyzed by this method.
7.3.3.2.1 The sample (for volatile organics) consists of
the entire contents of the sample container. Do not discard any
supernatant liquids. Mix the contents of the samp 1e container
with a narrow metal spatula. For sediment/soil and solid wastes
that are insoluble in methanol, weigh 4 g (wet weight) of sample
into a tared 20-ml vial. Use a top-loading balance. Note and
record the actual weight to 0.1 gram and determine the percent
moisture of the sample using the procedure in Step 7. 3. 3 .1. 5.
For waste that is soluble in methanol, tetraglyme, or PEG, weigh
1 g (wet weight) into a tared scintillation vial or culture tube
or a 10-ml volumetric flask. (If a vial or tube is used, it
must be calibrated prior to use. Pipet 10.0 ml of solvent into
the vial and mark the bottom of the meniscus. Discard this
sol vent.)
December 1987
7.3.3.2.2 Quickly add 9.0 ml of appropriate solvent; then
add 1.0 ml of the surrogate spiking solution to the vial. Cap
and shake for 2 minutes.
NOTE: Steps 7.3.3.2.1 and 7.3.3.2.2 must be performed rapidly and without
interruption to avoid loss of volatile organics. These steps must be
performed in a laboratory free from solvent fumes.
7.3.3.2.3 Pipet approximately 1 ml of the extract to a GC
vial for storage, using a disposable pipet. The remainder may
be disposed of. Transfer approximately 1 ml of appropriate
solvent to a separate GC vial for use as the method blank for
each set of samples. These extracts may be stored at 4°C in the
dark, prior to analysis.
7 .3.3.2.4 The GC system should be set up as in Section
7 .0 of the specific determinative method. This should be done
prior to the addition of the solvent extract to water.
7.3.3.2.5 Table 2 can be used to determine the volume of
solvent extract to add to the 5 ml of water for analysis. If a
screening procedure was followed, use the estimated
concentration to determine the appropriate volume. Otherwise,
estimate the concentration range of the sample from the low-
1eve l analysis to determine the appropriate volume. If the
sample was submitted as a high-level sample, start with 100 ul.
All dilutions must keep the response of the major constituents
(previously saturated peaks) in the upper half of the linear
range of the curve.
7.3.3.2.6 Remove the plunger from a 5.0-ml luerlock type
syringe equipped with a syringe valve and fill until overflowing
with water. Replace the plunger and compress the water to vent
trapped air. Adjust the volume to 4.9 ml. Pull the plunger
back to 5.0 ml to allow volume for the addition of the sample
extract and of standards. Add 10 ul of internal standard
solution. Also add the volume of solvent extract determined in
Step 7.3.3.2.5 and a volume of extraction or dissolution solvent
to total 100 ul (excluding solvent in standards).
7.3.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe valve
and inject the water/solvent sample into the purging chamber.
7.3.3.2.8 Proceed with the analysis as outlined in the
specific determinative method. Analyze all reagent bl an ks on
the same instrument as that used for the samples. The standards
and blanks should also contain 100 ul of solvent to simulate the
sample conditions.
7.3.3.2.9 For a matrix spike in the high-level
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution and 1.0 ml of matrix spike solution.
5030 - 11 Revision I
December 1987
Add a 100-ul aliquot of this extract to 5 ml of water for
purging (as per Step 7.3.3.2.6).
7.4 Sample analysis
7.4.1 The samples prepared by this method may be analyzed by Methods
8010, 8015, 8020, 8021, and 8030. Refer to these methods for appropriate
analysis conditions.
8.0 QUALITY CONTROL
8 .1 Refer to Chapter One for specific quality contra l procedures and
Method 3500 for sample preparation procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of a calibration blank that all glassware and reagents are
interference free. Each time a set of samples is extracted, or there is a
change in reagents, a reagent blank should be processed as a safe-guard
against chronic laboratory contamination. The blanks should be carried
through all stages of the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Laboratory replicates should be analyzed to validate the precision
of the analysis. Spiked samples should be carried through all stages of
sample preparation and measurement; they should be analyzed to validate the
sensitivity and accuracy of the analysis. If the spiked samples do not
indicate sufficient sensitivity to detect < 1 ug/g of the analytes in the
sample, then the sensitivity of the instrument should be increased, or the
sample should be subjected to additional cleanup.
10.0 REFERENCES
2. Gebhart, J.E.; Lucas, S.V.; Naber, S.J.; Berry, A.M.; Danison, T.H.;
Burkholder, H.M. "Validation of SW-846 Methods 8010, 8015, and 8020";
U.S. Environmental Protection Agency. Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268, July 1987, Contract No.
68-03-1760.
for Reagent Water"; ASTM: Philadelphia, PA, 1985; Dl193-77.
December 1987
TABLE 1.
PURGE-AND-TRAP OPERATING PARAMETERS
An~l~si~ Method
8010 8015 8020 8021 8030
Purge gas Nitrogen Nitrogen Nitrogen Nitrogen Nitrogen

U1 or Helium or Helium or Helium or Helium or Helium
0
w
0
Purge gas flow rate (ml/min) 40 20 40 25-40 20
-
I
w Purge time (min) 11.0 :t 0.1 15.0 :t 0.1 12.0 :t 0.1 11.0 :t 0.1 15.0 :t 0.1
Purge temperature c·c) Ambient 85 :t 2 Ambient Ambient 85 :t 2
Desorb temperature c·c) 180 180 180 180 180
Backflush inert gas flow 20-60 20-60 20-60 6 20-60
(ml/min)
Desorb time (min) 4 1.5 4 4 ± 0.1 1.5
CAI
ft) ft)
(') <
CD _,,
i5I UI
O"' ....
--
CD 0
.., ::I
'°
CD
"'
TABLE 2.
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS
OF HIGH-LEVEL SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extracta
500-10,000 ug/kg 100 ul

1,000-20,000 ug/kg 50 ul
5,000-100,000 ug/kg 10 UL
25,000-500,000 ug/kg 100 ul of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this

table.
aThe vo 1ume of methano 1 added to 5 ml of water being purged should be
kept constant. Therefore, add to the 5-ml syringe whatever volume of methanol
is necessary to maintain a volume of 100 ul added to the syringe.
boil ute an aliquot of the methanol extract and then take 100 ul for
analysis.
December 1987
FIGURE 1.
PURGING CHAMBER
OPTIONAL
FOAM TRAP
1.C mm 0. D.
I I
I f
I I
••
••
••
f I
2·W•v Syringe V1lvt
17 cm. 20 Gluge Svranve NHdlt
1' Inch O. D. Exit 6 mm 0. D. Rubber Sti:>tum
-10mm 0. D.
t+--
'
1 '16 Inch 0 0.
Su1nltss Stet:
c
ci
I
-g
• 13• Moltculu
Sieve Purge
-
G1s Filter
c
Purge Gas
Flow Control
10 mm G.... Frit
Medium Porol•'Y
December 1987
FIGURE 2.
TRAP PACKING MATERIALS AND CONSTRUCTION FOR METHOD 8010
Packing Procedure Construction
Compression
Glass Wool 5mm .,,._Fitting Nut
7n!Foot and Ferrules
Activated
Charcoal
l
7.7cm .,
Resistance
Wire Wrapped
Solid
Grade 15
Silica Gel
j
7.7cm
%
(Double Laverl
15 cm
Electronic
Temperature
Control and
1n1Foot Pyrometer
.,
Tenax
f ..''·
Resistance
Wire Wrapped
Solid
3% OV-1 Stainless Steel

Glau Wool Smm
Trap lnltt
December 1987
FIGURE 3.
TRAP PACKING MATERIALS AND CONSTRUCTION FOR METHODS 8020 AND 8030
Packing Procedure Construction
_Compression F ittil'l9 Nut

Glass Wool 5 mm ,..........--and Ferrules
14 Ft. 1n/Foot Resistance

Wirt Wrapped Solid
Thermocouple/Controller Sensor
Tenax 23 cm
Electronic
Temperature
Control and
Pyrometer
Tubing 25 cm
0. 105 In. 1.0 .
....~-+-- 0. 125 In. 0.0.
Stainless Stttl
3% OV-1 1 cm t
Glass Wool 5 mm
Trap Inlet
December 1987
FIGURE 4.
PURGE-AND-TRAP SYSTEM, PURGE-SORB MODE,
FOR METHODS 8010, 8020, AND 8030
COLUMN OVEN
CONFIRMATORY COLUMN
PRESSURE
REGULATOR
TO DETECTOR
ANALYTICAL COLUMN
OfSTIONAL ~PORT COLUMN
SEl.ECTION VAL V£
' - TRAP INLET

PURGE GAS
FlOW CONTROl.
' TRAP
22·c
13X MOLECULAR
SIEVE FILTEA
l PURGING NOTE:
DEVICE AU LINES BElW£EN TRAP
ANO GC SHOULD BE HEATEO
T080-C
December 1987
FIGURE 5.
PURGE-AND-TRAP SYSTEM, DESORB MODE,
FOR METHODS 8010, 8020, AND 8030
UOU40 INJECTION PORTS

COLUMN OVEN
CONFIRMATORY COLUMN
PRESSURE
REGULATOR
TO DETECTOR
ANALYTICAL COLUMN
TRAP INLET
PURGE GAS
FLOW CONTROL
'
13X MOLECULAR
SIEVE ALTER
VENT l
A PURGING NOTE:
DEVICE All LINES BE'TWEEN TRAP
ANO GC SHOULD BE HEATED
TO S>"C.
December 1987
METHOD 5030
PURGE-AND-TRAP
Ster-t
7. 1 7.1. ..
C•llbrete
GC system Carry out
and prepare our11e-anc:1-trap
stander-a• ane1ys1•
7. l.5
7. l.2 Calculate
reaponae or
Aaaelllble caltbratton factor•
pur-11•-•na-treo for aacl"I analyte
Clevtce ana (Metl"loct eooo.
cond1t1on trao Sect Jon 7. ~>
7. l.3 7. l.6
Connect to 11•• C•lcul•t•

cl"lro111eto11r-epl"I avere11e RF for
aacl"I COlllPGUnc:I
7. l.3
Prepar-e flnel
aoluttons
December 1987
METHOD 5030
(Continued)
B c
t.o .. -Je .. eJ for

so11/&ed1•cn HeOlu•-le~el
tor •oll/ 7.3.3.2 7.3.tl Intcct
Prcoer-c •••ol••
... ~~:~ =~O ~S!_!C~C~l~•~e:!'.n~t:.,J""""----:H t.~~~O 1
••t.rect t.o
•••pl
ourae: ocsarb
a
lnta che111ber;
•nCS set uo
GC systc.,
ree11cnt ..etcr
tor enalysls
trep 1nto
chra•etoorsot\
G••
Nater-
ena
•UC lb le
7. 3., I
7.3.3.a 7.3.tf
Screen •••oles orlar
to ourgc-ena-treo
NelDl'I •••ole en•lY•ls: d11ute Set VP GC Recondltlon
lnto ter-ca .. atcr-.,t•clble system tr•o eno stert
ourge CSevlce •••oles gas tlo ..
4.3.2.S 7 .3. sl 7.3.3.2

1"'11
7.3.sl
Nelgl'I syrlnge wlt.l'I
enotl'ler- •••ol•
ena aeter-•lnc
Preoerc •••olc
ena pur-gc-enci-
rc•a•nt water.
vent elr enc
Stoo a••
flaw
end cool trao
ll •olstur-e treo aevtce OCI j US t. VD lu111e tor next •••olo
4.3.2.8 Add
solked
7.3.S.7 7.3.3.2 &oa
lnt.er-
s.o I ••-a
•n•1rz•
•
r-eegent ••tcr: no 1 •t•noena by ••thoae
connect devlce 011utc ones -tl\onal 8010. 80l5. 8020.
to pur-11• end purgeabl• ••troct fro111 8030. .,. 82•0
c.r-ep syste• •••Pl es 7.3.3.2.5 •• •ooroorl•t.•
•.'3.2.7 7.3.ll Add 7.3.3.2

eurrogetc t-----Al\o l Y&•
enCI lnternal •• outll"•CI
Meet eno ourge
••...,1. sptlr.ln,
eolutlans lt
1ne11ceteal
l" •D•c U le
Cloterall\Otlve
••tl'lod
~
D c D
Ml•ly&• by
••thod
80l0. 80UI. 8020.
8030. or aa•O
December 1987
METHOD 6010
INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCOPY

1.1 Inductively coupled plasma-atomic emission spectroscopy (ICP)
determines trace elements including metals in solution. The method is
applicable to a large number of metals and wastes. All matrices, including
ground water, aqueous samples, EP extracts, industrial wastes, soils, sludges,
sediments, and other solid wastes, require digestion prior to analysis.
1.2 Elements for which Method 6010 is applicable are listed in Table 1.
Detection limits, sensitivity, and optimum ranges of the metals will vary with
the matrices and model of spectrometer. The data shown in Table 1 provide
concentration ranges for clean aqueous samples. Use of this method is
restricted to spectroscopi sts who are kn owl edgeabl e in the correction of
spectral, chemical, and physical interferences.
2.1 Prior to analysis, samples must be solubilized or dig,ested using
appropriate Sample Preparation Methods (e.g. Methods 3005-3050).
2.2 Method 6010 describes the simultaneous, or sequential, multielemental
determination of elements by ICP. The method measures element-emitted light by
optical spectrometry. Samples are nebulized and the resulting aerosol is
transported to the plasma torch. Element-specific atomic-line emission spectra
are produced by a radio-frequency inductively coupled plasma. The spectra are
dispersed by a grating spectrometer, and the intensities of the lines are
monitored by photomultiplier tubes. Background correction is required for
trace element determination. Background must be measured adjacent to analyte
lines on samples during analysis. The position selected for the background-
intensity measurement, on either or both sides of the analytical line, will be
determined by the complexity of the spectrum adjacent to the analyte line. The
position used must be free of spectral interference and reflect the same
change in background intensity as occurs at the analyte wavelength measured.
Background correction is not required in cases of 1i ne broadening where a
background correction measurement would actua 11 y degrade the ana 1yt i ca 1
result. The possibility of additional interferences named in Section 3.0
should also be recognized and appropriate corrections made; tests for their
presence are described in Step 8.5.
3.0 INTERFERENCES
3.1 Spectral interferences are caused by: (1) overlap of a spectral line
from another element; (2) unresolved overlap of molecular band spectra; (3)
background contribution from continuous or recombination phenomena; and ( 4)
stray light from the line emission of high-concentration elements.
6010 - 1 Revision I
December 1987
TABLE 1.
RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS
Detection Estimated
Element Wavelengtha (nm) Limitb (ug/L)
Aluminum 308.215 45
Antimony 206.833 32
Arsenic 193.696 53
Barium 455.403 2
Beryllium 313.042 0.'3
Cadmium 226.502 4
Calcium 317. 933 10
Chromium 267. 716 7
Cobalt 228.616 7
Copper 324.754 6
Iron 259.940 7
Lead 220.353 42
Lithium 670.784 5
Magnesium 279.079 30
Manganese 257.610 2
Molybdenum 202.030 8
Nickel 231.604 15
Phosphorus 213.618 51
Potassium 766.491 See note c
Selenium 196.026 75
Silver 328.068 7
Sodium 588.995 29
Strontium 407. 771 0.3
Thallium 190.864 40
Vanadium 292.402 8
Zinc 213.856 2
aThe wavelengths listed are recommended because of their sensitivity and

overall acceptance. Other wavelengths may be substituted if they can provide
the needed sensitivity and are treated with the same corrective techniques for
spectral interference (see Step 3.1). In time, other elements may be added as
more information becomes available and as required.
bThe estimated instrumental detection 1 imits shown are taken from
Reference 1 in Section 10.0 below. They are given as a guide for an
instrumental 1imit. The actual method detection 1imits are sample dependent
and may vary as the sample matrix varies.
CHighly dependent on operating conditions and plasma position.
6010 - 2 Revision 1
December 1987
Spectral overlap can be compensated for by computer-correcting the raw data
after monitoring and measuring the interfering element. Unresolved overlap
requires selection of an alternate wavelength. Background contribution and
stray light can usually be compensated for by a background correction adjacent
to the analyte line.
Users of simultaneous multielement instruments must verify the absence of
spectral interference from an element in a sample for which there is no
instrument detection channel . Potential spectral interferences for the
recommended wavelengths are given in Table 2. The data in Table 2 are intended
as rudimentary guides for indicating potential interferences; for this
purpose, linear relations between concentration and intensity for the analytes
and the interferents can be assumed.
3.1.1 The interference is expressed as analyte concentration

equivalents (i.e. false analyte concentrations) arising from 100 mg/L of
the interference element. For example, assume that As is to be determined
(at 193.696 nm) in a sample containing approximately 10 mg/L of Al.
According to Table 2, 100 mg/L of Al would yield a false signal for As
equivalent to approximately 1.3 mg/L. Therefore, the presence of 10 mg/L
of Al would result in a false signal for As equivalent to approximately
0.13 mg/L. The user is cautioned that other instruments may exhibit
somewhat different levels of interference than those shown in Table 2. The
interference effects must be evaluated for each individual instrument
since the intensities will vary with operating conditions, power, viewing
height, argon flow rate, etc.
3.1.2 The dashes in Table 2 indicate that no measurable

interferences were observed even at higher i nterferent concentrations.
Genera 11 y, interferences were discernible if they produced peaks, or
background shifts, corresponding to 2 to 5% of the peaks generated by the
analyte concentrations.
3.1.3 At present, information on the listed silver and potassium

wavelengths is not available, but it has been reported that second-order
energy from the magnesium 383.231-nm wavelength interferes with the listed
potassium line at 766.491 nm.
3. 2 Physical interferences are effects associated with the sample

nebulization and transport processes. Changes in viscosity and surface tension
can cause significant inaccuracies, especially in samples containing high
dissolved solids or high acid concentrations. If physical interferences are
present, they must be reduced by diluting the sample or by using a peristaltic
pump. Another problem that can occur with high dissolved solids is salt
buildup at the tip of the nebul izer, which affects aerosol flow rate and
causes instrumental drift. The problem can be controlled by wetting the argon
prior to nebulization, using a tip washer, or diluting the sample. Also, it
has been reported that better control of the argon flow rate improves
instrument performance; this is accomplished with the use of mass fl ow
controllers.
6010 - 3 Revision 1
December 1987
TABLE 2.
ANALYTE CONCENTRATION EQUIVALENTS ARISING FROM
INTERFERENCE AT THE 100-mg/L LEVEL
Interferent a,b
Wavelength -----------------------------------------------------------
Analyte (nm) Al Ca Cr Cu Fe Mg Mn Ni Tl v
---------------------------------------------------------------------------------
Aluminum 308.215 0.21 1.4
Antimony 206.833 0.47 2.9 0.08 0.25 0.45
Arsenic 193.696 1.3 0.44 1.1
Barium 455.403
Beryllium 313.042 0.04 0.05
Cadmium 226.502 0.03 0.02
Calcium 317.933 0.08 0.01 0.01 0.04 0.03 0.03
Chromium 267. 716 0.003 0.04 0.04
Cobalt 228.616 0.03 0.005 0.03 0.15
Copper 324.754 0.003 0.05 0.02
Iron 259.940 0.12
Lead 220.353 0.17
Magnesium 279.079 0.02 0.11 0.13 0.25 0.07 0.12
Manganese 257.610 0.005 0.01 0.002 0.002
Molybdenum 202.030 0.05 0.03
Nickel 231.604
Selenium 196.026 0.23 0.09
Sodium 588.995 0.08
Thallium 190.864 0.30
Vanadium 292.402 0.05 0.005 0.02
Zinc 213.856 0.14 0.29
aoashes indicate that no interference was observed even when interferents

were introduced at the following levels:
Al - 1000 mg/L Mg - 1000 mg/L
Ca - 1000 mg/L Mn - 200 mg/L
Cr - 200 mg/L Tl - 200 mg/L
Cu - 200 mg/L V- 200 mg/L
Fe - 1000 mg/L
bThe figures recorded as analyte concentrations are not the actual
observed concentrations; to obtain those figures, add the listed concentration
to the interferent figure.
6010 - 4 Revision 1
December 1987
3.3 Chemical interferences include molecular compound formation,
i oni zat ion effects, and solute vaporization effects. Normally, these effects
are not significant with the ICP technique. If observed, they can be minimized
by careful selection of operating conditions (incident power, observation
position, and so forth), by buffering of the sample, by matrix matching, and
by standard addition procedures. Chemical interferences are highly dependent
on matrix type and the specific analyte element.
4.1 Inductively coupled argon plasma emission spectrometer:
4 .1.1 Computer-controlled emission spectrometer with background
correction.
4.1.2 Radio frequency generator.
4.1.3 Argon gas supply - Welding grade or better.
4.2 Operating conditions - The analyst should follow the instructions
provided by the instrument manufacturer. For operation with organic solvents,
use of the auxiliary argon inlet is recommended, as are solvent-resistant
tubing, increased plasma (cool ant) argon fl ow, decreased nebul i zer fl ow, and
increased RF power to obtain stable operation and precise measurements.
Sensitivity, instrumental detection limit, precision, 1i near dynamic range,
and interference effects must be established for each individual analyte line
on that particular instrument. All measurements must be within the instrument
linear range where coordination factors are valid. The analyst must (1) verify
that the instrument configuration and operating conditions satisfy the
analytical requirements and (2) maintain quality control data confirming
instrument performance and analytical results.
5.0 REAGENTS
high purity to permit its use without 1es sen i ng the accuracy of the
determination.
5.1.1 Hydrochloric acid (cone), HCl.
5.1.2 Hydrochloric acid (1:1), HCl. Add 500 ml concentrated HCl to
400 ml water and dilute to 1 liter.
5.1.3 Nitric acid (cone), HN03.
5.1.4 Nitric acid (1: 1), HN03. Add 500 ml concentrated HN03 to
400 ml water and dilute to 1 liter.
6010 - 5 Revision 1
December 1987
5.3 Standard stock solutions may be purchased or prepared from ultra-
high purity grade chemicals or metals (99.99 to 99.999% pure). All salts must
be dried for 1 hour at 105°C, unless otherwise specified.
CAUTION: Many metal salts are extremely toxic if inhaled or swallowed.
Wash hands thoroughly after handling.
Typical stock solution preparation procedures follow. Concentrations are
calculated based upon the weight of pure metal added, or with the use of the
mole fraction and the weight of the metal salt added.
Metal
vo ume -l
. (ppm) = weinht
Concentration --r~--- fmrl
Metal salts
. (ppm) = weinht
Concentration .{mgl x mole fraction
---~---volume-\[} _________ _
5.3.1 Aluminum solution, stock, 1 ml= 100 ug Al: Dissolve 0.10 g

of aluminum metal, weighed accurately to at least four significant
figures, in an acid mixture of 4 ml of (1:1) HCl and 1 ml of concentrated
HN03 in a beaker. Warm gently to effect solution. When solution is
complete, transfer quantitatively to a liter flask, add an additional
10 ml of (1:1) HCl and dilute to 1,000 ml with water.
5.3.2 Antimony solution, stock, 1 ml = 100 ug Sb: Dissolve 0.27 g
K(SbO)C4H406 (mole fraction Sb = 0.3749), weighed accurately to at least
four significant figures, in water, add 10 ml (1:1) HCl, and dilute to
1,000 ml with water.
5.3.3 Arsenic solution, stock, 1 ml = 100 ug As: Dissolve 0.13 g of
As203 (mole fraction As = 0.7574), weighed accurately to at least four
significant figures, in 100 ml of water containing 0.4 g NaOH. Acidify the
solution with 2 ml concentrated HN03 and dilute to 1,000 ml with water
5.3.4 Barium solution, stock, 1 ml = 100 ug Ba: Dissolve 0.15 g
BaCl2 (mole fraction Ba= 0.6595), dried at 250°C for 2 hours, weighed
accurately to at least four significant figures, in 10 ml water with 1 ml
(1:1) HCl. Add 10.0 ml (1:1) HCl and dilute to 1,000 ml with water.
5.3.5 Beryllium solution, stock, 1 ml= 100 ug Be: Do not dry.
Dissolve 1.97 g BeS04·4H20 (mole fraction Be = 0.0509), weighed accurately
to at least four significant figures, in water, add 10.0 ml concentrated
HN03, and dilute to 1,000 ml with water.
5.3.6 Cadmium solution, stock, 1 ml = 100 ug Cd: Dissolve 0.11 g
CdO (mole fraction Cd = 0.8754), weighed accurately to at least four
significant figures, in a minimum amount of (1:1) HN03. Heat to increase
rate of dissolution. Add 10.0 ml concentrated HN03 and dilute to 1,000 ml
with water.
6010 - 6 Revision 1
December 1987
5.3.7 Calcium solution, stock, 1 ml = 100 ug Ca: Suspend 0.25 g
CaC03 (mole Ca fraction = 0.4005), dried at 180°C for 1 hour before
weighing, weighed accurately to at least four significant figures, in
water and dissolve cautiously with a minimum amount of (1:1) HN03. Add
10.0 ml concentrated HN03 and dilute to 1,000 ml with water.
5.3.8 Chromium solution, stock, 1 ml = 100 ug Cr: Dissolve 0.19 g
Cr03 (mole fraction Cr = 0.5200), weighed accurately to at least four
significant figures, in water. When solution is complete, acidify with
10 ml concentrated HN03 and dilute to 1,000 ml with water.
5.3.9 Cobalt solution, stock, 1 ml = 100 ug Co: Dissolve 0.1000 g
of cobalt metal, weighed accurately to at least four significant figures,
in a minimum amount of (1:1) HN03. Add 10.0 ml (1:1) HCl and dilute to
5.3.10 Copper solution, stock, 1 ml= 100 ug Cu: Dissolve 0.13 g CuO
(mole fraction Cu= 0.7989), weighed accurately to at least four
significant figures), in a minimum amount of (1:1) HN03. Add 10.0 ml
concentrated HN03 and dilute to 1,000 ml with water.
5.3.11 Iron solution, stock, 1 ml = 100 ug Fe: Dissolve 0.14 g
Fe203 (mole fraction Fe = 0.6994), weighed accurately to at least four
significant figures, in a warm mixture of 20 ml (1:1) HCl and 2 ml of
concentrated HN03. Cool, add an additional 5.0 ml of concentrated HN03,
and dilute to 1,000 ml with water.
5.3.12 Lead solution, stock, 1 ml = 100 ug Pb: Dissolve 0.16 g
Pb(N03)2 (mole fraction Pb= 0.6256), weighed accurately to at least four
significant figures, in a minimum amount of (1:1) HN03. Add 10 ml (1:1)
HN03 and dilute to 1,000 ml with water.
5.3.13 lithium solution, stock, 1 ml= 100 ug Li: Dissolve 0.5324 g
lithium carbonate (mole fraction Li = 0.1878), weighed accurately to at
least four significant figures, in a minimum amount of (1:1) HCl and
dilute to 1,000 ml with water.
5.3.14 Magnesium solution, stock, 1 ml= 100 ug Mg: Dissolve 0.17 g
MgO (mole fraction Mg = 0.6030), weighed accurately to at least four
significant figures, in a minimum amount of (1:1) HN03. Add 10.0 ml (1:1)
5.3.15 Manganese solution, stock, 1 ml = 100 ug Mn: Dissolve
0.1000 g of manganese metal, weighed accurately to at least four
significant figures, in acid mixture (10 ml concentrated HCl and 1 ml
concentrated HN03) and dilute to 1,000 ml with water.
5.3.16 Molybdenum solution, stock, 1 ml = 100 ug Mo: Dissolve
0.20 g (NH4)6Mo7024.4H20 (mole fraction Mo = 0.5772), weighed accurately
to at least four significant figures, in water and dilute to 1,000 ml with
water.
6010 - 7 Revision 1
December 1987
5.3.17 Nickel solution, stock, 1 ml= 100 ug Ni: Dissolve 0.1000 g
of nickel metal, weighed accurately to at least four significant figures,
in 10.0 ml hot concentrated HN03, cool, and dilute to 1,000 ml with water.
5.3.18 Phosphate solution, stock, 1 ml = 100 ug P: Dissolve 0.4393 g
anhydrous KH2P04 (mole fraction P = 0.2276), weighed accurately to at
least four significant figures, in water. Dilute to 1,000 ml.
5.3.19 Potassium solution, stock, 1 ml = 100 ug K: Dissolve 0.19 g
KCl (mole fraction K = 0.5244) dried at ll0°C, weighed accurately to at
least four significant figures, in water and dilute to 1,000 ml.
5.3.20 Selenium solution, stock, 1 ml = 100 ug Se: Do not dry.
Dissolve 0.17 g H2Se03 (mole fraction Se = 0.6123), weighed accurately to
at least four significant figures, in water and dilute to 1,000 ml.
5.3.21 Silver solution, stock, 1 ml= 100 ug Ag: Dissolve 0.16 g
AgN03 (mole fraction Ag = 0.6350), weighed accurately to at least four
significant figures, in water and 10 ml concentrated HN03. Dilute to
5.3.22 Sodium solution, stock, 1 ml = 100 ug Na: Dissolve 0.25 g
NaCl (mole fraction Na = 0.3934), weighed accurately to at least four
significant figures, in water. Add 10.0 ml concentrated HN03 and dilute to
5.3.23 Strontium solution, stock, 1 ml = 100 ug Sr: Dissolve
0.2415 g of strontium nitrate (Sr(N03)2) (mole fraction 0.4140), weighed
accurately to at least four significant figures, in a 1-l iter flask
containing 10 ml of concentrated HCl and 700 ml of water. Dilute to
1000 ml with water.
5.3.24 Thallium solution, stock, 1 ml= 100 ug Tl: Dissolve 0.13 g
T1N03 (mole fraction Tl = 0.7672), weighed accurately to at least four
significant figures, in water. Add 10.0 ml concentrated HN03 and dilute to
5.3.25 Vanadium solution, stock, 1 ml 100 ug V: Dissolve
0.23 g NH403 (mole fraction V = 0.4356), weighed accurately to at least
four significant figures, in a minimum amount of concentrated HN03. Heat
to increase rate of dissolution. Add 10.0 ml concentrated HN03 and dilute
to 1,000 ml wit~ water.
5.3.26 Zinc solution, stock, 1 ml = 100 ug Zn: Dissolve 0.12 g ZnO
(mole fraction Zn = 0.8034), weighed accurately to at least four
significant figures, in a minimum amount of dilute HN03. Add 10.0 ml
5.4 Mixed calibration standard solutions - Prepare mixed calibration
standard solutions by combining appropriate volumes of the stock solutions in
volumetric flasks (see Table 3). Add 2 ml (1:1) HN03 and 10 ml of (1:1) HCl
and dilute to 100 ml with water. Prior to preparing the mixed standards, each
stock solution should be analyzed separately to determine possible spectral
6010 - 8 Revision 1
December 1987
interference or the presence of impurities. Care should be taken when
preparing the mixed standards to ensure that the elements are compatible and
stable together. Transfer the mixed standard solutions to FEP fluorocarbon or
previously unused polyethylene or polypropylene bottles for storage. Fresh
mixed standards should be prepared, as needed, with the realization that
concentration can change on aging. Calibration standards must be initially
verified using a quality control sample (see Step 5.8) and monitored weekly
for stability. Some typical calibration standard combinations are listed in
Table 3. All mixtures should then be scanned using a sequential spectrometer
to verify the absence of interelement spectral interference in the recommended
mixed standard solutions.
NOTE: If the addition of silver to the recommended acid combination
results in an initial precipitation, add 15 ml of water and warm
the flask until the solution clears. Cool and dilute to 100 ml
with water. For this acid combination, the silver concentration
should be limited to 2 mg/L. Silver under these conditions is
stable in a tap-water matrix for 30 days. Higher concentrations of
silver require additional HCl.
TABLE 3.
MIXED STANDARD SOLUTIONS
Solution Elements
I Be, Cd, Mn, Pb, Se and Zn

II Ba, Co, Cu, Fe, and V
II I As, Mo
IV Al, Ca, Cr, K, Na, Ni, Li , and Sr
v Ag (see Note to Step 5.4),
Mg, Sb, and Tl
VI p
5.5 Two types of blanks are required for the analysis. The calibration
blank is used in establishing the analytical curve, and the reagent blank is
used to correct for possible contamination resulting from varying amounts of
the acids used in the sample processing.
5.5.l The calibration blank is prepared by diluting 2 ml of
(1:1) HN03 and 10 ml of (1:1) HCl to 100 ml with water. Prepare a
sufficient quantity to flush the system between standards and samples.
5. 5. 2 The reagent blank must contain a11 the reagents and in the
same volumes as used in the processing of the samples. The reagent blank
6010 - 9 Revision 1
December 1987
must be carried through the complete procedure and contain the same acid
concentration in the final solution as the sample solution used for
analysis.
5.6 The instrument check standard is prepared by the analyst by combining
compatible elements at concentrations equivalent to the midpoint of their
respective calibration curves (see Step 8.6.2.1 for use).
5. 7 The interference check solution is prep a red to contain known
concentrations of interfering elements that will provide an adequate test of
the correction factors. Spike the samp 1e with the elements of interest at
approximate concentrations of 10 times the instrumental detection limits. In
the absence of measurable analyte, overcorrection could go undetected because
a negative value could be reported as zero. If the particular instrument will
display overcorrection as a negative number, this spiking procedure will not
be necessary.
5.8 The quality control sample should be prepared in the same acid matrix
as the calibration standards at 10 times the instrumental detection limits and
in accordance with the instructions provided by the supplier.
6.1 See the introductory material in Chapter Three, Inorganic Analytes,
Steps 3.1 through 3.3.
7.0 PROCEDURE
7.1 Preliminary treatment of all matrices is always necessary because of
the complexity and variability of sample matrices. Solubilization and
digestion procedures are presented in Sample Preparation Methods (Methods
3005-3050).
7.2 Set up the instrument with proper operating parameters established in
Step 4.2. The instrument must be allowed to become thermally stable before
beginning (usually requiring at least 30 minutes of operation prior to
calibration).
7. 3 Profile and calibrate the instrument according to the instrument
manufacturer's recommended procedures, using the typical mixed calibration
standard solutions described in Step 5.4. Flush the system with the
calibration blank (Step 5.5.1) between each standard. (Use the average
intensity of multiple exposures for both standardization and sample analysis
to reduce random error.)
7 .4 Before beginning the sample run, reanalyze the highest mixed
calibration standard as if it were a sample. Concentration values obtained
should not deviate from the actual values by more than 5% (or the established
control limits, whichever is lower). If they do, follow the recommendations of
the instrument manufacturer to correct for this condition.
7.5 Flush the system with the calibration blank solution for at least
1 minute (Step 5.5.1) before the analysis of each sample (see Note to Step
December 1987
7.3). Analyze the instrument check standard (Step 5.6) and the calibration
blank (Step 5.5.1) after each 10 samples.
7. 6 Ca lcul at ions: If dilutions were performed, the appropriate factors
must be applied to sample values. All results should be reported in ug/L with
up to three significant figures.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Dilute and reanalyze samples that are more concentrated than the
linear calibration limit or use an alternate, less sensitive line for which
quality control data is already established.
8.3 Employ a minimum of one reagent blank per sample batch to determine
if contamination or any memory effects are occurring.
8.4 Analyze one replicate sample for every 20 samples or per analytical
batch, whichever is more frequent. A rep 1i cate sample is a samp 1e brought
through the whole sample preparation and analytical process.
8.5 It is recommended that whenever a new or unusual sample matrix is
encountered, a series of tests be performed prior to reporting concentration
data for analyte elements. These tests, as outlined in Steps 8.5.1 and 8.5.2,
will ensure the analyst that neither positive nor negative interferences are
operating on any of the analyte elements to distort the accuracy of the
reported values.
8.5.1 Serial dilution: If the analyte concentration is sufficiently
high (minimally, a factor of 10 above the instrumental detection limit
after dilution}, an analysis of a 1:4 dilution should agree within ± 10%
of the original determination. If not, a chemical or physical interference
effect should be suspected.
8.5.2 Matrix spike addition: An analyte spike added to a portion of
a prepared sample, or its dilution, should be recovered to within 75% to
125% of the known value. The spike addition should produce a minimum level
of 10 times and a maximum of 100 times the instrumental detection limit.
If the spike is not recovered within the specified limits, a matrix effect
should be suspected.
CAUTION: If spectral overlap is suspected, use of computerized
compensation, an alternate wavelength, or comparison with an
alternate method is recommended.
8.6 Check the instrument standardization by analyzing appropriate check
standards as follows.
8.6.1 Check instrument calibration using a calibration blank and two
appropriate standards.
December 1987
8. 6. 2 Verify ca 1 i brat ion every 10 samp 1es and at the end of the
analytical run, using a calibration blank (Step 5.5.1) and a check
standard (Step 5.6).
8.6.2.1 The results of the check standard are to agree within
10% of the expected value; if not, terminate the analysis, correct
the problem, and recalibrate the instrument.
8.6.2.2 The results of the calibration blank are to agree
within three standard deviations of the mean blank value. If not,
repeat the analysis two more times and average the results. If the
average is not within three standard deviations of the background
mean, terminate the analysis, correct the problem, recalibrate, and
reanalyze the previous 10 samples.
8.6.3 Verify the interelement and background correction factors at
the beginning and end of an analytical run or twice during every 8-hour
work shift, whichever is more frequent. Do this by analyzing the
interference check sample (Step 5.7). Results should be within± 20% of
the true value obtained in Step 8.6.2.1.
8.6.4 Spiked replicate samples are to be analyzed at a frequency of
20%.
8.6.4.1 The relative percent difference between replicate
determinations is to be calculated as follows:
RPO
where:
RPO = relative percent difference.
D1 = first sample value.
D2 =second sample value (replicate).
(A control limit of± 20% for RPD shall be used for sample values
greater than 10 times the instrument detection limit.)
8.6.4.2 The spiked replicate sample recovery is to be within
± 20% of the actual value.
9.1 In an EPA round-robin Phase 1 study, seven laboratories applied the
ICP technique to acid-distilled water matrices that had been spiked with
various metal concentrates. Table 4 lists the true values, the mean reported
values, and the mean percent relative standard deviations.
9.2 In a single laboratory evaluation, seven wastes were analyzed for 22
e1ements by this method. The mean percent relative standard deviation from
triplicate analyses for all elements and wastes was 9 ± 2%. The mean percent
recovery of spiked elements for all wastes was 93 ± 6%. Spike levels ranged
December 1987
from 100 ug/L to 100 mg/L. The wastes included sludges and industrial
wastewaters.
10. 0 REFERENCES
1. Winge, R.K.; Peterson, V.J.; Fassel, V.A. Inductively Coupled Plasma-
Atomic Emission Spectroscopy: Prominent Lines (final report, March 1977 -
February 1978); EPA-600/4-79-017, Environmental Research Laboratory,
Athens, GA, March 1979; Ames Laboratory: Ames IA.
2. Test Methods: Methods for Organic Chemical Analysis of Municipal and
Industrial Wastewater; U.S. Environmental Protection agency. Office of
Research and Development. Environmental Monitoring and Support
Laboratory. ORD Publication Offices of Center for Environmental Research
Information: Cincinnati, OH, 1982; EPA-600/4-82-057.
3. Patel, B.K.; Raab, G.A.; et al. Report on a Single Laboratory Evaluation
of Inductively Coupled Optical Emission Method 6010; EPA Contract No.
68-03-3050, December 1984.
4. Sampling and Analysis Methods for Hazardous Waste Combustion; U.S.
Environmental Protection Agency; Air and Energy Engineering Research
Laboratory, Office of Research and Development: Research Triangle Park,
NC, 1986; Prepared by Arthur D. Little, Inc.
5. Bowmand, P.W.J.M. Line Coincidence Tables for Inductively Coupled Plasma
Atomic Emission Spectrometry, 2nd ed.; Pergamon: 1984.
December 1987
TABLE 4.
ICP PRECISION AND ACCURACY DATAa
Sample No. 1 Sample No. 2 Sample No. 3

Mean Re- Mean Re- Mean Re-
True ported Mean True ported Mean True ported Mean
Ele- Value Value sob Value Value sob Value Value sob
ment (ug/L) (ug/L) (%) (ug/L) (ug/L) (%) (ug/L) (ug/L) (%)
------------------------------------------------------------------------------
Be 750 733 6.2 20 20 9.8 180 176 5.2
Mn 350 345 2.7 15 15 6.7 100 99 3.3
v 750 749 1.8 70 69 2.9 170 169 1.1
As 200 208 7.5 22 19 23 60 63 17
Cr 150 149 3.8 10 10 18 50 50 3.3
Cu 250 235 5 .1 11 11 40 70 67 7.9
Fe 600 594 3.0 20 19 15 180 178 6.0
Al 700 696 5.6 60 62 33 160 161 13
Cd 50 48 12 2.5 2.9 16 14 13 16
Co 700 512 10 20 20 4 .1 120 108 21
Ni 250 245 5.8 30 28 11 60 55 14
Pb 250 236 16 24 30 32 80 80 14
Zn 200 201 5.6 16 19 45 80 82 9.4
sec 40 32 21.9 6 8.5 42 10 8.5 8.3
aNot al 1 elements were analyzed by all laboratories.

bso = standard deviation.
CResults for Se are from two laboratories.
December 1987
METHOD 6010
INDUCTIVELY COUPLED ATOMIC EMISSION SPECTROSCOPY
Start
7 1 Prepare 1aaplt
u11ng Method 3006,
3010, 3040, 3040,
or 3060 u
appropriate
7 4 Set up and 7 6 Flu1h 1y1tea

1tab1l1ze and analyze 1aaple
in1tru•e11.t
7 6 Analyze check
7 3 Profile and 1tandard and
calibrate cal1brat1on blank
inatru•ent after each 10
1ample1
7 4 Reanalyze
h1gh11t •ixed 7 e Calculate
cal1br1tion concentrat1on1
1tandard
7.4 Adjut
iutruaont per
•aautacturer 1
1 Stop
r1coaae1.dation1
December 1987
METHOD 6020
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY

1.1 Inductively coupled plasma-mass spectrometry {ICP-MS) is a tech~ique
which is applicable to µg/L concentrations of a large number of elements in
water and wastes after appropriate sample preparation steps are taken [1,2].
When dissolved constituents are required, samples must be filtered and acid-
preserved prior to analysis. No further digestion is required prior to analysis
for dissolved elements. Acid-digestion prior to filtration and analysis is
required for groundwater, aqueous samples, industrial wastes, soils, sludges,
sediments, and other solid wastes for which total (acid-leachable) elements are
required.
1.2 Elements for which Method 6020 has shown acceptable performance in a
multi-laboratory study are listed in TABLE 1. Acceptability of the method for
an element was based upon the multi-laboratory performance compared with that of
either furnace atomic absorption spectroscopy or inductively coupled plasma-
atomic emission spectroscopy. Other elements may be added to Table 1 as more
information becomes available. Multi-laboratory performance data for the listed
elements {and others) are provided in Section 9. Instrument detection limits,
sensitivities, and linear ranges for these elements will vary with the matrices,
instrumentation, and operating conditions.
1.3 Use of this method is restricted to spectroscopists who are
knowledgeable in the recognition and the correction of spectral, chemical, and
physical interferences in ICP-MS.
1.4 An appropriate internal standard is required for each analyte
determined by ICP-MS. Recommended internal standards are 6 Li, 45 Sc, 89 Y, 103 Rh,
115
In, 159 Tb, 165 Ho, and 209 Bi. The lithium internal standard should have an
enriched abundance of 6 Li, so that interference from lithium native to the sample
is minimized. Other elements may need to be used as internal standards when
samples contain significant amounts of the recommended internal standards.

2.1 Prior to analysis, samples which require total values must be digested
using appropriate sample preparation methods (such as Methods 3005 - 3051).
2.2 Method 6020 describes the multi-elemental determination of analytes
by ICP-MS. The method measures ions produced by a radio-frequency inductively
coupled plasma. Analyte species originating in a liquid are nebulized and the
resulting aerosol transported by argon gas into the plasma torch. The ions
produced are entrained in the plasma gas and introduced, by means of a water-
6020-1 Revision 0
November 1992
cooled interface, into a quadrupole mass spectrometer. The ions produced in the
plasma are sorted according to their mass-to-charge ratios and quantified with
a channel electron multiplier. Interferences must be assessed and valid
corrections applied or the data flagged to indicate problems. Interference
corre~t ion must include compensation for background ions contributed by the
plasma gas, reagents, and constituents of the sample matrix.
3.0 INTERFERENCES
3.1 Isobaric elemental interferences in ICP-MS are caused by isotopes of
different elements forming atomic ions with the same nominal mass-to-charge ratio
(m/z). A data system must be used to correct for these interferences. This
involves determining the signal for another isotope of the interfering element
and subtracting the appropriate signal from the analyte isotope signal. Since
commercial ICP-MS instruments nominally provide unit resolution at 10% of the
peak height, very high ion currents at adjacent masses can also contribute to ion
signals at the mass of interest. Although this type of interference is uncommon,
it is not easily corrected, and samples exhibiting a significant problem of this
type could require resolution improvement, matrix separation, or use of another
method.
3.2 Isobaric molecular and.doubly-charged ion interferences in ICP-MS are
caused by ions consisting of more than one atom or charge, respectively. Most
isobaric interferences that could affect ICP-MS determinations have been
identified in the literature [3,4]. Examples include Arel+ ions on the 75 As
signal and Moo+ on the cadmium isotopes. Since the 35 Cl natural abundance of
75.8 percent is 3.13 times the 37 Cl abundance of 24.2 percent, the choride
corrections can be calculated as follows (where the 38 Ar37 Cl+ contribution at m/z
75 is a negligible 0.06 percent of the 40 Ar 35 Cl+ signal):
corrected arsenic signal = (m/z 75 signal} - (3.13} (m/z 77 signal} +
(2.53) (m/z 82 signal), (where the final term adjusts for any selenium
contribution at 77 m/z),
Similarly,
corrected cadmium signal = (m/z 114 signal) - (0.027)(m/z 118 signal) -
(1.63)(m/z 108 signal), (where last 2 terms adjust for any tin or Moo+
contributions at m/z 114).
The above equations are based upon the constancy of the isotopic ratios for the
interfering species. Corrections that presume a constant fraction of a molecular
ion relative to the "parent" ion have not been found [5] to be reliable, e.g.,
oxide levels can vary. If a correction for an oxide ion is based upon the ratio
of parent-to-oxide ion intensities, the correction must be adjusted for the
degree of oxide formation by the use of an appropriate oxide internal standard
previously demonstrated to form a similar level of oxide as the interferant.
6020-2 Revision 0
November 1992
This type of correction has been reported [5] for oxide-ion corrections using
ThO+/Th+ for the determination of rare earth elements.
3.3 Physical interferences are associated with the sample nebulization and
transport processes as well as with ion-transmission efficiencies. Nebulization
and transport processes can be affected if a matrix component causes a change in
surface tension or viscosity. Changes in matrix composition can cause
significant signal suppression or enhancement [6]. Dissolved solids can deposit
on the nebulizer tip of a pneumatic nebulizer and on the interface skimmers
{reducing the orifice size and the instrument performance). Total solid levels
below 0.2% {2,000 mg/l) have been recommended [7] to minimize solid deposition.
An internal standard can be used to correct for physical interferences, if it is
carefully matched to the analyte so that the two elements are similarly affected
by matrix changes [8]. When the intensity level of an internal standard is less
than 30 percent or greater than 120 percent of the intensity of the first
standard used during calibration, the sample must be reanalyzed after a fivefold
{1+4) dilution has been performed.
3.4 Memory interferences can occur when there are large concentration
differences between samples or standards which are analyzed sequentially. Sample
deposition on the sampler and skimmer cones, spray chamber design, and the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse period between samples must be long enough to eliminate significant
memory interference.

4.1 Inductively coupled plasma-mass spectrometer:
4.1.l A system capable of providing resolution, better than or
equal to 1 amu at 10% peak height is required. The system must have a
mass range from at least 6 to 240 amu and a data system that a11 ows
corrections for isobaric interferences and the application of the internal
standard technique. Use of a mass-flow controller for the nebulizer argon
and a peristaltic pump for the sample solution are recommended.
4.1.2 Argon gas supply: high-purity grade (99.99%).
5.0 REAGENTS
5.1 Acids used in the preparation of standards and for sample processing
must be of high purity. Redistilled acids are recommended because of the high
sensitivity of ICP-MS. Nitric acid at less than 2 per cent (v/v) is required for
ICP-MS to minimize damage to the interface and to minimize isobaric molecular-ion
interferences with the analytes. Many more molecular-ion interferences are
observed on the analytes when hydrochloric and sulfuric acids are used [3,4].
Concentrations of antimony and silver above 300 µg/l require 1% (v/v) HCl for
6020-3 Revision 0
November 1992
stability. If HCl is added as a stabilizer, then corrections for the chloride
molecular-ion interferences must be applied to all data generated.
5. 2 Reagent water: Reagent water will be interfere nee free. A11
references to water in the method refer to reagent water unless otherwise
specified. Refer to Chapter One for a definition of reagent water.
5.3 Standard stock solutions may be purchased or prepared from ultra-high
purity grade chemicals or metals (99.99 to 99.999% pure). See Method 6010A,
Section 5.3, for instructions on preparing standard solutions from solids.
5.3.l Bismuth internal standard solution, stock, 1 ml= 100 µg Bi:
Dissolve 0.1115 g Bi 2 03 in a minimum amount of dilute HN0 3 • Add 10 ml
cone. HN0 3 and dilute to 1,000 ml with reagent water.
5.3.2 Holmium internal standard solution, stock, 1 ml = 100 µg Ho:
Dissolve 0.1757 g Ho 2 (C0 3 } 2 ·5H 20 in 10 ml reagent water and 10 ml HN0 3 •
After di sso l ut ion is complete, warm the solution to degas. Add 10 ml
cone. HN0 3 and dilute to 1,000 ml with reagent water.
5.3.3 Indium internal standard solution, stock, 1 ml = 100 µg In: ,
Dissolve 0.1000 g indium metal in 10 ml cone. HN0 3 • Dilute to 1,000 ml
with reagent water.
5.3.4 Lithium internal standard solution, stock, 1ml=100 µg 6 Li:
Dissolve 0.6312 g 95-atom-% 6 Li, Li 2C0 3 in 10 ml of reagent water and 10 ml
HN0 3 • After dissolution is complete, warm the solution to degas. Add
10 ml cone. HN0 3 and dilute to 1,000 ml with reagent water.
5.3.5 Rhodium internal standard solution, stock, 1 ml = 100 µg Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (III) (NH 4 ) 3 RhCl 6 in 10 ml
reagent water. Add 100 ml cone. HCl and dilute to 1,000 ml with reagent
water.
5.3.6 Scandium internal standard solution, stock, 1 ml= 100 µg Sc:
Dissolve 0.15343 g Sc 203 in 10 ml (l+l) hot HN0 3 • Add 5 ml cone. HN0 3 and
dilute to 1,000 ml with reagent water.
5.3.7 Terbium internal standard solution, stock, 1 ml= 100 µg Tb:
Dissolve 0.1828 g Tb 2 (C0 3 ) 3 ·5H 20 in 10 ml (l+l) HN0 3 • After dissolution is
complete, warm the solution to degas. Add 5 ml cone. HN0 3 and dilute to
1,000 ml with reagent water.
5.3.8 Yttrium internal standard solution, stock, 1 ml = 100 µg Y:
Dissolve 0.2316 g Y2 (C0 3 ) 3 .3H 20 in 10 ml (l+l) HN0 3 • Add 5 ml cone. HN0 3
and dilute to 1,000 ml with reagent water.
6020-4 Revision 0
November 1992
5.3.9 Titanium solution, stock, 1ml=100 µg Ti: Dissolve 0.4133 g
(NH 4 ) 2 TiF 6 in reagent water. Add 2 drops cone. HF and dilute to l;-000 ~l
with reagent water.
5.3.10 Molybdenum solution, stock, 1 ml = 100 µg Mo: Dissolve
0. 2043 g (NH 4 ) 2 Mo0 4 in reagent water. Dilute to 1, 000 ml with reagent
water.
5.4 Mixed calibration standard solutions -- Dilute the stock-standard
solutions to levels in the linear range for the instrument in a sol vent
consisting of 1 percent (v/v) HN0 3 in reagent water. The calibration standard
solutions must contain a suitable concentration of an appropriate internal
standard for each analyte. Generally, an internal standard should be no more
than 4550 amu removed from the analvte. Recommended internal standards include
6
li, Sc, 89 Y, 103 Rh, 115 In, 159Te, r69 Ho, and 209 Bi. Prior to preparing the mixed
standards, each stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities. Care must be taken when
preparing the mixed standards that the elements are compatible and stable.
Transfer the mixed standard solutions to freshly acid-cleaned FEP fluorocarbon
bottles for storage. Fresh mixed standards must be prepared as needed with the
realization that concentrations can change on aging. Calibration standards must
be initially verified using a quality control sample (see Section 5.8) and
monitored weekly for stability.
5.5 Blanks: Three types of blanks are required for the analysis. The
calibration blank is used in establishing the calibration curve. The reagent
blank is used to monitor for possible contamination resulting from the sample
preparation procedure. The rinse blank is used to flush the system between all
samples and standards.
5.5.1 The calibration blank consists of 1 percent HN0 (v/v) in 3
reagent water along with the selected concentrations of internal standards
such that there is an appropriate internal standard element for each of
the analytes.
5.5.2 The reagent blank must contain all the reagents in the same
volumes as used in processing the samples. The reagent blank must be
carried through the complete procedure and contain the same acid
concentration in the final solution as the sample solutions used for
analysis.
5.5.3 The rinse blank consists of 1 to 2 percent HN0 3 (v/v) in
reagent water. Prepare a sufficient quantity to flush the system between
standards and samples.
5.6 The instrument check standard is prepared by the analyst by combining
compatible elements at concentrations equivalent to the midpoint of their
respective calibration ranges.
6020-5 Revision 0
November 1992
5.7 The interference check solution(s) (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the magnitude of
interferences and provide an adequate test of any corrections. Chloride in the
ICS provides a means to evaluate software corrections for chloride-related
interferences such as 35Cl 160+ on 51 V+ and 40Ar 35 Cl + on 75As+. Iron is used to
demonstrate adequate resolution of the spectrometer for the determination of
manganese. Molybdenum serves to indicate oxide effects on cadmium isotopes. The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences. The ICS is used to
verify that the interference 1evel s are corrected by the data system within
quality control limits.
5.7.1 The final concentrations of elements in ICS A and ICS AB are
shown in Table 2. These solutions must be prepared from ultra-pure
reagents. They can be obtained commercially or prepared by the following
procedure.
5.7.1.1 Mixed ICS solution I may be prepared by adding
13.903 g Al(N0 3 ) 3 ·9H 2 0, 2.498 g CaC0 3 (dried at 180 C for 1 h before
weighing), 1.000 g Fe, 1.658 g MgO, 2.305 g Na 2 C0 3 , and 1.767 g K2 C0 3
to 25 ml of reagent water. Slowly add 40 ml of (l+l) HN0 3 • After
dissolution is complete, warm the solution to degas. Cool and
dilute to 1,000 ml with reagent water.
5.7.1.2 Mixed ICS solution II may be prepared by slowly
adding 7.444 g 85 % H3 P04 , 6.373 g 96% H2 S0 4 , 40.024 g 37% HCl, and
10.664 g citric acid C607H8 to 100 ml of reagent water. Dilute to
1,000 ml with reagent water.
5.7.1.3 Mixed ICS solution III may be prepared by adding 5 ml
each of 100 µg/ml arsenic stock solution, chromium stock solution,
copper stock so 1ut ion, manganese stock so 1ut ion, se 1en i um stock
solution, silver stock solution, and zinc stock solution, 10 ml each
of 100 µg/ml cobalt stock solution, nickel stock solution, and
vanadium stock solution, and 2.5 ml of 100 µg/ml cadmium stock
solution. Dilute to 100 ml with 2% HN0 3 •
5.7.1.4 Working ICS Solutions
5. 7 .1.4.1 ICS A may be prepared by adding 50 ml of
mixed JCS solution I (5.7.1.1), 10 ml each of 100 µg/ml
titanium stock solution (5.3.9) and molybdenum stock solution
(5.3.10), and 25 ml of mixed ICS solution II (5.7.1.2).
Dilute to 100 ml with reagent water. ICS solution A must be
prepared fresh weekly.
5. 7.1. 4. 2 ICS AB may be prepared by adding 50 ml of
mixed JCS solution I (5.7.1.1), 10 ml each of 100 µg/ml
titanium stock solution (5.3.9) and molybdenum stock solution
6020-6 Revision 0
November 1992
(5.3.10), 25 ml of mixed ICS solution II (5.7.1.2), and 2 ml
of Mixed ICS solution III (5.7.1.3). Dilute to 100 ml with
reagent water. ICS solution AB must be prepared fresh weekly.
5.8 The quality control sample is the initial calibration verification
solution, which must be prepared in the same acid matrix as the calibration
standards. This solution must be an independent standard near the midpoint of
the 1i near range at a concentration other than that used for instrument
calibration. An independent standard is defined as a standard composed of the
analytes from a source different from those used in the standards for instrument
calibration.

6.1 Sample collection procedures should address the considerations
described in Chapter Nine of this Manual.
6.2 See the introductory material in Chapter Three, Inorganic Analytes,
Sections 3.1.3 for information on sample handling and preservation. Only
polyethylene or Teflon containers are recommended for use in Method 6020.
7. 0 PROCEDURE
7.1 Solubilization and digestion procedures are presented in the Sample
Preparation Methods (e.g. Methods 3005 - 3050).
7.2 Initiate appropriate operating configuration of the instrument
computer.
7.3 Set up the instrument with the proper operating parameters.
7 .4 Operating conditions: In general, the analyst should follow the
instructions provided by the instrument manufacturer. The following is a
suggested listing of operating conditions which may be useful.
Perkin-Elmer Sciex
Elan 500 VG Plasmaguad
Plasma Gas (lpm) 12 13
Aux. Gas (lpm) 1.2 0.65
Neb. Gas (lpm) 0.95 0.69
Forward power (kW) 1. 2 1.30
Reflected power (W) < 5 < 5
Sampling Height 18 12
(mm above load coil)
Note: Addition of nitrogen to the plasma argon has been reported to
decrease many molecular interferences [9].
6020-7 Revision 0
November 1992
Allow at least 30 minutes for the instrument to equilibrate before analyzing
any samples. This must be verified by analyzing a tuning solution (such as 100
µg/L Li, Co, In, and Tl) at least four times with relative standard deviations
of less than 103 for the analytes contained in the tuning solution.
Note: Precautions must be taken to protect the channel electron multiplier
from high ion currents. The channel electron multiplier suffers from fatigue
after being exposed to high ion currents. This fatigue can last from several
seconds to hours depending on the extent of exposure. During this time period,
response factors are constantly changing, which invalidates the calibration
curve, causes instability, and invalidates sample analyses.
7.5 Conduct mass calibration and resolution checks in the mass regions of
interest. The mass calibration and resolution parameters are required criteria
which must be met prior to any samples being analyzed. If the mass calibration
exceeds a difference of more than 0.1 amu from the actual value, then the mass
calibration must be adjusted to the correct values. The resolution must also be
verified to be less than 1.0 amu full width at 10 percent peak height.
7 .6 Calibrate the instrument for the analytes of interest for the isotopes
shown in Table 3 using the calibration blank and at least a single standard
according to the manufacturer's recommended procedure. Flush the system with the
rinse blank (5.5.3) between each standard solution. Use the average of the
multiple integrations for both standardization and sample analysis.
7.7 Some elements (such as Hg, W, and Mo) require extended flushing times
which need to be determined for each instrumental system.
7.8 All masses which could affect data quality should be monitored to
determine potential effects from matrix components on the analyte peaks. These
masses must be monitored either simultaneously in a separate scan or at the same
time quantification occurs.
7.9 Immediately after the calibration has been established, the
calibration must be verified and documented for every analyte by the analysis of
the initial calibration verification solution (Section 5.8). When measurements
exceed± 10% of the accepted value the analysis must be terminated, the problem
corrected, the instrument rec a1 i brated, and the ca 1i brat ion reverified. Any
samples analyzed under an out-of-control calibration must be reanalyzed.
7.10 Flush the system with the rinse blank solution (5.5.3) for at least
30 seconds before the analysis of each sample (see Section 7.7). Aspirate each
sample for at least 30 seconds before collecting data. Analyze the instrument
check standard (Section 5.6) and the calibration blank (Section 5.5.1) at a
frequency of at least once every 10 analytical samples.
7 .11 Dilute and reanalyze samples that are more concentrated than the
linear range for an analyte (or species needed for a correction) or measure an
alternate less-abundant isotope.
6020-8 Revision O
November 1992
7.12 Calculations: The quantitative values shall be reported in units of
micrograms per liter {µg/L) for aqueous samples and milligrams per kilogram
(mg/kg) for sol id samples. If dilutions were performed, the appropriate
corrections must be applied to the sample values.
7.12.1 Results for solids must be reported on a dry-weight basis as
follows:
(1) A separate determination of percent solids must be
performed.
(2) The concentrations determined in the digest are to be
reported on the basis of the dry weight of the sample.
Concentration (dry weight)(mg/kg) = ~ ~ ~
Where,
C Digest Concentration (mg/L)
V = Final volume in liters after sample preparation
W= Weight in kg of wet sample
% Solids
s
100
Calculations should include appropriate interference corrections (see
Section 3. 2 for ex amp 1es), i nterna 1 standard norma 1 i zat ion, and the
summation of signals at 206, 207, and 208 m/z for lead to compensate for
any differences in the abundances of these isotopes between samples and
standards.
8.0 QUALITY CONTROL

8.1 All quality control data should be maintained and be available for
easy reference or inspection.
8.2 Instrument Detection Limits (IDL's) (in µg/L) can be estimated by
multiplying by three the average of the standard deviations obtained on three
nonconsecutive days from the analysis of a standard solution {each analyte in
reagent water) at a concentration 3x-25x IDL, with seven consecutive measurements
per day. Each measurement must be performed as though it were a separate
analytical sample {i.e., each measurement must be followed by a rinse and/or any
other procedure normally performed between the analysis of separate samples).
IDL's must be determined at least every three months and kept with the instrument
log book. Refer to Chapter One for additional guidance.
6020-9 Revision 0
November 1992
8.3 The intensities of all internal standards must be monitored for every
analysis. When the intensity of any internal standard fails to fall between 30
and 120 percent of the intensity of that internal standard in the initial
calibration standard, the following procedure is followed. The sample must be
diluted fivefold (1+4) and reanalyzed with the addition of appropriate amounts
of internal standard. This procedure must be repeated unt i1 the i nterna 1
standard intensities fall within the prescribed window. The intensity levels of
the internal standards for the calibration blank (Section 5.5.1) and instrument
check standard (Section 5.6) must agree within ± 20 percent of the intensity
level of the internal standard of the original calibration blank solution. If
they do not agree, terminate the analysis, correct the problem, recalibrate, and
reanalyze the affected samples.
8.4 To obtain analyte data of known quality, it is necessary to measure
more than the analytes of interest in order to determine whether interference
corrections are necessary. If the concentrations of interference sources (such
as C, Cl, Mo, Zr, W} are below the levels that show an effect on the analyte
level, uncorrected equations may be used provided all QC criteria are met. Note
that monitoring the interference sources does not necessarily require monitoring
the interferant itself, but that a molecular species may be monitored to indicate
the presence of the i nterferent. When corrected equat i ans are used, a11 QC
criteria must al so be met. Extensive QC for interference corrections are
required at all times. The monitored masses must include those elements whose
hydrogen, oxygen, hydroxyl, chlorine, nitrogen, carbon and sulfur molecular ions
could impact the analytes of interest. Unsuspected interferences may be detected
by adding pure major matrix components to a sample to observe any impact on the
analyte signals. When an interference source is present, the sample elements
impacted must be flagged to indicate (a} the percentage interference correction
applied to the data or (b} an uncorrected interference by virtue of the elemental
equation used for quant it at ion. The isotope proportions for an e1ement or
molecular-ion cluster provide information useful for quality assurance.
NOTE: Only isobaric elemental, molecular, and doubly charged interference
corrections which use established isotopic response ratios or parent-to-oxide
ratios (provided an oxide internal standard is used as described in Section 3.2)
are acceptable corrections for use in Method 6020.
8.5 Serial dilution: If the analyte concentration is within the linear
dynamic range of the instrument and sufficiently high (minimally, a factor of 100
above the instrumental detection limit}, an analysis of a fivefold dilution must
agree within ± 10% of the original determination. If not, an interference effect
must be suspected. One serial dilution must be analyzed for each twenty samples
or less of each matrix in a batch.
8.6 Matrix spike addition: An analyte spike added to a portion of a
prepared sample, or its dilution, should be recovered to within 75 to 125 percent
of the known value. The spike addition should produce a minimum signal level of
10 times and a maximum of 100 times the instrumental detection limit. If the
spike is not recovered within the specified limits, a matrix effect should be
suspected. The use of a standard-addition analysis procedure can usually
6020-10 Revision 0
November 1992
compensate for this effect. See Section 8.5.3 of Method 6010 for information on
standard additions.
8.7 A Laboratory Control Sample (LCS) should be analyzed for each analyte
using the same sample preparations, analytical methods and QA/QC procedures
employed for the test samples. One LCS should be prepared and analyzed for each
sample batch at a frequency of one LCS for each 20 samples or less.
8.8 Check the instrument standardization by analyzing appropriate quality
control solutions as follows:
8.8.1 Check instrument calibration using a calibration blank
(Section 5.5.1) and the initial calibration verification solution
(Sections 5.8 and 7.9).
8.8.2 Verify calibration at a frequency of every 10 analytical
samples with the instrument check standard (Section 5.6) and the
calibration blank (Section 5.5.1). These solutions must also be analyzed
for each analyte at the beginning of the analysis and after the last
sample.
8.8.3 The results of the initial calibration verification solution
and the instrument check standard must agree within ± 10% of the expected
value. If not, terminate the analysis, correct the problem, and
recalibrate the instrument. Any sample analyzed under an out-of-control
calibration must be reanalyzed at no additional cost to the government.
8.8.4 The results of the calibration blank must be less than 3
times the current IDL for each element. If this is not the case, the
reason for the out-of-control condition must be found and corrected, and
affected samples must be reanalyzed.
8.9 Verify the magnitude of elemental and molecular-ion isobaric
interferences and the adequacy of any corrections at the beginning of an
analytical run or once every 12 hours, whichever is more frequent. Do this by
analyzing the interference check solutions A and AB
8.10 Analyze one duplicate sample for every matrix in a batch at a
frequency of one matrix duplicate for every 20 samples.
6020-11 Revision 0
November 1992
8.10.l The relative percent difference (RPO) between duplicate
determinations must be calculated as follows:
Io, - 02 I
RPO = x 100
where:
RPO = relative percent difference.
01 = first sample value.
02 = second sample value (duplicate)
A control limit of 20% RPO should not be exceeded for analyte values
greater than 100 times the instrumental detection limit. If this limit is
exceeded, the reason for the out-of-control situation must be found and
corrected, and any samples analyzed during the out-of-control condition
must be reanalyzed.

9.1 In an EPA multi-laboratory study, 10 laboratories applied the
ICP-MS technique to both aqueous and solid samples. TABLE 5 summarizes the
method performance data for aqueous samples. Performance data for solid samples
is provided in TABLE 6.
10.0 REFERENCES
1. Horlick, G., et al., Spectrochim. Acta 40B, 1555 {1985).
2. Gray, A.L., Spectrochim. Acta 408, 1525 (1985); 418, 151 (1986).
3. Tan, S.H., and Horlick, G., Appl. Spectrosc. 40, 445 (1986).
4. Vaughan, M.A., and Horlick, G., Appl. Spectrosc. 40, 434 {1986).
5. Lichte, F.E., et al., Anal. Chem. 59, 1150 (1987).
6. Beauchemin, 0., et al., Spectrochim. Acta 42B, 467 (1987).
7. Houk, R.S., Anal. Chem. 58, 97A (1986).
8. Thompson, J.J., and Houk, R.S., Appl. Spectrosc. 41, 801 (1987).
9. Evans, E.H., and Ebdon, L., J. Anal. At. Spectrom. 4, 299 (1989).
6020-12 Revision O
November 1992
TABLE 1. ELEMENTS APPROVED FOR ICP-MS DETERMINATION
Estimated Detection
Element CAS* # Limit (µg/L)
Aluminum 7429-90-5 0.1

Antimony 7440-36-0 0.02
Arsenic 7440-38-2 0.4
Barium 7440-39-3 0.02
Beryllium 7440-41-7 0.1
Cadmium 7440-43-9 0.07
Chromium 7440-47-3 0.02
Cobalt 7440-48-4 0.01
Copper 7440-50-8 0.03
Lead 7439-92-1 0.02
Manganese 7439-96-5 0.04
Nickel 7440-02-0 0.03
Silver 7440-22-4 0.04
Thallium 7440-28-0 0.05
Zinc 7440-66-6 0.08
6020-13 Revision 0
November 1992
TABLE 2. RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS ANO CONCENTRATIONS.
Interference Solution A Solution AB

component Concentration (mg/L) Concentration (mg/L.
Al 500.0 500.0
Ca 500.0 500.0
Fe 500.0 500.0
Mg 500.0 500.0
Na 500.0 500.0
p 500.0 500.0
K 500.0 500.0
s 500.0 500.0
c 1000.0 1000.0
Cl 3600.0 3600.0
Mo 10.0 10.0
Ti 10.0 10.0
As 0.0 0.100
Cd 0.0 0.050
Cr 0.0 0.100
Co 0.0 0.200
Cu 0.0 0.100
Mn 0.0 0.100
Ni 0.0 0.200
Ag 0.0 0.100
Zn 0.0 0.100
6020-14 Revision 0
November 1992
TABLE 3. RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Mass Element of interest
27 Aluminum
121, 123 Antimony
75 Arsenic
138, 137' 136, 135, 134 Barium
~ Beryllium
209 Bismuth (IS)
114, 112, 111, 110, 113, 116, 106 Cadmium
42, 43, 44, 46, 48 Calcium {I)
35, 37, {77, 82) 8 Chlorine (I)
52' 53' 50) 54 Chromium
59 Caba lt
63, 65 Copper
165 Holmium (IS)
. 115, 113 Indium (IS)
56, 54, 57, 58 Iron {I)
139 Lanthanum (I)
~) 207, 206, 204 Lead
6 ) 7 Lit hi um ( IS)
24, 25, 26 Magnesium (I)
55 Manganese
98, 96, 92, 97, 94, {108) 8 Molybdenum (I)
58, 60, 62, §1, 64 Ni eke l
39 Potassium (I)
103 Rhodium (IS)
45 Scandium (IS)
107) 109 Silver
23 Sodium (I)
159 Terbium (IS)
205, 203 Thallium
120, 118 Tin (I)
89 Yttrium (IS)
64, 66, 68, 67, 70 Zinc
NOTE: Method 6020 is recommended for only those analytes listed in Table
1. Other elements are included in this table because they are potential
interferents {labeled I) in the determination of recommended analytes, or because
they are commonly used internal standards (labeled IS). Isotopes are listed in
descending order of natural abundance. The most generally useful isotopes are
underlined and in boldface, although certain matrices may require the use of
alternative isotopes. a These masses are also useful for interference correction
(Section 3.2). b Internal standard must be enriched in the 6 Li isotope. This
minimizes interference from indigenous lithium.
6020-15 Revision 0
November 1992
TABLE 4. SPIKING LEVELS FOR ICP-MS ANALYSIS (µg/L)
Element Water Soil
Aluminum 500 *
Antimony 100 100
Arsenic 100 100
Barium 200 200
Beryllium 50 50
Cadmium 50 50
Chromium 50 50
Cobalt 100 100
Copper 50 50
Lead 50 50
Manganese 50 50
Nickel 100 100
Silver 50 50
Tha 11 i um 50 50
Vanadium 100 100
Zinc 100 100
* No spike required.
6020-16 Revision 0
November 1992
"ABLE 5. ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR AQUEOUS
SOLUTIONS
Comparability 8 %RSD
::lement Range Range
\l umi num 95 - 100 11 - 14 14 - 14 4

\nt imony d 5.0 - 7.6 16 - 16 3
\rsenic 97 114 7.1 - 48 12 - 14 4
3ari um 91 - 99 4.3 - 9.0 16 16 5
3eryl l i um 103 107 8.6 - 14 13 14 3
:admium 98 102 4.6 - 7.2 18 20 3
Calcium 99 107 5.7 - 23 17 18 5
Chromium 95 105 13 - 27 16 18 4
Cobalt 101 - 104 8.2 - 8.5 18 18 3
Copper 85 101 6.1 - 27 17 18 5
Iron 91 - 900 11 - 150 10 12 5
Lead 71 137 11 - 23 17 18 6
Magnesium 98 102 10 - 15 16 16 5
Manganese 95 101 8.8 - 15 18 18 4
Nickel 98 101 6.1 - 6.7 18 18 2
Potassium 101 114 9.9 - 19 11 12 5
Selenium 102 107 15 - 25 12 12 3
Silver 104 105 5.2 - 7.7 13 16 2
Sodium 82 104 24 - 43 9 10 5
Thallium 88 97 9.7 - 12 18 18 3
Vanadium 107 142 23 - 68 8 13 3
Zinc 93 102 6.8 - 17 16 18 5
a Comparability refers to the percent agreement of mean ICP-MS values to those

of the reference technique. b N is the range of the number of ICP-MS
measurements where the analyte values exceed the 1imit of quantitation (3.3 times
the average IDL value). c S is the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
6020-17 Revision 0
November 1992
TABLE 6. ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Comparability8 %RSD
Element Range Range
Aluminum 83 - 101 11 - 39 13 - 14 7
Antimony d 12 -
21 15 -
16 2
Arsenic 79 - 102 12 -
23 16 -
16 7
Barium 100 - 102 4.3 -
17 15 -
16 7
Beryllium 50 - 87 19 -
34 12 -
14 5
Cadmium 93 - 100 6.2 -
25 19 -
20 5
Ca lei um 95 - 109 4.1 -
27 15 -
17 7
Chromium 77 - 98 11 -
32 17 -
18 7
Cobalt 43 - 102 15 -
30 17 -
18 6
Copper 90 - 109 9.0 -
25 18 -
18 7
Iron 87 - 99 6.7 -
21 12 -
12 7
Lead 90 - 104 5.9 -
28 15 -
18 7
Magnesium 89 - 111 7.6 -
37 15 -
16 7
Manganese 80 - 108 11 -
40 16 -
18 7
Ni eke l 87 - 117 9.2 -
29 16 -
18 7
Potassium 97 - 137 11 - 62 10 - 12 5
Selenium 81 39 12 1
Silver 43 - 112 12 - 33 15 - 15 3
Sodium 100 - 146 14 - 77 8 - 10 5
Thallium 91 33 18 1
Vanadium 83 - 147 20 - 70 6 - 14 7
Zinc 84 - 124 14 - 42 18 - 18 7
a Comparability refers to the percent agreement of mean ICP-MS values to those

of the reference technique. b N is the range of the number of I CP-MS
measurements where the analyte values exceed the limit of quantitation (3.3 times
the average IDL value). c Sis the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
6020-18 Revision 0
November 1992
METHOD 6020
INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY
Slarl
7 l An.alyae 7. 6 Calibrate
by Melhod 7 .1 u•• lhe •nalruaenl
7000 or Melhod 3040 !or lhe
M•lhod 6010 anal1h• a!
inl•r•al
7.1 u.. 7.7 l:atend

M•lhod 3005
or Melliod
!luahinf ti••
!or ••all
3015 inatru..nl
anal1aia
Ila
7 l u•• 7 8 Monitor .all Ad J1••

l
Method 3020 •••••• wh•ch •nalru•onl par
or M•thod could a!C.ol manu£act.\4rer
3015 data quali t1 H r•c:o-•ndalJ.on•
roao-•ndod
Fl.AA/ICP Solid r ••
7.l u.. 7.l u..

M•lhod 3010 M•lhod 3050 7.9 Var.£1
or Molliod or M•thod calibrahon
3015 3051 villi ICV
No
7 .2 Inithte 7 10 Analyzo 7 10 Fhuh

operal•ng chaclc alandard ayala• and
con!iguralion and calibration analyza
o! inatru-nt blank a!hr a amp la
coaput•r oach lO aa•plH
7 3 Sot up ll Ddut•
and alab•lia• ax tract
.z.n•tru••nl
No
7 4 Sol
opera ling 7 12
condihona aa C.alcul.ale
roco-endod c:onc•nt.ralJ.on
7 5 Por!orm
••••
cahbrahon and Slop
reeolu.li.on
check•
6020-19 Revis ion 0

November 1992
METHOD 7000
ATOMIC ABSORPTION METHODS

I.I Metals in solution may be readily determined by atomic absorption
spectroscopy. The method is simple, rapid, and applicable to a large number of
metals in drinking, surface, and saline waters and domestic and ·industrial
wastes. While drinking water free of particulate matter may be analyzed
directly, ground water, other aqueous samples, EP extracts, industrial wastes,
soils, sludges, sediments, and other solid wastes require digestion prior to
analysis.
1.2 Detection limits, sensitivity, and optimum ranges of the metals will
vary with the matrices and models of atomic absorption spectrophotometers. The
data shown in Table 1 provide some indication of the detection limits
obtainable by direct aspiration and by furnace techniques. For clean aqueous
samples, the detection limits shown in the table by direct aspiration may be
extended downward with scale expansion and upward by using a less sensitive
wavelength or by rotating the burner head. Detection limits by direct
aspiration may also be extended through concentration of the sample and/or
through solvent extraction techniques. For certain samples, lower
concentrations may also be determined using the furnace techniques. The
detection limits given in Table 1 are somewhat dependent on equipment (such as
the type of spectrophotometer and furnace accessory, the energy source, the
degree of electrical expansion of the output signal), and are greatly
dependent on sample matrix. When using furnace techniques, however, the
analyst should be cautioned as to possible chemical reactions occurring at
elevated temperatures which may result in either suppression or enhancement of
the analysis element. To ensure valid data with furnace techniques, the
analyst must examine each matrix for interference effects (see Step 3.2.1)
and, if detected, treat them accordingly, using either successive dilution,
matrix modification, or method of standard additions (see Step 8.7).
1.3 Where direct-aspiration atomic absorption techniques do not provide
adequate sensitivity, reference is made to specialized procedures (in addition
to the furnace procedure) such as the gaseous-hydride method for arsenic and
selenium and the cold-vapor technique for mercury.
2. I Although methods have been reported for the analysis of sol ids by
atomic absorption spectroscopy, the technique generally is limited to metals
in solution or solubilized through some form of sample processing.
2.2 Preliminary treatment of waste water, ground water, EP extracts, and
industrial waste is always necessary because of the complexity and variability
of sample matrix. Solids, slurries, and suspended material must be subjected
to a solubilization process before analysis. This process may vary because of
the metals to be determined and the nature of the sample being analyzed.
7000 - 1 Revision 1
December 1987
Solubilization and digestion procedures are presented in Step 3.2 (Sample
Preparation Methods).
2.3 In direct-aspiration atomic absorption spectroscopy, a sample is
aspirated and atomized in a flame. A light beam from a hollow cathode lamp or
an electrodeless discharge lamp is directed through the flame into a
monochromator, and onto a detector that measures the amount of absorbed light.
Absorption depends upon the presence of free unexcited ground-state atoms in
the flame. Because the wavelength of the light beam is characteristic of only
the metal being determined, the light energy absorbed by the flame is a
measure of the concentration of that metal in the sample. This principle is
the basis of atomic absorption spectroscopy.
2.4 When using the furnace technique in conjunction with an atomic
absorption spectrophotometer, a representative aliquot of a sample is placed
in the graphite tube in the furnace, evaporated to dryness, charred, and
atomized. As a greater percentage of available analyte atoms is vaporized and
dissociated for absorption in the tube rather than the flame, the use of
smaller sample volumes or detection of lower concentrations of elements is
possible. The principle is essentially the same as with direct aspiration
atomic absorption, except that a furnace, rather than a flame, is used to
atomize the sample. Radiation from a given excited element is passed through
the vapor containing ground-state atoms of that element. The intensity of the
transmitted radiation decreases in proportion to the amount of the ground-
state element in the vapor. The metal atoms to be measured are placed in the
beam of radiation by increasing the temperature of the furnace, thereby
causing the injected specimen to be volatilized. A monochromator isolates the
characteristic radiation from the hollow cathode lamp or electrodeless
discharge 1 amp, and a photosensitive device measures the attenuated
transmitted radiation.
3.0 INTERFERENCES
3.1 Direct aspiration
3.1.1 The most troublesome type of interference in atomic
absorption spectrophotometry is usually termed "chemical" and is caused
by lack of absorption of atoms bound in mo 1ecul ar combination in the
flame. This phenomenon can occur when the flame is not sufficiently hot
to dissociate the molecule, as in the case of phosphate interference with
magnesium, or when the dissociated atom is immediately oxidized to a
compound that wi 11 not dissociate further at the temperature of the
flame. The addition of lanthanum will overcome phosphate interference in
magnesium, calcium, and barium determinations. Similarly, silica
interference in the determination of manganese can be eliminated by the
addition of calcium.
3.1.2 Chemical interferences may also be eliminated by separating
the metal from the interfering material. Although complexing agents are
employed primarily to increase the sensitivity of the analysis, they may
also be used to eliminate or reduce interferences.
7000 - 2 Revision 1
December 1987
3.1.3 The presence of high dissolved solids in the sample may
result in an interference from nonatomi c absorbance such as light
scattering. If background correction is not available, a nonabsorbing
wavelength should be checked. Preferably, samples containing high solids
should be extracted.
3.1.4 Ionization interferences occur when the flame temperature is
sufficiently high to generate the removal of an electron from a neutral
atom, giving a positively charged ion. This type of interference can
generally be controlled by the addition, to both standard and sample
solutions, of a large excess (1,000 mg/L) of an easily ionized element
such as K, Na, Li or Cs.
3.1.5 Spectral interference can occur when an absorbing wavelength
of an element present in the sample but not being determined falls within
the width of the absorption line of the element of interest. The results
of the determination will then be erroneously high, due to the
contribution of the interfering element to the atomic absorption signal.
Interference can also occur when resonant energy from another element in
a multielement lamp, or from a metal impurity in the lamp cathode, falls
within the bandpass of the slit setting when that other metal is present
in the sample. This type of interference may sometimes be reduced by
narrowing the slit width.
3.1.6 Samples and standards should be monitored for viscosity
differences that may alter the aspiration rate.
3.1.7 All metals are not equally stable in the digestate,
especially if it contains only nitric acid, not nitric acid and
hydrochloric acid. The digestate should be analyzed as soon as possible,
with preference given to Sn, Sb, Mo, Ba, and Ag.
3.2 Furnace procedure
3.2.1 Although the problem of oxide formation is greatly reduced
with furnace procedures because atomization occurs in an inert atmosphere,
the technique is still subject to chemical interferences. The composition
of the sample matrix can have a major effect on the analysis. It is those
effects which must be determined and taken into consideration in the
analysis of each different matrix encountered. To help verify the absence
of matrix or chemical interference, the serial dilution technique (see
Step 8.6) may be used. Those samples which indicate the presence of
interference should be treated in one or more of the following ways:
1. Successively dilute and reanalyze the samples to eliminate
interferences.
2. Modify the sample matrix either to remove interferences or to
stabilize the analyte. Examples are the addition of ammonium
nitrate to remove alkali chlorides and the addition of ammonium
phosphate to retain cadmium. The mixing of hydrogen with the
inert purge gas has al so been used to suppress chemical
7000 - 3 Revision 1
December 1987
interference. The hydrogen acts as a reducing agent and aids in
molecular dissociation.
3. Analyze the sample by method of standard additions while
noticing the precautions and limitations of its use (see Step
8.7.2).
3. 2. 2 Gases generated in the furnace during atomization may have
molecular absorption bands encompassing the ana lyt i cal wavelength. When
this occurs, use either background correction or choose an alternate
wavelength. Background correction may also compensate for nonspecific
broad-band absorption interference.
3. 2. 3 Conti nu um background correction cannot correct for a11 types
of background interference. When the background interference cannot be
compensated for, chemically remove the analyte or use an alternate form of
background correction, e.g., Zeeman background correction.
3.2.4 Interference from a smoke-producing sample matrix can
sometimes be reduced by extending the charring ti me at a higher
temperature or utilizing an ashing cycle in the presence of air. Care
must be taken, however, to prevent loss of the analyte.
3.2.5 Samples containing large amounts of organic materials should
be oxidized by conventional acid digestion before being placed in the
furnace. In this way, broad-band absorption will be minimized.
3.2.6 Anion interference studies in the graphite furnace indicate
that, under conditions other than isothermal, the nitrate anion is
preferred. Therefore, nitric acid is preferable for any digestion or
solubilization step. If another acid in addition to nitric acid is
required, a minimum amount should be used. This applies particularly to
hydrochloric and, to a lesser extent, to sulfuric and phosphoric acids.
3.2.7 Carbide formation resulting from the chemical environment of
the furnace has been observed. Molybdenum may be cited as an example. When
carbides form, the metal is released very slowly from the resulting metal
carbide as atomization continues. Molybdenum may require 30 seconds or
more atomization time before the signal returns to baseline levels.
Carbide formation is greatly reduced and the sensitivity increased with
the use of pyro l yt i ca 11 y coated graphite. Elements that readily form
carbides are noted with the symbol (p) in Table 1.
3.2.8 For comments on spectral interference, see Step 3.1.5.
3.2.9 Cross-contamination and contamination of the sample can be
major sources of error because of the extreme sensitivities achieved with
the furnace. The sample preparation work area should be kept scrupulously
clean. All glassware should be cleaned as directed in Step 4.8. Pipet
tips are a frequent source of contamination. If suspected, they should be
acid soaked with 1:5 nitric acid and rinsed thoroughly with tap and Type
II water. The use of a better grade of pipet tip can greatly reduce this
problem. Special attention should be given to reagent blanks in both
7000 - 4 Revision 1
December 1987
analysis and in the correction of analytical results. Lastly, pyrolytic
graphite, because of the production process and handling, can become
contaminated. As many as five to ten high-temperature burns may be
required to clean the tube before use.
4.1 Atomic absorption spectrophotometer - Single- or dual-channel,
single- or double-beam instrument having a grating monochromator,
photomultiplier detector, adjustable slits, a wavelength range of 190 to
800 nm, and provisions for interfacing with a strip-chart recorder.
4.2 Burner - The burner recommended by the particular instrument
manufacturer should be used. For certain elements the nitrous oxide burner is
required.
4.3 Hollow cathode lamps - Single-element lamps are preferred but
multielement lamps may be used. Electrodeless discharge lamps may also be used
when available.
4.4 Graphite furnace - Any furnace device capable of reaching the
specified temperatures is satisfactory.
4.5 Strip-chart recorder - A recorder is recommended for furnace work so
that there will be a permanent record and that any problems with the analysis
such as drift, incomplete atomization, losses during charring, changes in
sensitivity, peak shape, etc., can be easily recognized.
4.6 Pipets - Microliter, with disposable tips. Sizes can range from 5 to
100 ul as required. Pipet tips should be checked as a possible source of
contamination prior to their use.
4.7 Pressure-reducing valves - The supplies of fuel and oxidant should be
maintained at pressures somewhat higher than the controlled operating pressure
of the instrument by suitable valves.
4.8 Glassware - All glassware, polypropylene, or Teflon containers,
including sample bottles, should be washed in the following sequence:
detergent, tap water, 1:1 nitric acid, tap water, 1:1 hydrochloric acid, tap
water, and Type II water. (Chromic acid should not be used as a cleaning agent
for glassware if chromium is to be included in the analytical scheme.) If it
can be documented through an active analytical quality control program using
spiked samples and reagent blanks that certain steps in the cleaning procedure
are not required for routine samples, those steps may be eliminated from the
procedure.
5.0 REAGENTS
7000 - 5 Revision 1
December 1987
determination.
5.3 Nitric acid (concentrated}, HN03. Use a spectrograde acid certified
for AA use. Prepare a 1:1 dilution with water by adding the concentrated acid
to an equal volume of water.
5.4 Hydrochloric acid (1:1), HCl. Use a spectrograde acid certified for
AA use. Prepare a 1:1 dilution with water by adding the concentrated acid to
an equal volume of water.
5.5 Fuel and oxidant - Commercial grade acetylene is generally
acceptable. Air may be supplied from a compressed air line, a laboratory
compressor, or a cylinder of compressed air. Nitrous oxide is also required
for certain determinations. Standard, commercially available argon and
nitrogen are required for furnace work.
5.6 Stock standard metal solutions - Stock standard solutions are
prepared from high purity metals, oxides, or nonhygroscopic salts using
water and redistilled nitric or hydrochloric acids. (See individual methods
for specific instructions.) Sulfuric or phosphoric acids should be avoided as
they produce an adverse ef feet on many elements. The stock sol ut i ans are
prepared at concentrations of 1,000 mg of the metal per liter. Commercially
available standard solutions may also be used. Where the sample viscosity,
surface tension, and components cannot be accurately matched with standards,
the method of standard addition (MSA) may be used (see Step 8.7).
5.7 Calibration standards - For those instruments which do not read out
directly in concentration, a calibration curve is prepared to cover the
appropriate concentration range. Usually, this means the preparation of
standards which produce an absorbance of 0.0 to 0.7. Calibration standards are
prepared by diluting the stock metal solutions at the time of analysis. For
best results, calibration standards should be prepared fresh each time a batch
of samples is analyzed. Prepare a blank and at least three calibration
standards in graduated amounts in the appropriate range of the linear part of
the curve. The calibration standards should be prepared using the same type of
acid or combination of acids and at the same concentration as will result in
the samples following processing. Beginning with the blank and working toward
the highest standard, aspirate the solutions and record the readings. Repeat
the operation with both the calibration standards and the samples a sufficient
number of times to secure a reliable average reading for each solution.
Calibration standards for furnace procedures should be prepared as described
on the individual sheets for that metal.
6.1 See the introductory material in Chapter Three, Metallic Analytes.
7000 - 6 Revision 1
December 1987
7. 0 PROCEDURE
7.1 Preliminary treatment of waste water, ground water, EP extracts, and
industrial waste is always necessary because of the complexity and variability
of sample matrices. Solids, slurries, and suspended material must be subjected
to a solubilization process before analysis. This process may vary because of
the metals to be determined and the nature of the sample being analyzed.
Solubilization and digestion procedures are presented in Chapter Three, Step
3.2, Sample Preparation Methods.
7.2 Direct aspiration (flame) procedure
7.2.l Differences between the various makes and models of
satisfactory atomic absorption spectrophotometers prevent the formulation
of detailed instructions applicable to every instrument. The analyst
should follow the manufacturer's operating instructions for a particular
instrument. In general, after choosing the proper lamp for the analysis,
allow the lamp to warm up for a minimum of 15 minutes, unless operated in
a double-beam mode. During this period, align the instrument, position the
monochromator at the correct wavelength, select the proper monochromator
slit width, and adjust the current according to the manufacturer's
recommendation. Subsequently, light the flame and regulate the fl ow of
fue 1 and oxidant. Adjust the burner and nebul i zer fl ow rate for maximum
percent absorption and stability. Balance the photometer. Run a series of
standards of the element under analysis. Construct a calibration curve by
plotting the concentrations of the standards against absorbances. Set the
curve corrector of a direct reading instrument to read out the proper
concentration. Aspirate the samples and determine the concentrations
either directly or from the calibration curve. Standards must be run each
time a sample or series of samples is run.
7.3 Furnace procedure
7.3.1 Furnace devices (flameless atomization) are a most useful
means of extending detection limits. Because of differences between
various makes and models of satisfactory instruments, no detailed
operating instructions can be given for each instrument. Instead, the
analyst should follow the instructions provided by the manufacturer of a
particular instrument.
7 .3.2 Background correction is important when using flameless
atomization, especially below 350 nm. Certain samples, when atomized, may
absorb or scatter light from the lamp. This can be caused by the presence
of gaseous molecular species, salt particles, or smoke in the sample beam.
If no correction is made, sample absorbance will be greater than it should
be, and the analytical result will be erroneously high. Zeeman background
correction is effective in overcoming composition or structured background
interferences. It is particularly useful when analyzing for As in the
presence of Al and when analyzing for Se in the presence of Fe.
7.3.3 Memory effects occur when the analyte is not totally
volatilized during atomization. This condition depends on several factors:
volatility of the element and its chemical form, whether pyrolytic
7000 - 7 Revision 1
December 1987
graphite is used, the rate of atomization, and furnace design. This
situation is detected through blank burns. The tube should be cleaned by
operating the furnace at full power for the required time period, as
needed, at regular intervals during the series of determinations.
7 .3.4 Inject a measured microl iter aliquot of sample into the
furnace and atomize. If the concentration found is greater than the
highest standard, the sample should be diluted in the same acid matrix and
reanalyzed. The use of multiple injections can improve accuracy and help
detect furnace pipetting errors.
7 .3.5 To verify the absence of interference, follow the serial
dilution procedure given in Step 8.6.
7 .3.6 A check standard should be run after approximately every 10
sample injections. Standards are run in part to monitor the life and
performance of the graphite tube. Lack of reproducibility or significant
change in the signal for the standard indicates that the tube should be
replaced. Tube life depends on sample matrix and atomization temperature.
A conservative estimate would be that a tube will last at least 50
firings. A pyrolytic coating will extend that estimated life by a factor
of three.
7.4 Calculation
7.4.1 For determination of metal concentration by direct aspiration
and furnace: Read the metal value in ug/L from the calibration curve or
directly from the read-out system of the instrument.
7.4.2 If dilution of sample was required:
ug/L metal in sample = A (~)

c
where:
A= ug/L of metal in diluted aliquot from calibration curve.
B = Acid blank matrix used for dilution, ml.
C =Sample aliquot, ml.
7.4.3 For solid samples, report all concentrations as ug/kg based on

wet weight. Hence:
ug metal/kg sample = A x V
where: w
A= ug/L of metal in processed sample from calibration curve.

V = Final volume of the processed sample, ml.
W= Weight of sample, grams.
7000 - 8 Revision 1
December 1987
7.4.4 Different injection volumes must not be used for samples and
standards. Instead, the sample should be diluted and the same size
injection volume be used for both samples and standards. If dilution of
the sample was required:
ug/L of metal in sample Z ( C + B)

c
where:
Z = ug/L of metal read.from calibration curve or read-out system.
B = Acid blank matrix used for dilution ml.
C =Sample aliquot, ml.
8.0 QUALITY CONTROL
8.2 A calibration curve must be prepared each day with a minimum of a
reagent blank and three standards, verified by use of at least a reagent blank
and one check standard at or near the mid-range. Checks throughout the day
must be within 20% of original curve.
8.3 If 20 or more samples per day are analyzed, the working standard
curve must be verified by running an additional standard at or near the mid-
range every 10 samples. Checks must be within ± 20% of true value.
8.4 At least one spiked matrix and one replicate sample should be run
every 20 samples or per analytical batch, whichever is greater. At least one
spiked replicate sample should also be run with each matrix type to verify
precision of the method.
8.5 Where the sample matrix is so complex that viscosity, surface
tension, and components cannot be accurately matched with standards, the
method of standard addition may be used (see Step 8.7 below).
8.6 Serial dilution - Withdraw from the sample two equal aliquots. To one
of the aliquots add a known amount of analyte and dilute both aliquots to the
same predetermined volume. (The dilution volume should be based on the
analysis of the undiluted sample. Preferably, the dilution should be 1:4,
while keeping in mind that the diluted value should be at least 5 times the
instrument detection "limit. Under no circumstances should the dilution be less
than 1: I.) The diluted a1i quots should then be analyzed, and the unspi ked
results, multiplied by the dilution factor, should be compared to the original
determination. Agreement of the results (within 10%) indicates the absence of
interference. Comparison of the actual signal from the spike with the expected
response from the analyte in an aqueous standard should help confirm the
finding from the dilution analysis.
8.7 Method of standard additions - The standard addition technique
involves adding known amounts of standard to one or more a1i quo ts of the
processed sample solution. This technique compensates for a sample constituent
7000 - 9 Revision 1
December 1987
that enhances or depresses the analyte signal, thus producing a different
slope from that of the calibration standards. It will not correct for additive
interferences which cause a baseline shift.
8.7.1 In the simplest version of this technique is the single
addition method, in which two identical aliquots of the sample solution,
each of volume Vx, are taken. To the first (labeled A) is added a known
volume Vs of a standard analyte solution of concentration Cs. To the
second aliquot (labeled B) is added the same volume Vs of the solvent. The
analytical signals of A and B are measured and corrected for nonanalyte
signals. The unknown sample concentration Cx is calculated:
SsVscs
Cx = (SA-Ss)Vx
where SA and Ss are the analytical signals (corrected for the blank) of
solutions A and B, respectively. Vs and Cs should be chosen so that SA is
roughly twice Ss on the average, avoiding excess dilution of the sample.
If a separation or concentration step is used, the additions are best made
first and carried through the entire procedure.
8.7.2 Improved results can be obtained by employing a series of
standard additions. Equal volumes of the sample are added to a series of
standard so 1ut i ans containing different known quantities of the test
analyte, all diluted to the same volume. For example, addition 1 should be
prepared so that the resulting concentration is approximately 50 percent
of the expected sample absorbance. Additions 2 and 3 should be prepared so
that the concentrations are approximately 100 and 150 percent of the
expected sample absorbances, respectively. The absorbance of each solution
is determined and then plotted on the vertical axis of a graph, with the
concentrations of the known standards plotted on the horizontal axis. When
the resulting line is extrapolated back to zero absorbance, the point of
interception of the abscissa is the concentration of the unknown. The
abscissa on the left of the ordinate is scaled the same as on the right
side, but in the opposite direction from the ordinate. An ex amp 1e of a
plot so obtained is shown in Figure 1.
8.7.3 For the results of this technique to be valid, the following
limitations must be taken into consideration:
1. The absorbance plot of sample and standards must be 1i near over
the concentration range of concern. For best results, the slope of the
plot should be nearly the same as the slope of the standard curve. If the
slope is significantly different (greater than 20%), caution should be
exercised.
2. The effect of the interference should not vary as the ratio of
analyte concentration to sample matrix changes, and the standard addition
should respond in a similar manner as the analyte.
3. The determination must be free of spectra 1 interference and
corrected for nonspecific background interference.
December 1987
8.8 All quality control measures descibed in Chapter One should be
followed.
9.1 See individual methods.
10.0 REFERENCES
I. Methods for Chemical Analysis of Water and Wastes; U.S. Environmental
Protection Agency. Office of Research and Deve 1opment. Envi ronmenta 1
Environmental Research Information: Cincinnati, OH, 1983; EPA-
600/4-79-020.
December 1987
TABLE 1.
ATOMIC ABSORPTION CONCENTRATION RANGES
Direct Aspiration
Furnace Procedurea,c
Detect ion Limit Sensitivity Detection Limit
Metal (mg/L) (mg/L) (ug/L)
Aluminum 0 .1 1
Antimonb 0.2 0.5 3
Arsenic 0.002 1
Barium 0.1 0.4
Beryllium 0.005 0.025 0.2
Cadmium 0.005 0.025 0 .1
Calcium 0.01 0.08
Chromium 0.05 0.25 1
Cobalt 0.05 0.2 1
Copper 0.02 0 .1
Iron 0.03 0 .12
Lead 0 .1 0.5 1
Lit hi um 0.002 0.04
Magnesium 0.001 0.007
Manganese 0.01 0.05
Mercuryd 0.0002
Molybdenum(p) 0 .1 0.4 1
Nickel 0.04 0 .15
Osmium 0.03 1
Potassium 0.01 0.04
Seleniumb 0.002 2
Silver 0.01 0.06
Sodium 0.002 0.015
Strontium 0.03 0 .15
Thallium 0.1 0.5 1
Tin 0.8 4
Vanadium(p) 0.2 0.8 4
Zinc 0.005 0.02
NOTE: The symbol (p) indicates the use of pyrolytic graphite with the
furnace procedure.
a For furnace sensitivity values, consult instrument operating manual.
b Gaseous hydride method.
c The 1 i sted furnace values are those expected when using a 20-uL
injection and norma 1 gas fl ow, except in the cases of arsenic and
selenium, where gas interrupt is used.
d Cold vapor technique.
December 1987
FIGURE 1.
STANDARD ADDITION PLOT
Zero
Absorb1nce
Co nee ntr at ion
Cone. of AddnO Addn 1 Addn 2 Addn 3

S.mple No Addn Addn of 50% Addn of 100'!0 Addn of T50'!o
of Expected of Expected of Expected
Amount Amount Amount
December 1987
METHOD 7000
ATOMIC ABSORPTION METHODS
Start
7. l
Oo
prc11•1nary
treat•ent t,,roug,,
eolublltz•tton end
dlQ••tlon procedures
(C,,•oter 3.
Sect1on 3.21
7.2. l
C,,oo•e end
oreo.,·• ,,o 1 low
C8t,,Od8 la-c>
7 .2.1 7.3.2
Ad,u•t and Mete• background

•llon aqulPMent correct ton
7 .2. l
L1g,,t t laMe
end regulate
7 .2.1 7.3.3 7.3.•
Aun •t•nd•rd• Cleen tub• Insect end

eto•lz:e pert
ot ••-oh
December 1987
METHOD 7000
(Continued)
7.2.t 7.3.•
Construct
a c:•l11:1ratlon Cl lute SH•Ol•
curve and set.
curve c:orrec:tor
1. 2. t 7.3.5 vertty
abaanc:e
of 1nt.erferenc•
uslny serlal
cu uc1on
I••• a.el
1.4 7.3.I
Oat.er•tn• Aun • Cl,.Ck

canc:entl"at.tan •tender-Cl
Stao
December 1987
METHOD 7060A
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
.0 SCOPE AND APPLICATION

1.1 Method 7060 is an atomic absorption procedure approved for
etermining the concentration of arsenic in wastes, mobility procedure extracts,
:oils, and ground water. All samples must be subjected to an appropriate
issolution step prior to analysis.
~.O SUMMARY OF METHOD

2.1 Prior to analysis by Method 7060, samples must be prepared in order
;o convert organic forms of arsenic to inorganic forms, to min-imize organic
nterferences, and to convert the sample to a suitable solution for analysis.
'he sample preparation procedure varies depending on the sample matrix. Aqueous
;amples are subjected to the acid digestion procedure described in this method.
iludge samples are prepared using the procedure described in Method 3050.
2.2 Following the appropriate dissolution of the sample, a representative
liquot of the digestate is spiked with a nickel nitrate solution and is placed
anually or by means of an automatic sampler into a graphite tube furnace. The
;ample aliquot is then slowly evaporated to dryness, charred (ashed), and
1tomized. The absorption of hollow cathode or EDL radiation during atomization
~ill be proportional to the arsenic concentration. Other modifiers may be used
·n place of nickel nitrate if the analyst documents the chemical and
:oncentration used.
2.3 The typical detection limit for water samples using this method is
1 ug/L. This detection limit may not be achievable when analyzing waste samples.
3.0 INTERFERENCES
3.1 Elemental arsenic and many of its compounds are volatile; therefore,
samples may be subject to losses of arsenic during sample preparation. Spike
samples and relevant standard reference materials should be processed to
jetermine if the chosen dissolution method is appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all digestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, arsenic analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Arsenic
analysis is particularly susceptible to these problems because of its low
analytical wavelength (193.7 nm). Simultaneous background correction must be
employed to avoid erroneously high results. Aluminum is a severe positive
7060A - l Revision l
November 1992
interferent in the analysis of arsenic, especially using D2 arc backgroun
correction. Zeeman background correction is very useful in this situation.
3.4 If the analyte is not completely volatilized and removed from th,
furnace during atomization, memory effects will occur. If this situation i
detected by means of blank burns, the tube should be cleaned by operating th,
furnace at full power at regular intervals in the analytical scheme.

4.1 Griffin beaker or equivalent: 250 ml.
4.2 Class A Volumetric flasks: 10-ml.
4.3 Atomic absorption spectrophotometer: Single or dual channel, single·
or double-beam instrument having a grating monochromator, photo-multiplie
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provision:
for simultaneous background correction and interfacing with a strip-char·
recorder.
4.4 Arsenic hollow cathode lamp, or electrodeless discharge lamp (EDL):
EDLs provide better sensitivity for arsenic analysis.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4. 6 Data systems recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during charring,
changes in sensitivity, etc., can easily be recognized.
4.7 Pipets: Microliter with disposable tips. Sizes can range from
5 to 1,000 ul, as required.
5.0 REAGENTS
5.1 Reagent water: Water should be monitored for impurities.
All references to water will refer to reagent water.
5.2 Concentrated nitric acid: Acid should be analyzed to determine levels
of impurities. If a method blank using the acid is <MDL, the acid can be used.
5.3. Hydrogen peroxide (30%): Oxidant should be analyzed to determine
levels of impurities. If a method blank using the H202 is <MDL, the acid can be
used.
5.4 Arsenic standard stock solution (1,000 mg/l): Either procure a
certified aqueous standard from a supplier and verify by comparison with a second
standard, or dissolve 1.320 g of arsenic trioxide (As 2 03 , analytical reagent
7060A - 2 Revision 1
November 1992
grade) or equivalent in 100 ml of reagent water containing 4 g NaOH. Acidify the
solution with 20 ml concentrated HN0 3 and dilute to 1 liter (1 ml= 1 mg As).
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent grade
Ni (N0 3 ) 2 ·6H 20 or equivalent in reagent water and dilute to 100' ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel nitrate
to 100 ml with reagent water.
5.7 Arsenic working standards: Prepare dilutions of the stock solution
to be used· as calibration standards at the time of the analysis. Withdraw
appropriate aliquots of the stock solution, add concentrated HN0 3 , 30% H202 , and
5% nickel nitrate solution. Amounts added should be representative of the
concentrations found in the samples. Dilute to 100 ml with reagent water.

reagent water. Plastic and glass containers are both suitable.
6.3 Special containers {e.g., containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid and
refrigerated prior to analysis.
6.5 Although waste samples do not need to be refrigerated sample handling
and storage must comply with the minimum requirements established in Chapter One.
7. 0 PROCEDURE
7.1 Samp 1e preparation: Aqueous samples should be prepared in the manner
described in Paragraphs 7.1.1-7.1.3. Sludge-type samples should be prepared
according to Method 3050A. The applicability of a sample-preparation technique
to a new matrix type must be demonstrated by analyzing spiked samples and/or
relevant standard reference materials.
7.1.1 Transfer a known volume of well-mixed sample to a 250-ml
Griffin beaker or equivalent; add 2 ml of 30% H2 02 and sufficient
concentrated HN0 3 to result in an acid concentration of 1% (v/v). Heat,
until digestion is complete, at 95°C or until the volume is slightly less
than 50 ml.
7.1.2 Cool and bring back to 50 ml with reagent water.
November 1992
7 .1.3 Pipet 5 ml of this digested solution into a 10-ml volumetric
fl ask, add 1 ml of the 1% nickel nitrate solution, and dilute to 10 ml
with reagent water. The sample is now ready for injection into the
furnace.
7.2 The 193.7-nm wavelength line and a background correction system are
required. Follow the manufacturer's suggestions for all other spectrophotometer
parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering the
furnace parameters while analyzing a standard. In this manner, losses of analyte
due to overly high temperature settings or losses in sensitivity due to less than
optimum settings can be minimized. Similar verification of furnace parameters
may be required for complex sample matrices.
7.4 Inject a measured microliter aliquot of sample into the furnace and
atomize. If the concentration found is greater than the highest standard, the
sample should be diluted in the same acid matrix and reanalyzed. The use of
multiple injections can improve accuracy and help detect furnace pipetting
errors.
8.0 QUALITY CONTROL

8.1 Refer to section 8.0 of Method 7000.

9.1 Precision and accuracy data are available in Method 206.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The optimal concentration range for aqueous samples using this method
is 5-100 ug/L. Concentration ranges for non-aqueous samples will vary with
matrix type.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
November 1992
TABLE 1. METHOD PERFORMANCE DATA
iample Preparation Laboratory

.atrix Method Replicates
:ontaminated soil 3050 2.0, 1. 8 ug/g

>ily soil 3050 3.3, 3.8 ug/g
rns SRM 1646 Estuarine sediment 3050 8.1, 8.33 ug/ga
:m1ssion control dust 3050 430, 350 ug/g
Bias of -30 and -28% from expected, respectively.
November 1992
METHOD 7060A
ARSENIC {ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
7.l.l Tran•f•r 7 l Pr•p•r•

•••pl• lo •••pl••
b•alc•r,add H,O, accord1.n9 to
and cone HNO,, M•thod 3050
h•at
7 l 2 Cool
aad br1.n9 t.o
volua• w1.lh
r•ag•nt wat•r
7.l 3 P1.p•t 7 2 S•l "P

•olulion 1.nto 1.n•trua•nt
flHJc, add op•r•l1.ng
n1.clc•l n1.trat•, par•••l•r
d1.lul•
7 3 .
P•r1.od1.cally
v•r1.{y
!urnac•
paraa•l•r•
7 4 Ini•cl
aliquot of 7 4 Ddul•
•••pl• 1.nlo •••pl• and
!u.rnae•, r•analya•
aloa1.a•
No
7 4 R•cord lb
conc•nlral1.on
Stop
November 1992
METHOD 7061
ARSENIC (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
1.0 SCOPE ANO APPLICATION

1.1 Method 7061 is an atomic absorption procedure for determining the
concentration of arsenic in wastes, mobility procedure extracts, soils, and
ground water. Method 7061 is approved only for sample matrices that do not
contain high concentrations of chromium, copper, mercury, nickel, silver,
cobalt, and molybdenum. All samples must be subjected to an appropriate
dissolution step prior to analysis. Spiked samples and relevant standard
reference materials are employed to determine the applicability of the method
to a given waste.
2.1 Samples are prepared according to the nitric/sulfuric acid digestion
procedure described in this method (Step 7.1). Next, the arsenic in the
digestate is reduced to the trivalent form with tin chloride. The trivalent
arsenic is then converted to a volatile hydride using hydrogen produced from a
zinc/hydrochloric acid reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer. The resulting
absorption of the lamp radiation is proportional to the arsenic concentration.
2.3 The typical detection limit for this method is 0.002 mg/l.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury,
molybdenum, nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample work-up can result
in analytical interferences. Nitric acid must be distilled off by heating the
sample until fumes of sulfer trioxide (S03) are observed.
3.3 Elemental arsenic and many of its compounds are volatile; therefore,
certain samples may be subject to losses of arsenic during sample preparation.
4.0 APPARATUS ANO MATERIALS
4.1 Beaker - 100-ml.
4.2 Electric hot plate.
4.3 A commercially available zinc slurry/hydride generator or a
generator constructed from the following materials (see Figure 1):
4.3.l Medicine dropper - Capable of fitting into a size "O" rubber
stopper and delivering 1.5 ml.
7061 - 1 Revision 1
December 1987
'I.' j
4.3.2 Pear-shaped reaction flask - 50-mL, with two 14/20 necks
(Scientific Glass JM-5835 or equivalent).
4.3.3 Gas inlet-outlet tube - Constructed from a micro cold-finger
condenser (JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stirrer - To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube - 10-cm, filled with glass to
prevent particulate matter from entering the burner.
4.3.6 Flow meter - Capable of measuring I liter/min.
4.4 Atomic absorption spectrophotometer - Single or dual channel,
single- or double-beam instrument having a grating monochromator, photo-
multiplier detector, adjustable slits, a wavelength range of 190 to 800 nm,
and provisions for interfacing with a strip-chart recorder.
4.5 Burner - Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Arsenic hollow cathode lamp or arsenic electrodeless discharge lamp.
4.7 Strip-chart recorder.
5.0 REAGENTS
determination.
determine levels of impurities. If a method blank is < MDL, the acid can be
used.
5.4 Sulfuric acid (concentrated), H2S04. Acid should be analyzed to
used.
used.
7061 - 2 Revision I
December 1987
5.6 Diluent - Add 100 ml 18N H2S04 and 400 ml concentrated HCl to 400 ml
water and dilute to a final volume of 1 liter with water.
5.7 Potassium iodide solution - Dissolve 20 g KI in 100 ml water.
5.8 Stannous chloride solution - Dissolve 100 g SnCl2 in 100 ml
concentrated HCl.
5.9 Arsenic solutions
5.9.1 Arsenic standard solution (1,000 mg/l) - Either procure a
certified aqueous standard from a supplier and verify by comparison with
a second standard, or dissolve 1.320 g of arsenic trioxide As203 in
100 ml of water containing 4 g NaOH. Acidify the solution with 20 ml
concentrated HN03 and dilute to 1 liter.
5.9.2 Intermediate arsenic solution - Pipet 1 ml stock arsenic
solution into a 100-ml volumetric flask and bring to volume with water
containing 1.5 ml concentrated HN03/liter (1 ml = 10 ug As).
5.9.3 Standard arsenic solution - Pipet 10 ml intermediate arsenic
solution into a 100-ml volumetric flask and bring to volume with water
containing 1.5 ml concentrated HN03/liter (1 ml= 1 ug As).
water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g. containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of < 2 with nitric acid.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Place a 50-ml aliquot of digested sample (or, in the case of
analysis of EP extracts, 50 ml) of the material to be analyzed in a 100-ml
beaker. Add 10 ml concentrated HN03 and 12 ml 18N H2S04. Evaporate the
sample in the hood on an electric hot plate until white S03 fumes are observed
(a volume of about 20 ml). Do not let the sample char. If charring occurs,
immediately turn off the heat, cool, and add an additional 3 ml of HN03.
Continue to add additional HN03 in order to maintain an excess (as evidenced
7061 - 3 Revision 1
December 1987
by the formation of brown fumes) . Do not let the solution darken, because
arsenic may be reduced and lost. When the sample remains colorless or straw
yellow during evolution of S03 fumes, the digestion is complete. Cool the
sample, add about 25 ml water, and again evaporate until S03 fumes are
produced in order to expel oxides of nitrogen. Cool. Transfer the digested
sample to a 100-ml volumetric flask. Add 40 ml of concentrated HCl and bring
to volume with water.
7 .2 Prepare working standards from the standard arsenic solution.
Transfer O, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-ml volumetric
flasks and bring to volume with diluent. These concentrations will be 0, 5,
10, 15, 20, and 25 ug As/liter.
7.3 If EP extracts are being analyzed or if a matrix interference is
encountered, take the 15-, 20-, and 25-mg/liter standards and quantitatively
transfer 25 ml of each of these standards into separate 50-ml volumetric
flasks. Add 10 ml of the prepared sample to each flask. Bring to volume with
water containing 1.5 ml HCl/liter.
7.4 Add 10 ml of prepared sample to a 50-ml volumetric flask. Bring to
volume with water containing 1.5 ml HCl/liter. This is the zero addition
aliquot.
NOTE: The absorbance from the zero addition aliquot will be one-fifth that
produced by the prepared sample. The absorbance from the spiked
samples will be one-half that produced by the standards plus the
contribution from one-fifth of the prepared sample. Keeping these
absorbances in mind will assist in judging the correct dilutions to
produce optimum absorbance.
7.5 Transfer a 25-ml portion of the digested sample or standard to the
reaction vessel and add 1 ml KI solution. Add 0.5 ml SnCl2 solution. Allow
at least 10 minutes for the metal to be reduced to its lowest oxidation state.
Attach the reaction vessel to the special gas inlet-outlet glassware. Fill
the medicine dropper with 1.50 ml zinc slurry that has been kept in suspension
with the magnetic stirrer. Firmly insert the stopper containing the medicine
dropper into the side neck of the reaction vessel. Squeeze the bulb to
introduce the zinc slurry into the sample or standard solution. The metal
hydride will produce a peak almost immediately. After the recorder pen begins
to return to the base line, the reaction vessel can be removed.
CAUTION: Arsine is very toxic. Precautions must be taken to avoid
inhaling arsine gas.
7.6 Use the 193.7-nm wavelength and background correction for the
analysis of arsenic.
7.7 Follow the manufacturer's instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame is colorless; therefore, it may be
useful to aspirate a low concentration of sodium to ensure that ignition has
occurred.
7061 - 4 Revision 1
December 1987
7.8 If the method of standard additions was employed, plot the
absorbances of spiked samples and blank vs. the concentrations. The
extrapolated value will be one-fifth the concentration of the original sample.
If the plot does not result in a straight line, a nonlinear interference is
present. This problem can sometimes be overcome by dilution or addition of
other reagents if there is some knowledge about the waste. If the method of
standard additions was not required, then the concentration can be part of the
calibration curve.
8.0 QUALITY CONTROL
8.2 Calibration curves must be composed of a minimum of a calibration
blank and three standards. A calibration curve should be made for every hour
of continuous sample analysis.
8.3 Oil ute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
8.5 Verify calibration with an independently prepared quality control
reference sample every 10 samples.
8.6 Run one matrix spiked replicate or one replicate sample for every 20
samples or per anal yt i cal batch, whichever is more frequent. A replicate
sample is a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions shall be used for the analysis of
all EP extracts, on all analyses submitted as part of a delisting petition,
and whenever a new sample matrix is being analyzed.
8.8 See Section 8.0 of Method 7000 for additional quality control
requirements.
10.0 REFERENCES
1. Methods For Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
7061 - 5 Revision 1
December 1987
2. Rohrbaugh, W.G.; et al. Reagent Chemicals. American Chemical Society
7061 - 6 Revision 1
December 1987
Figure 1.
Zinc sJurry hydride generator apparatus set-Yp and AAS sample introduction system.
Argon
Flow Meter
(Auxtliarv A1rt
JM-3325 "'» Argon !Nebuliztr Air)
Hydrogen
Medicine (Fuel)
Dropf)tr in
Size '°O"
Aubbtr
Stopper
7061 - 7 Revision I
December 1987
M~THOD 7061
AASENIC (ATOMIC A8SOAPTION, GASEOUS HYOAIOEJ
Start
7. l 7. t Wl'len
1--~~~atgesttan
Place ts COfftPlete.
al1Quat of coal sample: aCICI
Cl1gestea sample Type I I wate,.:
ln beaker evaporate: coo 1
7. I 7.t
T,.er1s re,.
1.00 cone. CllgesteCI sa11111le
HNO, ana HaSO~: ta r lesk: eCIO
evaporate cane. HCl:
sample t1r1no ta volume
7.t 7.2 Prepare

worktng
stanClerCls;
Tu,.n off l'leat. transfer ta
coo 1. ano •Cid r laslls; tirtng
HNOJ to volume
7.J
7 .1
Telle stanc:terCls and
transfer P•,.t of eecn
Canttnue ac:1c:11no ta separate flasks:
HNO.J •Cid prepared samole
ta eacn r l•sk;
tlrtno to volulBe
7061 - 8 Revision 1
December 1987
METHOO 7061
ARSENIC (ATOMIC 48SORPT10H, GASEOUS HYORlOEl
(Cont lnuedl
7.• 7.5
Add t----Introauc:e
oreoered ••"'Ol• z: 1nc: slurry
to fl •sk~ t1r 1ng into sample
to YO 11J01•: or st•ndera
u•• ••t:l lenk solution
7.5 Trensfer 7.6 use

oort1on 193.7-nm
or dlg••ted wavel•ngtn
••11101• 01" •nd tlec:kgrouna
st.end•rd to c:orrectlon for
r••ct.1on ve•••l en•ly•l•
7.5 7.7 To
operet.e
•rgon nyorogen
Add KI tl•me, follow
ao lut 1or.i: Sdd 81enut•ctur•r·a
SnClz solution 1nstruc:t.1ona
7. !5 7.8
Plot
•baorti•nc:es of
Reduce 111ete l to sp lk•d a•mp lea.
lta lowest Dl•nk va tne
0•1det.1on st•t• c:oncentr•tlona
7.5
7.e
Att•c" reect1on H•ve
ves•el to 7•s concentr•t1on
tl•••w•re: 111 tie o•rt. or
••dlclne aroooer wlt" cel1tlr•t1on
t 1nc slurry: lnsert CUI"¥&
lnto re•ct.1on ve•••l
St.oo
7061 - 9 Revision 1
December 1987
METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDE)

1.1 Method 7062 is an atomic absorption procedure for determining 1 µg/L
to 400µg/L concentrations of antimony and arsenic in wastes, mobility procedure
extracts, soils, and ground water. Method 7062 is approved for sample matrices
that contain up to 4000 mg/L concentrations of cobalt, copper, iron, mercury, and
nickel. A solid sample can contain up to 40% by weight of the interferents
before exceeding 4000 mg/L in a digested sample. All samples including aqueous
matrices must be subjected to an appropriate dissolution step prior to analysis.
Spiked samples and relevant standard reference materials are used to determine
the applicability of the method to a given waste.

2.1 Samples are prepared according to the nitric acid digestion procedure
described in Method 3010 for aqueous and extract samples and the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for sediments, soils, and sludges. Excess peroxide is
removed by evaporating samples to near dryness at the end of the digestion
followed by degassing the samples upon addition of urea. L-cystine is then added
as a masking agent. Next, the antimony and arsenic in the digest are reduced to
the trivalent forms with potassium iodide. The trivalent antimony and arsenic
are then converted to volatile hydrides using hydrogen produced from the reaction
of the acidified sample with sodium borohydride in a continuous-flow hydride
generator.
2.2 The volatile hydrides are swept into an air-acetylene flame heated
quartz absorption cell located in the optical path of an atomic absorption
spectrophotometer. The resulting absorption of the lamp radiation is
proportional to the arsenic or antimony concentration.
2.3 The typical detection limit for this method is 1.0 µg/L.
3.0 INTERFERENCES
3.1 Very high (>4000 mg/L) concentrations of cobalt, copper, iron,
mercury, and nickel can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.
3.2 Traces of peroxides left following the sample work-up can result in
analytical interferences. Peroxides must be removed by evaporating each sample
to near dryness followed by reaction with urea and allowing sufficient time for
degassing before analysis (see Sections 7.1 and 7.2).
7062-1 Revision 0
November 1992
4.1 Electric hot plate: Large enough to hold at least several 100 ml
Pyrex digestion beakers.
4.2 A continuous-flow hydride generator: A commercially available
continuous-flow sodium borohydride/HCl hydride generator or a generator
constructed similarly to that shown in Figure 1 (P. S. Analytical or equivalent).
4.2.1 Peristaltic Pump: A four-channel, variable-speed peristaltic
pump to permit regulation of liquid-stream flow rates (lsmatec Reglo-100
or equivalent). Pump speed and tubing diameters should be adjusted to
provide the following flow rates: sample/blank flow = 4.2 ml/min;
borohydride flow= 2.1 ml/min; and potassium iodide flow= 0.5 ml/min.
4.2.2 Sampling Valve (optional): A sampling valve (found in the
P. S. Analytical Hydride Generation System or equivalent) that allows
switching between samples and blanks (rinse solution) without introduction
of air into the system will provide more signal stability.
4.2.3 Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
mixing T's, and connectors are made of teflon and are of compatible sizes
to form tight, leak-proof connections (Latchat, Technicon, etc. flow
injection apparatus accessories or equivalent).
4.2.4 Mixing Coil: A 20-turn coil made by wrapping transfer tubing
around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).
4.2.5 Mixing Coil Heater: A 250-ml Erlenmeyer flask containing 100
ml of water heated to boiling on a dedicated one-beaker hotplate (Corning
PC-35 or equivalent). The mixing coil in 4.2.4 is immersed in the boiling
water to speed kinetics of the hydride forming reactions and increase
solubility of interfering reduced metal precipitates.
4.2.6 Gas-Liquid Separator: A glass apparatus for collecting
liquid and gaseous products (P.T. Analytical accessory or equivalent)
which allows the liquid fraction to drain to waste and gaseous products
above the liquid to be swept by a regulated carrier gas (argon) out of the
cell for analysis. To avoid undue carriei gas dilution, the gas volume
above the liquid should not exceed 20 ml. See Figure 1 for an acceptable
separator shape.
4. 2. 7 Condensor: Mai sture pi eked up by the carrier gas must be
removed before encountering the hot absorbance cell. The moist carrier
gas with the hydrides is dried by passing the gasses through a small (< 25
ml) volume condensor coil (Ace Glass Model 6020-02 or equivalent) that is
cooled to 5°C by a water chiller {Neslab RTE-110 or equivalent). Cool tap-
water in place of a chiller is acceptable.
7062-2 Revision 0
November 1992
4.2.8 Flow Meter: A meter capable of regulating up to 1 L/min of
argon carrier gas is recommended.
4.3 Absorbance Cell: A 17 cm or longer quartz tube T-cell (windowless is
trongly suggested) is recommended, as shown in Figure 1 (Varian Model VGA-76
ccessory or equivalent). The cell is held in place by a holder that positions
he cell about 1 cm over a conventional AA air-acetylene burner head. In
peration, the cell is heated to around 900°C by an air-acetylene flame.
4.4 Atomic absorption spectrophotometer: Single or dual channel, single-
r double-beam instrument having a grating monochromator, photomultiplier
etector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
or interfacing with a strip-chart recorder.
4.5 Burner: As recommended by the particular instrument manufacturer for
n air-acetylene flame. An appropriate mounting bracket attached to the burner
hat suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
s required.
4.6 Antimony and arsenic hollow cathode lamps or antimony and arsenic
lectrodeless discharge lamps and power supply. Super-charged hollow-cathode
amps or EDL lamps are recommended for maximum sensitivity.
4.7 Strip-chart recorder (optional}: Connect to output of
pectrophotometer.
1. 0 REAGENTS
5.1 Reagent water: Water must be monitored for impurities. Refer to
:hapter 1 for definition of Reagent water.
5.2 Concentrated nitric acid (HN0 3 ): Acid must be analyzed to determine
evels of impurities. If a method blank is <MDL, the acid can be used.
5.3 30% Hydrogen peroxide (H 2 02 }: Peroxide must be a tin-free grade.
5.4 Concentrated hydrochloric acid {HCl}: Acid must be analyzed to
etermine levels of impurities. If a method blank is <MDL, the acid can be used.
7062-3 Revision 0
November 1992
QUARTZ CELL -+
TO
WASTE
-
PUt1P
r CONOEHSER--+
H~Oll<t
111 >CI HG
TE Es
ARGOH
I
·i.o I SCOHHECTE UALUE
OURIHG Sel'Sn (SAt1PLlHG)
\... nUALYSIS
THERt10t1ETER _ _.,. L_. DRAIH
20 TUltH COIL
(TEFLOH)
HOTPLATE~
Figure I. Continuous-flow sodium borohydride/hydride generator apparatus set-

up and an AAS sample introduction system.
7062-4 Revision 0
November 1992
5.5 Diluent solution: A 3% HCl solution in reagent water must be prepared
as a diluent solution if excessive levels of analytes or interfering metals are
found in the undiluted samples.
5.6 Urea (H 2 NCONH 2 ): A 5.00-g portion of reagent grade urea must be added
to a 25-ml aliquot of each sample for removal of excess peroxide through
degassing (see Section 7.2).
5.7 l-cystine (C 6 H12 N2 04 S2 ): A 1.00-g portion of reagent grade l-cystine
must be added to a 25-ml aliquot of each sample for masking the effects of
suppressing transition metals (see Section 7.2).
5.8 20% Potassium iodide (KI): A 20% KI solution (20 g reagent-grade KI
dissolved and brought to volume in 100 ml reagent water) must be prepared for
reduction of antimony and arsenic to their +3 valence states.
5.9 4% Sodium borohydride {NaBH 4 ): A 4% sodium borohydride solution (20
g reagent-grade NaBH 4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the antimony and arsenic to their
hydrides.
5.10 Analyte solutions:
5.10.l Antimony and arsenic stock standard solution (1,000 mg/l):
Either procure certified aqueous standards from a supplier (Spex,
Inorganic Ventures, or equivalent) and verify by comparison with a second
standard, or dissolve 1.197 g of antimony trioxide Sb 203 and 1.320 g of
arsenic trioxide As 203 in 100 ml of reagent water containing 4 g NaOH.
Acidify the solution with 20 ml concentrated HN0 3 and dilute to 1 liter.
5.10.2 Intermediate antimony and arsenic solution: Pipet 1 ml
stock antimony and arsenic solution into a 100-ml volumetric flask and
bring to volume with reagent water containing 1.5 ml concentrated
HN0 3 /liter (1 ml= 10 µg each of Sb and As).
5.10.3 Standard antimony and arsenic solution: Pipet 10 ml
intermediate antimony and arsenic solution into a 100-mL volumetric flask
and bring to volume with reagent water containing 1.5 ml concentrated
HN0 3 /liter (1 ml= 1 µg each of Sb and As).

7062-5 Revision 0
November 1992
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile antimony and arsenic compounds are
suspected to be present in the samples.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
7. 0 PROCEDURE
7.1 Place a 100-ml portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-ml digestion beaker. Digest aqueous samples and
extracts according to Method 3010. Digest solid samples according to Method 3050
(furnace AA option) with the following modifications: add 5 ml of concentrated
hydrochloric acid just prior to the final volume reduction stage to aid in
antimony recovery; the final volume reduction should be to less than 5 ml but not
to dryness to adequately remove excess hydrogen peroxide (see note). After
dilution to volume, further dilution with diluent may be necessary if analytes
are known to exceed 400µg/l or if interferents are expected to exceed 5000 mg/l
in the digest.
Note: For solid digestions, the volume reduction stage is critical to obtain
accurate data, especially for arsenic. Close monitoring of each sample is
necessary when this critical stage is reached.
7.2 Prepare samples for hydride analysis by adding 5.00 g urea, 1.00 g l-
cystine, and 20 ml concentrated HCl to a 25-ml aliquot of digested sample in a
50-ml volumetric flask. Heat in a water bath until the l-cystine has dissolved
and effervescence has subsided (At least 30 minutes is suggested. If
effervescense is still seen, repeat step 7.1 with more volume reduction.). Bring
flask to volume with reagent water before analyzing. A 1:1 dilution correction
must be made in the final concentration calculations.
7 .3 Prepare working standards from the standard antimony and arsenic
solution. Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-ml
volumetric flasks and bring to volume with diluent. These concentrations will
be 0, 5, 10, 15, 20, and 25 µg Sb and As/liter.
7.4 If EP extracts (Method 1310) are being analyzed for arsenic, the
method of standard additions must be used. Spike appropriate amounts of
intermediate or standard antimony and arsenic solution to three 25 ml aliquots
of each unknown. Spiking volumes should be kept less than 0.250 ml to avoid
excessive spiking dilution errors.
7. 5 Set up instrumentation and hydride generation apparatus and fi 11
reagent containers. The sample and blank flows should be set around 4.2 ml/min,
the borohydride flow around 2.1 ml/min, and the potassium iodide flow around 0.5
ml/min. The argon carrier gas flow is adjusted to about 200 ml/min. For the AA,
7062-6 Revision 0
November 1992
use the 217.6-nm wavelength and 0.7-nm slit width without background correction
if analyzing for antimony. Use the 193.7-nm wavelength and 0.7-nm slit width
without background correction for the analysis of arsenic. Begin all flows and
allow 10 minutes for warm-up.
7.6 Place sample feed line into a prepared sample solution and start pump
to begin hydride generation. Wait for a maximum steady-state signal on the
strip-chart recorder or output meter. Switch to blank sample and watch for
signal to decline to baseline before switching to the next sample and beginning
the next analysis. Run standards first (low to high), then unknowns. Include
appropriate QA/QC solutions, as required. Prepare calibration curves and convert
absorbances to concentration. See following analytical flowchart.
CAUTION: The hydrides of antimony and arsenic are very toxic.
Precautions must be taken to avoid inhaling the gas.
7.7 If the method of standard additions was employed, plot the measured
concentration of the spiked samples and unspiked sample versus the spiked
concentrations. The spiked concentration axis intercept will be the method of
standard additions concentration. If the plot does not result in a straight
line, a nonlinear interference is present. This problem can sometimes be
overcome by dilution or addition of other reagents if there is some knowledge
about the waste. If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
8.0 QUALITY CONTROL

8.1 See section 8.0 of Method 7000.

9.1 The relative standard deviations obtained by a single laboratory for
7 replicates of a contaminated soil were 18% for antimony at 9.1 ug/L in solution
and 4.6% for arsenic at 68 ug/L in solution.
10.0 REFERENCES
2. "Evaluation of Hydride Atomic Absorption Methods for Antimony, Arsenic,
Selenium, and Tin", an EMSL-LV internal report under Contract 68-03-3249,
Job Order 70.16, prepared for T. A. Hinners by D. E. Dobb, and J. D.
Lindner of Lockheed Engineering and Sciences Co., and L. V. Beach of the
Varian Corporation.
7062-7 Revision 0
November 1992
METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDE)
St.rt
7 1 u.. Method 1 1 u..

3050 (furnace Solid Aqueoua Method 3010
AA option) to to dig .. t 100
dig .. t 1 0 g ml aample
a ample
7 1-7 4 7.2 Add to

Dig .. t with aliquot urea,
H,O, aa L-cyatine, HCl; H-~~~~~~~~
deacribed in hHt H,O bath;
Method 3050 bring to volume
7 3 Pr•par•
1 S Add atandarda from
concentrat•d atandard atock
HCl aolutiona of Sb
and Aa
7 6 Do final 1 4 Uae the

val um• Extract• method of
reduction and atandard
dilution, aa addition• on
deacribed extracta, only
All
Other
7 4 Spik• 3 1 S-1 6 Analyze

aliquota with the aampl•
working uaing hybrid
atandard s. generation
aolution apparatua
'!ea
7. S-7. 6 Analyze 1 1 Determine

7 1 Further th• •ample Sb and Aa
dilute with uaing hybrid coneentrationa
diluent generation from lin•ar
apparatua plot
1 1 D.t.rmin•
Sb and Aa cone
from atandard
calibration
curv•
Stop
7062-8 Revision O
November 1992
METHOD 7080A
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)

I.I See Section 1.0 of Method 7000.

2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 High hollow cathode current settings and a narrow spectral band pass
must be used, because both barium and calcium emit strongly at barium's
analytical wavelength.
3.3 Barium undergoes significant ionization in the nitrous oxide/
acetylene flame, resulting in a significant decrease in sensitivity. All
samples and standards must contain a ionization suppressant. Type of
suppressant and concentration must be documented.

4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters {general):
4.2.1 Barium hollow cathode lamp.
4.2.2 Wavelength: 553.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.7787 g barium chloride
{BaCl 2·2H 20) analytical reagent grade in reagent water and dilute to I
7080A - I Revision I
November 1992
liter (1000 mg/L). Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5. 2. 2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after
processing. All calibration standards and samples should contain the
ionization suppressant. KCl is detailed in Section 5.2.3.

6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7. 0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
given in Chapter Three, Section 3.2.
7.2 See Method 7000, Section.7.2, Direct Aspiration.
8.0 QUALITY CONTROL


9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 553.6 nm.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic waste
effluent, digested with Method 3010, at concentrations of 0.4 and 2 mg Ba/L gave
standard deviations of ±0.043 and ±0.13, respectively. Recoveries at these
levels were 94% and 113%, respectively.
10.0 REFERENCES
I. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
November 199:
METHOD 7080A
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
Start
5 0 Prepare
al;andarda
7 l for •ample
preparation •••
Ch;apler 3, Secl1on
3 2
7 2 Analyze ua1ng
Method 7000
Section 7 2
Stop
November 1992
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)


3.0 INTERFERENCES
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, cadmium analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Simultaneous
background correction is required to avoid erroneously high results.
3.3 Excess chloride may cause premature volatilization of cadmium.
Ammonium phosphate used as a matrix modifier minimizes this loss. Other
modifiers may be used as long as it is documented with the type of suppressant
and concentration.
3.4 Many plastic pipet tips (yellow} contain cadmium. Use "cadmium-
free" tips.

4.2 Instrument parameters (general}:
4.2.l Drying time and temp: 30 sec at 125°C.
4.2.2 Ashing time and temp: 30 sec at 500°C.
4.2.3 Atomizing time and temp: 10 sec at 1900°C.
4.2.4 Purge gas: Argon.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
November 1992
NOTE: The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20-ul injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller sizes
of furnace devices or those employing faster rates of atomization
can be operated using lower atomization temperatures for shorter
time periods than the above-recommended settings.
5.0 REAGENTS
5.2 Preparation of standards:
5.2.l Stock solution: Dissolve 1.000 g of cadmium metal
(analytical reagent grade) in 20 ml of 1:1 HN0 3 and dilute to 1 liter with
reagent water. Alternatively, procure a certified standard from a
5.2.2 Prepare dilutions of the stock cadmium solution to be used
as calibration standards at the time of analysis. To each 100 nil of
standard and sample alike add 2.0 ml of the ammonium phosphate solution.
The calibration standards shou1d be prepared to contain 0.5% (v/v) HN0 3 •
5.2.3 Ammonium phosphate solution (40%): Dissolve 40 g of
ammonium phosphate, (NH 4 ) 2HP0 4 (analytical reagent grade), in reagent water

6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7. 0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL

8.1 See Section 8.0 of Method 7000 .

November 1992
9.2 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.5-10 ug/L.
Detection limit: 0.1 ug/L.
contractor laboratories. The data are intended to show the precision. of. the
10. 0 REFERENCES
November 1992
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory

Matrix Method Replicates
Lagoon soil 3050 0.10, 0.095 ug/g

NBS SRM 1646 Estuarine sediment 3050 0.35 ug/g 8
Solvent extract of oily waste 3030 1.39, 1.09 ug/L
aBias of -33 from expected value.
November 1992
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
Start
S 0 Pr•pilr•
atandarda
7 1 for aampl•
preparation tee
Chapter 3, Sect1on
3 2
7 2 Analyz• u11ng
Method 7000
S•ct1on 7 3
Stop
November 1992
METHOD 7196
CHROMIUM. HEXAVALENT (COLORIMETRIC)

1.1 Method 7196 is used to determine the concentration of dissolved
hexaval ent chromium [Cr(VI)] in Extract ion Procedure (EP) toxicity charac-
teristic extracts and ground waters. This method may also be applicable to
certain domestic and industrial wastes, provided that no interfering
substances are present (see Step 3.1 below).
1.2 Method 7196 may be used to analyze samples containing from 0.5 to
50 mg of Cr(VI) per liter.
2.1 Dissolved hexavalent chromium, in the absence of interfering amounts
of substances such as molybdenum, vanadium, and mercury, may be determined
colorimetrically by reaction with diphenylcarbazide in acid solution. A red-
violet color of unknown composition is produced. The reaction is very
sensitive, the absorbancy index per gram atom of chromium being about 40,000
at 540 nm. Addition of an excess of diphenylcarbazide yields the red-violet
product, and its absorbance is measured photometrically at 540 nm.
3.0 INTERFERENCES
3.1 The chromium reaction with diphenylcarbazide is usually free from
interferences. However, certain substances may interfere if the chromium
concentration is relatively low. Hexavalent molybdenum and mercury salts also
react to form color with the reagent; however, the red-violet intensities
produced are much lower than those for chromium at the specified pH.
Concentrations of up to 200 mg/L of molybdenum and mercury can be tolerated.
Vanadium interferes strongly, but concentrations up to 10 times that of
chromium will not cause trouble.
3.2 Iron in concentrations greater than 1 mg/L may produce a yellow
color, but the ferric iron color is not strong and difficulty is not normally
encountered if the absorbance is measured photometrically at the appropriate
wavelength.
4.1 Colorimetric equipment - One of the following is required: Either a
spectrophotometer, for use at 540 nm, providing a 1 ight path of 1 cm or
longer, or a filter photometer, providing a light path of 1 cm or longer and
equipped with a greenish-yellow filter having maximum transmittance near
540 nm.
7196 - 1 Revision 1
December 1987
5.0 REAGENTS
determination.
5.3 Potassium dichromate stock solution - Dissolve 141.4 mg of dried
potassium dichromate, K2Cr207, in water and dilute to 1 liter (1 ml = 50 ug
Cr).
5.4 Potassium dichromate standard solution - Dilute 10.00 ml potassium
dichromate stock solution to 100 ml (1 ml= 5 ug Cr).
5.5 Sulfuric acid ((10%) (v/v)), H2S04. Dilute 10 ml of distilled
reagent grade or spectrograde quality H2S04 to 100 ml with water.
5.6 Diphenylcarbazide solution - Dissolve 250 mg 1,5-diphenylcarbazide
in 50 ml acetone. Store in a brown bottle. Discard when the solution becomes
discolored.
5.7 Acetone, CH3COCH3. Avoid or redistill material that comes in
containers with metal or metal-lined caps.
6.2 Since the stability of Cr( VI) in EP extracts is not completely
understood at this time, the analysis should be carried out as soon as
possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4°C until analyzed. The maximum holding time
prior to analysis is 24 hours.
7.0 PROCEDURE
7.1 Color development and measurement - Transfer 95 ml of the extract to
be tested to a 100-ml volumetric flask. Add 2.0 ml diphenylcarbazide solution
and mix. Add H2S04 solution to give a pH of 2 ± 0.5, dilute to 100 ml with
water, and let stand 5 to 10 minutes for full color development. Transfer an
appropriate portion of the solution to a 1-cm absorption cell and measure its
absorbance at 540 nm. Use water as a reference. Correct the absorbance
reading of the sample by subtracting the absorbance of a blank carried through
the method (see Note below). An aliquot of the sample containing all reagents
7196 - 2 Revision 1
December 1987
except di phenyl semi carbaz i de should be prepared and used to correct the
sample for turbidity (i.e. a turbidity blank). From the corrected absorbance,
determine the mg/L of chromium present by reference to the calibration curve.
NOTE: If the solution is turbid after dilution to IOO ml in Step 7.I, above,
take an absorbance reading before adding the carbaz i de reagent and
correct the absorbance reading of the final colored solution by
subtracting the absorbance measured previously.
7.2 Preparation of calibration curve
7.2.I To compensate for possible slight losses of chromium during
digestion or other operations of the analysis, treat the chromium
standards by the same procedure as the sample. Accordingly, pipet a
chromium standard solution in measured volumes into 250-ml beakers or
conical flasks to generate standard concentrations ranging from IO to
200 ug/L Cr(VI) when diluted to the appropriate volume.
7.2.2 Develop the color of the standards as for the samples.
Transfer a suitable portion of each colored solution to a I-cm absorption
ce 11 and measure the absorbance at 540 nm. As reference, use water.
Correct the absorbance readings of the standards by subtracting the
absorbance of a reagent blank carried through the method. Construct a
calibration curve by plotting corrected absorbance values against mg/L of
Cr(VI).
7.3 Verification
7.3.I For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference is
affecting color development. This must be accomplished by analyzing a
second IO-ml aliquot of the pH-adjusted filtrate that has been spiked with
Cr(VI). The amount of spike added should double the concentration found
in the original aliquot. The increase must be~ 30 ug Cr(VI)/L. To verify
the absence of an interference, the spike recovery must be between 85% and
II5%.
7.3.2 If addition of the spike extends the concentration beyond the
calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.3.3 If the result of verification indicates a suppressive
interference, the sample should be diluted and reanalyzed.
7.3.4 If the interference persists after sample dilution, an
alternative method (Method 7I95, Coprecipitation, or Method 7197,
Chelation/Extraction) should be used.
7 .4 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the 1ow spike recovery is due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using IN sodium
hydroxide and then respiking and analyzing. If a spike recovery of 85-II5% is
7I96 - 3 Revision I
December I987
obtained in the alkaline aliquot of an acidic extract that initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified.
7.5 Analyze all EP extracts, all samples analyzed as part of a delisting
petition, and all samples that suffer from matrix interferences by the method
of standard additions (see Method 7000, Step 8.7).
8.0 QUALITY CONTROL
8.2 Dilute samples if they are more concentrated than the highest
8.3 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.4 Verify calibration with an independently prepared QC reference sample
every 15 samples.
8.5 Run one matrix spike replicate or one replicate sample for every 10
samples. A replicate sample is a sample brought through the whole sample
preparation and analytical process.
8.6 The method of standard additions (see Method 7000, Step 8.7) shall be
used for the analysis of all EP extracts, on all analyses submitted as part of
a delisting petition, and whenever a new sample matrix is being analyzed.
10. 0 REFERENCES
December 1982, Methods 218.4 and 218.5.
3. Rohrbough, W.G.; et al. Reagent Chemicals, American Chemical Society
7196 - 4 Revision 1
December 1987
TABLE 1.
METHOD PERFORMANCE DATA

Wastewater treatment sludge Not known 0.096, 0.107 ug/g

Sediment from chemical
storage area 3060 115 , 11 7 ug/ g
7196 - 5 Revision 1
December 1987
M£THOO 71915
H~XAYALfNT CHROMIUM (CCLOAIH£TAlCJ
Start
7. s
For color develop•ent
trensfer extract to
flask: add
dlphenylcarbezld•
solutlon: •1•
7. s
ACIO
H1 SO. solut ton:
01 lute: let
stand
7. l
Meaaure anCI correct

aosoroance reaa1ng:
Cleter•tne cnro•1u•
present
7.2.l
Treat
chro•tu•
standards by
s••• procedure
es aa•ple
7 .2. l
Pt pet
cnro•lu•
standard
aolutlon lnto
bealcera
7196 - 6 Revision I
December 1987
METHOD 7196
HEXAVALENT CHROMIUM (COLORIMETRIC)
(Cont lnuedl
7.2.2
7 ...
Oeveloo color of
• t•nderos: me•sure
eno correct re•Otng; Retest
construct celtbr•tton
curve
7.J.t
No
Anely%• • 2nd
•l touot of oH-
•Olusteo ftltr•te
sotk•O wtth Cr (VII
tor vertftc•tton
7.3.2 7.4
Ollute Anelyttc:al
•nelyata 111ethoO vertfteo
solutton wtth -weste 1• not
blenk solutton heterCIOUS
7.3.J 7.5
Anelyt•
Ct lute semc>l• by met,,oo
ena reenely%e o t st•nderCI
•CIOtttons
No
Stoa
7.3.•
Uee elternettve
11ethod
7196 - 7 Revision 1
December 1987
METHOD 7430
LITHIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)

3.0 INTERFERENCES
4.2 Instrument parameters (general):
4.2.1 Lithium hollow cathode lamp.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background Correction: Not required.
5. 0 REAGENTS
5.2 Preparation of standards
5. 2 . 1 St oc k sol ut i on : ( 1. 0 mL = 1. 0 mg Li ) . Di s so l ve 5. 324 g
lithium carbonate, Li2C03, in a minimum volume of 1:1 HCl and dilute to
1 liter with water. Alternatively, procure a certified standard from a
5.2.2 Prepare dilutions of the stock solution to be used as
should be prepared using the same type of acid as the samples used to
prepare the samples and cover the range of expected concentrations in the
samples.
7430 - 1 Revision 0
December 1987
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation - The procedures for preparation of the sample
are given in Chapter Three, Step 3.2.
7.2 See Method 7000, Step 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
9 .1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.1-2 mg/L at a wavelength of 670.8 nm.
10.0 REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water
Works Association, Water Pollution Control Federation, American Public
Health Association: Washington, DC, 1985.
7430 - 2 Revision 0
December 1987
METHOD 7430
LITHIUM (ATOMIC ASORPTION, DIRECT ASIRATION)
Start
6.2 Prepare
et••dard1
7.1 ror Hapll

pr1paratioa, 1ee
Ckapt1r 3, Step 3.2
7.2 Aaal7ze a1ia1

Metkod 7000, Step
7.3
Stop
7430 - 3 Revision 0
December 1987
METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)

1.1 Method 7470 is a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury in mobility-procedure extracts, aqueous
wastes, and ground waters. (Method 7470 can also be used for analyzing certain
solid and sludge-type wastes; however, Method 7471 is usually the method of
choice for these waste types.) All samples must be subjected to an appropriate
dissolution step prior to analysis.

2.1 Prior to analysis, the liquid samples must be prepared according to
the procedure discussed in this method.
2.2 Method 7470, a cold-vapor atomic absorption technique, is based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury is reduced
to the elemental state and aerated from solution in a closed system. The mercury
vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function of mercury
concentration.
2.3 The typical detection limit for this method is 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/L of sulfide as sodium sulfide do
not interfere with the recovery of added inorganic mercury from reagent water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/L had no effect on recovery of mercury from spiked
samples.
3.3 Seawaters, brines, and industrial effluents high in chlorides require
additional permanganate {as much as 25 ml) because, during the oxidation step,
chlorides are converted to free chlorine, which also absorbs radiation of 253.7
nm. Care must therefore be taken to ensure that free chlorine is absent before
the mercury is reduced and swept into the cell. This may be accomplished by
using an excess of hydroxylamine sulfate reagent (25 ml). In addition, the dead
air space in the BOD bottle must be purged before adding stannous sulfate. Both
inorganic and organic mercury spikes have been quantitatively recovered from
seawater by using this technique.
3.4 Certain volatile organic materials that absorb at this wavelength may
also cause interference. A preliminary run without reagents should determine if
this type of interference is present.
November 1992
4.1 Atomic absorption spectrophotometer or equ i va 1ent: Any atomic
absorption unit with an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed. Instruments designed specifically for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrodeless discharge lamp.
4.3 Recorder: Any multi range variable-speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption cell: Standard spectrophotometer cells 10 cm long with
quartz end windows may be used. Suitable cells may be constructed from Plexiglas
tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to the
longitudinal axis, and quartz windows (1 in. diameter x 1/16 in. thickness) are
cemented in place. The cell is strapped to a burner for support and aligned in
the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter holes are cut
in the middle of each card. The cards are then placed over each end of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance. ·
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter air/min
may be used. A Masterflex pump with electronic speed control has been found to
be satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter/min.
4.7 Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of mag-
nesium perchlorate or a small reading lamp with 60-W bulb which may be used to
prevent condensation of moisture inside the cell. The lamp should be positioned
to shine on the absorption cell so that the air temperature in the cell is about
l0°C above ambient.
4.9 The cold-vapor generator is assembled as shown in Figure 1.
4.9.1 The apparatus shown in Figure 1 is a closed system. An open
system, where the mercury vapor is passed through the absorption cell only
once, may be used instead of the closed system.
4.9.2 Because mercury vapor is toxic, precaution must be taken to
avoid its inhalation. Therefore, a bypass has been included in the system
either to vent the mercury vapor into an exhaust hood or to pass the vapor
through some absorbing medium, such as:
November 1992
1. Equal volumes of 0.1 M KMn0 4 and 10% H2S0 4 ; or
2. 0.25% Iodine in a 3% KI solution.
A specially treated charcoal that will adsorb mercury vapor is also
available from Barnebey and Cheney, East 8th Avenue and North Cassidy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
4.10 Hot plate or equivalent - Adjustable and capable of maintaining a
temperature of 90-95°C.
4.11 Graduated cylinder or equivalent.
5.0 REAGENTS
5 .1 Reagent Water: Reagent water wi 11 be interference free. A11
references to water in this method will refer to reagent water unless otherwise
specified.
5.2 Sulfuric acid {H 2 S0 4 ), concentrated: Reagent grade.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfuric acid
to 1. O l it er.
5.4 Nitric acid {HN0 3 }, concentrated: Reagent grade of low mercury
content. If a high reagent blank is obtained, it may be necessary to distill the
nitric acid.
5. 5 Stannous sulfate: Add 25 g stannous sulfate to 250 ml of 0. 5 N
• H2 S0 4 • This mixture is a suspension and should be stirred continuously during
use. (Stannous chloride may be used in place of stannous sulfate.)
5.6 Sodium chloride-hydroxylamine sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 ml. {Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.)
5.7 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate in 100 ml of reagent water.
5.8 Potassium persulfate, 5% solution (w/v): Dissolve 5 g of potassium
persulfate in 100 ml of reagent water.
5.9 Stock mercury solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water. Add 10 ml of concentrated HN0 3 and adjust the volume to
100.0 ml (1 ml= 1 mg Hg). Stock solutions may also be purchased.
5.10 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 g per ml. This
working standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be maintained at
November 1992
0.15% nitric acid. This acid should be added to the flask, as needed, before
addition of the aliquot.

6.3 Aqueous samples must be acidified to a pH <2 with HN0 3 • The
suggested maximum holding times for mercury is 28 days.
7. 0 PROCEDURE
7.1 Sample preparation: .Transfer 100 ml, or an aliquot diluted to
100 ml, containing <1.0 g of mercury, to a 300-ml BOD bottle or equivalent. Add
5 ml of H2 S0 4 and 2.5 ml of concentrated HN0 3 , mixing after each addition. Add
15 ml of potassium permanganate solution to each sample bottle. Sewage samples
may require additional permanganate. Ensure that equal amounts of permanganate
are added to standards and blanks. Shake and add additional portions of
potassium permanganate solution, if necessary, until the purple color persists
for at least 15 min. Add 8 ml of potassium persulfate to each bottle and heat
for 2 hr in a water bath maintained at 95°C. Coo 1 and add 6 ml of sodium
chloride-hydroxyl amine sulfate to reduce the excess permanganate. After a delay,
of at least 30 sec, add 5 ml of stannous sulfate, immediately attach the bottle
to the aeration apparatus, and continue as described in Paragraph 7.3.
7.2 Standard preparation: Transfer 0-, 0.5-, 1.0-, 2.0-, 5.0-, and 10.0-
ml aliquots of the mercury working standard, containing 0-1.0 ug of mercury, to
a series of 300-ml BOD bottles. Add enough reagent water to each bottle to make
a total volume of 100 ml. Mix thoroughly and add 5 ml of concentrated H2 S0 4 and
2.5 ml of concentrated HN0 3 to each bottle. Add 15 ml of KMn0 4 solution to each
bottle and allow to stand at least 15 min. Add 8 ml of potassium persulfate to
each bottle and heat for 2 hr in a water bath maintained at 95°C. Cool and add
6 ml of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate. When the solution has been decolorized, wait 30 sec, add 5 ml of
the stannous sulfate solution, immediately attach the bottle to the aeration
apparatus, and continue as described in Paragraph 7.3.
7.3 Analysis: At this point the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of I liter/min, is allowed to run continuously. The
absorbance will increase and reach a maximum within 30 sec. As soon as the
recorder pen levels off (approximately I min), open the bypass valve and continue
the aeration until the absorbance returns to its minimum value. Close the bypass
7470A - 4 Revision I
November 1992
valve, remove the stopper and frit from the BOD bottle, and continue the
aeration. Because of instrument variation refer to the manufacturers recommended
operating conditions when using this method.
7.4 Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve.
7.5 Calculate metal concentrations (l} by the method of standard
additions, or (2} from a calibration curve. All dilution or concentration
factors must be taken into account. Concentrations reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL


10.0 REFERENCES
1. Methods for Chemi ca 1 Ana 1ys is of Water and Wastes, EPA-600/4-82-055,
November 1992
METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
Start
! !
7 1 Tran•f•r 7.2 Tran•f•r
aliquot to aliquot of th•
bot tl•, add Hg working
H,SO, and •tandard to
HNO,, and mix botti.
l l
7 2 Add r•ag•nt
7.1 Add I<MnO, wal•r,mix,add
and •hak• concentrat•d
H,SO, and HNO,
l
7.2 Add I<MnO,,
I• aampl• 7 1 Add mor• potaa•ium
from permanganate peraul!at•,h•at
••wag•? if nece••ary !or 2 hr• and
cool
No 1
7 l Add 7 2 Add aodium
pota••ium chloride·
per•ulfate,h•at 1+-~~~~~~~ hydroxylamin•
for 2 hr•,cool •ulfat•,wait 30
••c
l l
7.1 Add •odium 7 3 For 7 2 Add
chlorid•· analy•1• run alannau.a
hydroxyl amine ---+ circulating i.-~~~~ •ulfat•,attach
aulfal•,wait 30 pump to aeration
aec continuou•ly apparatu•
l
7 1 Add 7 4 Conatruct
atilnnoua calibration
aulfat•,attach ~ curve 1 datarmJ.n•
to a•r.a.tion peak height and
apparatu• Hg value
7 S Analyze
a ample
7 6 Routinely
analyze
duplicalea,
a piked
aampl•a
7 7 Calculate
metal
concenlra.lJ.ona
c Stop
Revision 1
7470A - 6 November 1992
METHOD 7471A
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE}

1.1 Method 7471 is approved for measuring total mercury (organic and
inorganic) in soils, sediments, bottom deposits, and sludge-type materials. All
samples must be subjected to an appropriate dissolution step prior to analysis.
If this dissolution procedure is not sufficient to dissolve a specific matrix
type or sample, then this method is not applicable for that matrix.

2.1 Prior to analysis, the solid or semi-solid samples must be prepared
according to the procedures discussed in this method.
2.2 Method 7471, a cold-vapor atomic absorption method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The mercury
is reduced to the elemental state and aerated from solution in a closed system.
The mercury vapor passes through a cell positioned in the light path of an atomic
absorption spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/Kg of sulfide, as sodium sulfide,
do not interfere with the recovery of added inorganic mercury in reagent water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/Kg had no effect on recovery of mercury from spiked
samples.
3.3 Brines and industrial effluents high in chlorides require additional
permanganate (as much as 25 ml) because, during the oxidation step, chlorides are
converted to free chlorine, which also absorbs radiation of 253 nm. Care must
therefore be taken to ensure that free chlorine is absent before the mercury is
reduced and swept into the cell. This may be accomplished by using an excess of
hydroxylamine sulfate reagent (25 ml). In addition, the dead air space in the
BOD bottle must be purged before adding stannous sulfate.
3.4 Certain volatile organic materials that absorb at this wavelength may
also cause interference. A preliminary run without reagents should determine if
this type of interference is present.
November 1992
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absorption unit with an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed. Instruments designed specifically for the
measurement of mercury using the cold-vapor technique are commercially available
and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrodeless discharge lamp.
4.3 Recorder: Any multi range variable-speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption cell: Standard spectrophotometer cells 10 cm long with
quartz end windows may be used. Suitable cells may be constructed from Plexiglas
tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to the
longitudinal axis, and quartz windows (1 in. diameter x 1/16 in. thickness) are
cemented in place. The cell is strapped to a burner for support and aligned in
the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter holes are cut
in the middle of each card. The cards are then placed over each end of the cell.
The cell is then positioned and a9justed vertically and horizontally to give the
maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of delivering 1 L/min air may
be used. A Masterflex pump with electronic speed control has been found to be
satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 L/min.
4.7 Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of
magnesium perchlorate or a small reading lamp with 60-W bulb which may be used
to prevent condensation of moisture inside the cell. The lamp should be
positioned to shine on the absorption cell so that the air temperature in the
cell is about 10°C above ambient.
4.9 The cold-vapor generator is assembled as shown in Figure 1.
4.9.1 The apparatus shown in Figure 1 is a closed system. An open
system, where the mercury vapor is passed through the absorption cell only
once, may be used instead of the closed system.
4.9.2 Because mercury vapor is toxic, precaution must be taken to
avoid its inhalation. Therefore, a bypass has been included in the system
either to vent the mercury vapor into an exhaust hood or to pass the
vapor through some absorbing medium, such as:
1. equal volumes of 0.1 MKMn0 4 and 10% H2 S0 4 , or
2. 0.25% iodine in a 3% KI solution.
November 1992
A specially treated charcoal that will adsorb mercury vapor is also
available from Barneby and Cheney, East 8th Avenue and North Cassidy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
4.10 Hot plate or equivalent - Adjustable and capable of maintaining a
temperature of 90-95°C.
4.11 Graduated cylinder or equivalent.
5.0 REAGENTS
5 .1 Reagent Water: Reagent water will be interference free. All
references to water in this method refer to reagent water unless otherwise
specified.
5.2 Aqua regia: Prepare immediately before use by carefully adding three
volumes of concentrated HCl to one volume of concentrated HN0 3 •
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfuric acid
to 1 liter.
5.4 Stannous sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N
sulfuric acid. This mixture is a suspension and should be stirred continuously
during use. A 10% solution of stannous chloride can be substituted for stannous
sulfate.
5.5 Sodium chloride-hydroxylamine sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 ml. Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.
5.6 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate in 100 ml of reagent water.
5.7 Mercury stock solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water. Add 10 ml of concentrated nitric acid and adjust the
volume to 100.0 ml (1.0 ml= 1.0 mg Hg).
5.8 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug/ml. This working
standard and the dilution of the stock mercury solutions should be prepared fresh
daily. Acidity of the working standard should be maintained at 0.15% nitric
acid. This acid should be added to the flask, as needed, before adding the
a1 i quot.

November 1992
6.3 Non-aqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible."
7.0 PROCEDURE
7.1 Sample preparation: Weigh triplicate 0.2-g portions of untreated
sample and place in the bottom of a BOD bottle. Add 5 ml of reagent water and
5 ml of aqua regia. Heat 2 min in a water bath at 95°C. Cool; then add 50 ml
reagent water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place in the water bath for 30 min at 95°C. Cool and add 6
ml of sodium chloride-hydroxylamine sulfate to reduce the excess permanganate.
CAUTION: Do this addition under a hood, as Cl 2 could be evolved.
Add 55 ml of reagent water. Treating each bottle
individually, add 5 ml of stannous sulfate and immediately
attach the bottle to the aeration apparatus. Continue as
described under step 7.4.
7.2 An alternate digestion procedure employing an autoclave may also be
used. In this method, 5 ml of concentrated H2 S04 and 2 ml of concentrated HN0 3
are added to the 0.2 g of sample. Add 5 ml of saturated KMn0 4 solution and cover
the bottle with a piece of aluminum foil. The samples are autoclaved .at 121°C
and 15 lb for 15 min. Cool, dilute to a volume of 100 ml with reagent water, and
add 6 ml of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate. Purge the dead air space and continue as described under step 7.4.
Refer to the caution statement in section 7.1 for the proper protocol in reducing
the excess permanganate solution and adding stannous sulfate.
7.3 Standard preparation: Transfer 0.0-, 0.5-, 1.0-, 2.0-, 5.0-, and 10-
ml aliquots of the mercury working standard, containing 0-1.0 ug of mercury, to
a series of 300-ml BOD bottles or equivalent. Add enough reagent water to each
bottle to make a total volume of 10 ml. Add 5 ml of aqua regia and heat 2 min
in a water bath at 95°C. Allow the sample to cool; add 50 ml reagent water and
15 ml of KMn0 4 solution to each bottle and return to the water bath for 30
min. Cool and add 6 ml of sodium chloride-hydroxylamine sulfate solution to
reduce the excess permanganate. Add 50 ml of reagent water. Treating each
bottle individually, add 5 ml of stannous sulfate solution, immediately attach
the bottle to the aeration apparatus, and continue as described in
Step 7.4.
7.4 Analysis: At this point, the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 l/min, is allowed to run continuously. The absorbance,
as exhibited either on the spectrophotometer or the recorder, will increase and
reach maximum within 30 sec. As soon as the recorder pen levels off
(approximately 1 min), open the bypass valve and continue the aeration until the
absorbance returns to its minimum value. Close the bypass valve, remove the
fritted tubing from the BOD bottle, and continue the aeration.
November 1992
7.5 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.6 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or concentration factors must be taken into
account. Concentrations reported for multiphased or wet samples must be
appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL


10.0 REFERENCES
November 1992
TABLE I. METHOD PERFORMANCE DATA

Emission control dust Not known 12, 12 ug/g

Wastewater treatment sludge Not known 0.4, 0.28 ug/g
November 1992
METHOD 7471A
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
Start
Sample Preparation Standard Preparation
Typ• 7 3 Trana!•r
Type a! 2 aliquata a!
Digeatian Hg warlcing
Mat had? atandarda ta
battl••
Type
1
7 1 Weigh 7 2 P.dd to 7 3 P.dd
triplicata aampl• r•ag•nt wat•r
aamplaa,add concantrat•d to volum•,add
raagant w&tar H,SO, and aqua. regi~,
and aqua regia HNO, h•at and coal
l
7 1 Haat, 7.2 Add 7 3 Add
caal,add I<MnO, , cover, r•ag•nt wat•r
r•ag•nt water haat and cool, and [(MnO,
and KMnO, diluta with aolulJ.on,
raagant water h•at and coal
l
7.1 Haat,caol, 7 2 Add aodium 7.3 P.dd aodium
&dd aodium chlorida· chlorid•·
chloride· hydraxylaaun• hydroxyl&min•
hydraxyl&min• aul!&t•,purg• aul!at• and
aul!at• dead a£r •pace reagent waler
l
7 1 Add raag•nt 7 4 For 7.3 Add
Wiltar,•tilnnoua analyaia run alannaua
aul!ate, attach
to aeration
----+t circulating
pump
l+-----1 aul!ah,attach
lo aeration
apparatua conti.nuoualy app&ratua
7 5 Canatruct
calibration
curve;dat.armin•
pealc height and
Hg value
7 6 Analyze
aamplaa
7 7 Routinely
&nalyz•
duplic& t••,
•pik•d
aamplaa
7 8 Calculate
metal
cancentraliona
Stop
November 1992
METHOD 7741A
SELENIUM (ATOMIC ABSORPTION, GASEOUS HYDRIDE)

1.1 Method 7741 is an atomic absorption procedure that is approved for
determining the concentration of selenium in wastes, mobility-procedure extracts,
soils, and ground water, provided that the sample matrix does not contain high
concentrations of chromium, copper, mercury, silver, cobalt, or molybdenum. All
samples must be subjected to an appropriate dissolution step prior to analysis.
Spiked samples and relevant standard reference materials are employed to
determine applicability of the method to a given waste. If interferences are
present the analyst should consider using Method 7740.

2.1 Samples are prepared according to the nitric/sulfuric acid digestion
procedure described in this method. Next, the selenium in the digestate is
reduced to Se(IV) with tin chloride. The Se(IV) is then converted to a volatile
hydride with hydrogen produced from a zi nc/HCl or sodium borohydrate/HCl
reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer; the resulting
absorbance is proportional to the selenium concentration.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury, molybdenum,
nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample work-up can result
in analytical interferences. Nitric acid must be distilled off the sample by
heating the sample until fumes of S0 3 are observed.
3.3 Elemental selenium and many of its compounds are volatile; therefore,
certain samples may be subject to losses of selenium during sample preparation.

4.1 100-mL beaker.
4.2 Electric hot plate or equivalent - Adjustable and capable of
maintaining a temperature of 90-95°C.
November 1992
4.3 A commercially available zinc slurry hydride generator or a generator
constructed from the following material {see Figure 1):
4.3.1 Medicine dropper: Fitted into a size "O" rubber stopper
capable of delivering 1.5 ml.
4.3.2 Reaction flask: 50-mL, pear-shaped, with two 14/20 necks
(Scientific Glass, JM-5835).
4.3.3 Gas inlet-outlet tube: Constructed from a micro cold-finger
condenser {JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stirrer: To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube: 10-cm, filled with glass wool to
prevent particulate matter from entering the burner.
4.3.6 Flow meter: Capable of measuring 1 liter/min.
4.4 Atomic absorption spectrophotometer: Single or dual channel, single-
or double-beam instrument with a grating monochromator, photomultiplier detector,
adjustable slits, a wavelength range of 190-800 nm, and provisions for
interfacing with a strip-chart recorder and simultaneous background correction.
4.5 Burner: Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Selenium hollow cathode lamp or electrodeless discharge lamp.
4.7 Strip-chart recorder (optional).
5. 0 REAGENTS
5.1 Reagent water: Water should be monitored for impurities. Reagent
water will be interference free. All references to water will refer to reagent
water.
5.2 Concentrated nitric acid: Acid should be analyzed to determine
levels of impurities. If a method blank made with the acid is <MDL, the acid can
be used.
5.3 Concentrated sulfuric acid: Acid should be analyzed to determine
be used.
5.4 Concentrated hydrochloric acid: Acid should be analyzed to determine
be used.
November 1992
5.5 Diluent: Add 100 ml 18 N H2S0 4 and 400 ml concentrated HCl to 400
ml reagent water and dilute to a final volume of 1 liter with reagent water.
5.6 Potassium iodide solution: Dissolve 20 g KI in 100 ml reagent water.
5.7 Stannous chloride solution: Dissolve 100 g SnC1 2 in 100 ml of
concentrated HCl.
5.8 Selenium standard stock solution: 1,000 mg/L solution may be
purchased, or prepared as follows: Dissolve 0.3453 g of selenious acid (assay
94.6% of H2 Se03 ) in reagent water. Add to a 200-ml volumetric flask and bring
to volume (1 ml= 1 mg Se).

analysis) may have to be used if very volatile selenium compounds are to be
analyzed.
7. 0 PROCEDURE
7.1 Sample preparation:
7.1.1 To a 50-ml aliquot of digested sample (or, in the case of
extracts, a 50-ml sample) add 10 ml of concentrated HN03 and 12 ml of
18 N H2 S0 4 • Evaporate the sample on a hot plate until white S0 3 fumes are
observed (a volume of about 20 ml). Do not 1et it char. If it chars,
stop the digestion, cool, and add additional HN0 3 • Maintain an excess of
HN0 3 (evidence of brown fumes) and do not let the solution darken because
selenium may be reduced and lost. When the sample remains colorless or
straw yellow during evolution of S0 3 fumes, the digestion is complete.
Caution: Venting reaction vessels should be done with
caution and only under a fume hood or well ventilated
area.
7.1.2 Cool the sample, add about 25 ml reagent water, and again
evaporate to S0 3 fumes just to expel oxides of nitrogen. Cool. Add 40 ml
concentrated HCl and bring to a volume of 100 ml with reagent water.
November 1992
7.2 Prepare working standards from the standard stock solutions. The
following procedures provide standards in the optimum range.
7.2.1 To prepare a working stock solution, pipet 1 ml standard
stock solution (see Paragraph 5.8) into a I-liter volumetric flask. Bring
to volume with reagent water containing 1.5 ml concentrated HN0 3 /liter.
The concentration of this solution is 1 mg Se/l (1 ml= 1 ug Se).
7.2.2 Prepare six working standards by transferring 0, 0.5, 1.0,
1.5, 2.0, and 2.5 ml of the working stock solution (see Paragraph 7.2.1)
into 100-ml volumetric flasks. Bring to volume with diluent. The
concentrations of these working standards are 0, 5, 10, 15, 20, and 25 ug
Se/l.
7.3 Standard additions:
7 .3 .1 Take the 15-, 20-, and 25-ug standards and transfer
quantitatively 25 ml from each into separate 50-ml volumetric flasks. Add
10 ml of the prepared sample to each. Bring to volume with reagent water
containing 1.5 ml HNO~liter.
7.3.2 Add 10 ml of prepared sample to a 50-ml volumetric flask.
Bring to volume with reagent water containing 1.5 ml HN0 3 /liter. This is
the blank.
7.4 Follow the manufacturer's instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame is colorless; therefore, it may be
useful to aspirate a low concentration of sodium to ensure that ignition has
occurred.
7.5 The 196.0-nm wavelength shall be used for the analysis of selenium.
7.6 Transfer a 25-ml portion of the digested sample or standard to the
reaction vessel. Add 0.5 ml SnCl 2 solution. Allow at least 10 min for the metal
to be reduced to its lowest oxidation state. Attach the reaction vessel to the
special gas inlet-outlet glassware. Fill the medicine dropper with 1.50 ml
sodium borohydrate or zinc slurry that has been kept in suspension with the
magnetic stirrer. Firmly insert the stopper containing the medicine dropper into
the side neck of the reaction vessel. Squeeze the bulb to introduce the zinc
slurry or sodium borohydrate into the sample or standard solution. The metal
hydride will produce a peak almost immediately. When the recorder pen returns
partway to the base line, remove the reaction vessel.
8.0 QUALITY CONTROL

November 1992
10.0 REFERENCES
I. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
November 1992
METHOD 7741A
SELENIUM (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
c
Standard Preparation
Start
Sample Preparation
l l
7 2.1 Pipet 7.1 1 Add
a tock concentrated
aolution into H,SO, and HNO,
flaalc; bring to •ample and
to volu... evaporate
l
7.2.2 Prepare 6
Se working 7 1. 1 Stop r •• Did
atandarda from d1ge•t1on,cool, a ample
atock; bring lo add HNO, char?
valu.me
1 Na
7 3 1 Tranafer 7 1 2 Caal
3 alandard aample,add
porliona,add '--~~~~~~~~reagent water,
aampl•,bring to avaporat•,cool
volume
1
7.3.2 To 7. l. 2 Add
prepare blank concentrated
add •ample lo a HCl and bring
flaak and bring to volume
to volume
1
7.4 follow
in•truction•
for operating
argon-hydrogen
flame
1
7 £. Tranafar
7 s u.. 196.0 digaatad aampl•
nm wavelength t--~~~~ lo reaction 1+-~~~~~~~~
Vaaaal,add
SnCl,
7 6 Allow to
atand,attach
veaael to
glaaaware,add
Zn alurry
7 6 Racord Se
cancan tra ti on
Stop
November 1992
METHOD 7742
SELENIUM (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDEl

1.1 Method 7742 is an atomic absorption procedure for determining 3 µg/L
to 750 µg/L concentrations of selenium in wastes, mobility procedure extracts,
soils, and ground water. Method 7742 is approved for sample matrices that
contain up to 1000 mg/L concentrations of cobalt, copper, iron, mercury, and
nickel. A solid sample can contain up to 10% by weight of the interferents before
exceeding 1000 mg/Lin a digested sample. All samples including aqueous matrices
must be subjected to an appropriate dissolution step prior to analysis. Spiked
samples and relevant standard reference materials are employed to determine the
applicability of the method to a given waste.

2.1 Samples are prepared according to the nitric acid digestion procedure
described in Method 3010 for aqueous and extract samples and the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for sediments, soils, and sludges. Excess peroxide is
removed by evaporating samples to near-dryness at the end of the digestion
followed by dilution to volume and degassing the samples upon addition of urea.
The selenium is converted to the +4 oxidation state during digestion in HCl.
After a 1:10 dilution, selenium is then converted to its volatile hydride using
hydrogen produced from the reaction of the acidified sample with sodium
borohydride in a continuous-flow hydride generator.
2. 2 The volatile hydride is swept into an air-acetylene flame heated
quartz absorption ce 11 located in the optical path of an atomic absorption
spectrophotometer. The resulting absorption of the lamp radiation is
proportional to the selenium concentration.
2.3 The typical detection limit for this method is 3 µg/L.
3.0 INTERFERENCES
3.1 Very high (>1000 mg/L) concentrations of cobalt, copper, iron,
mercury, and, nickel can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.
3.2 Traces of peroxides left following the sample work-up can result in
analytical interferences. Peroxides must be removed by evaporating each sample
to near-dryness followed by reacting each sample with urea and allowing
sufficient time for degassing before analysis (see Sections 7.1 and 7.2}.
7742-1 Revision 0
November 1992
4.1 Electric hot plate: Large enough to hold at least several 100 ml
Pyrex digestion beakers.
4.2 A continuous-flow hydride generator: A commercially available
continuous-flow sodium borohydride/HCl hydride generator or a generator
constructed similarly to that shown in Figure 1 (P. S. Analytical or equivalent).
4.2.l Peristaltic Pump: A four-channel, variable-speed peristaltic
pump to permit regulation of liquid-stream flow rates (lsmatec Reglo-100
or equivalent). Pump speed and tubing diameters should be adjusted to
provide the following flow rates: sample/blank flow = 4.2 ml/min;
borohydride flow= 2.1 ml/min.
4.2.2 Sampling Valve (optional): A sampling valve (found in the
P. S. Analytical Hydride Generation System or equivalent) that allows
switching between samples and blanks (rinse solution) without introduction
of air into the system will provide more signal stability.
4.2.3 Transfer Tubing and Connectors: Transfer tubing (1 mm l.D.),
mixing T's, and connectors are made of teflon and are of compatible sizes
to form tight, leak-proof connections (Latchat, Technicon, etc. flow
injection apparatus accessories or equivalent).
4.2.4 Mixing Coil: A 20-turn coil made by wrapping transfer tubing
around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).
4.2.5 Mixing Coil Heater: A 250-ml Erlenmeyer flask containing 100
ml of water heated to boiling on a dedicated one-beaker hotplate (Corning
PC-35 or equivalent). The mixing coil in 4.2.4 is immersed in the boiling
water to speed kinetics of the hydride forming reactions and increase
solubility of interfering reduced metal precipitates.
4.2.6 Gas-Liquid Separator: A glass apparatus for collecting
liquid and gaseous products (P. S. Analytical accessory or equivalent)
which allows the liquid fraction to drain to waste and gaseous products
above the liquid to be swept by a regulated carrier gas (argon) out of the
cell for analysis. To avoid undue carrier gas dilution, the gas volume
above the liquid should not exceed 20 ml. See Figure 1 for an acceptable
separator shape.
4.2.7 Condenser: Moisture picked up by the carrier gas must be
removed before encountering the hot absorbance cell. The moist carrier
gas with the hydrides is dried by passing the gasses through a small (< 25
ml) volume condenser coil (Ace Glass Model 6020-02 or equivalent) that is
cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent). Cool tap-
water in place of a chiller is acceptable.
7742-2 Revision 0
November 1992
4.2.8 Flow Meter: A meter capable of regulating up to 1 L/min of
argon carrier gas is recommended.
4.3 Absorbance Cell: A 17-cm or longer quartz tube T-cell (windowless is
strongly suggested) is recommended, as shown in Figure 1 (Varian Model VGA-76
accessory or equivalent). The cell is held in place by a holder that positions
the cell about 1 cm over a conventional AA air-acetylene burner head. In
operation, the cell is heated to around 900°C by an air-acetylene flame.
4.4 Atomic absorption spectrophotometer: Single- or dual- channel,
single- or double-beam instrument having a grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with a strip-chart recorder.
4.5 Burner: As recommended by the particular instrument manufacturer for
an air-acetylene flame. An appropriate mounting bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.
4.6 Selenium hollow cathode lamp or selenium electrodeless discharge lamp
and power supply. Super-charged hollow-cathode lamps or EDL lamps are
recommended for maximum sensitivity.
4.7 Strip-chart recorder (optional): Connect to output of
spectrophotometer.
5.0 REAGENTS
5.1 Reagent water : Water must be monitored for impurities. Refer to
Chapter 1 for definition of Reagent water.
5.2 Concentrated nitric acid (HN0 3 ): Acid must be analyzed to determine
levels of impurities. If a method blank is <MDL, the acid can be used.
5.3 30% Hydrogen peroxide (H 202 ): Peroxide must be a tin-free grade.
5.4 Concentrated hydrochloric acid (HCl): Acid must be analyzed to
determine levels of impurities. If a method blank is <MDL, the acid can be used.
5.5 Diluent solution: A 3% HCl solution in reagent water must be prepared
as a diluent solution if excessive levels of analytes or interfering metals are
found in the undiluted samples.
5.6 Urea (H 2 NCONH 2 ): A 5.00-g portion of reagent grade urea must be added
to a 25-ml aliquot of each sample for removal of excess peroxide through
degassing (see Section 7.2).
7742-3 Revision 0
November 1992
jlll 1111 DURHER - - •
TO
WASTE
PUHP
r---------!.r__ COHDEHSER--+
t1J)C J HO
TE Es
I< r *
I
·;.o l SCOHHECTEO VALVE
l (SAt1PLIHG)
u-ORAIH
OURIHG S•/Sn
-.. ntlAL YS IS
TtlERt1011ETER _ __.
L
20 TURH COIL
(TEFLOH)
HOTPLATE-+
Figure 1. Continuous-flow sodium borohydride/hydride generator apparatus setup

and an AAS sample introduction system
7742-4 Revision 0
November 1992
5.7 4% Sodium Borohydride (NaBH 4 ): A 4 % sodium borohydride solution (20
g reagent-grade NaBH 4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the selenium to its hydride.
5.8 Selenium solutions:
5.8.l Selenium standard stock solution (1,000 mg/L): Either
procure certified aqueous standards from a supplier (Spex, Inorganic
Ventures, or equivalent) and verify by comparison with a second standard,
or dissolve 0.3453 g of selenious acid (assay 96.6% of H2 Se0 3 ) in 200 ml
of reagent water (1 ml= I mg Se).
5.8.2 Selenium working stock solution: Pipet 1 ml selenium
standard stock solution into a 1 L volumetric flask and bring to volume
with reagent water containing 1.5 ml concentrated HN0 3/liter. The
concentration of this solution is 1 mg Se/L (1 ml= 1 µg Se).

analysis) may have to be used if very volatile selenium compounds are suspected
to be present in the samples.
7. 0 PROCEDURE
7.1 Place a 100-ml portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-ml digestion beaker. Digest aqueous samples and
extracts according to Method 3010. Digest solid samples according to Method 3050
(furnace AA option) with the following modifications: add 5 ml of concentrated
hydrochloric acid just prior to the final volume reduction stage to aid in
conversion of selenium to its plus four state; the final volume reduction should
be to less than 5 ml but not to dryness to adequately remove excess hydrogen
peroxide (see note). After dilution to volume, further dilution with diluent may
be necessary if the analyte is known to exceed 750 µg/L or if interferents are
expected to exceed 1000 mg/L in the digestate.
7742-5 Revision 0
November 1992
Note:For solid digestions, the volume reduction stage is critical to obtain
accurate data. Close monitoring of each sample is necessary when this
critical stage in the digestion is reached.
7.2 Prepare samples for hydride analysis by adding 1.00 g urea, and 20 ml
concentrated HCl to a 5.00 ml aliquot of digested sample in a 50-ml volumetric
flask. Heat in a water bath to dissolve salts and reduce selenium (at least 30
minutes is suggested). Bring fl ask to volume with reagent water before
analyzing. A ten-fold dilution correction must be made in the final
concentration calculations.
7.3 Prepare working standards from the standard stock selenium solution.
Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-ml volumetric
flasks and bring to volume with diluent. These concentrations will be 0, 5, 10,
15, 20, and 25 µg Se/L.
7.4 If EP extracts (Method 1310) are being analyzed for selenium, the
method of standard additions must be used. Spike appropriate amounts of working
standard selenium solution to three 25 ml aliquots of each unknown. Spiking
volumes should be kept less than 0.250 ml to avoid excessive spiking dilution
errors.
7.5 Set up instrumentation and hydride generation apparatus and fill
reagent containers. The sample and blank flows should be set around 4.2 ml/min,
and the borohydride flow around 2.1 ml/min. The argon carrier gas flow is
adjusted to about 200 ml/min. For the AA, use the 196.0-nm wavelength and 2.0-nm
slit width without background correction. Begin all flows and allow 10 minutes
for warm-up.
7.6 Place sample feed line into a prepared sample solution and start pump
to begin hydride generation. Wait for a maximum steady-state signal on the
strip-chart recorder. Switch to blank sample and watch for signal to decline to
baseline before switching to the next sample and beginning the next analysis.
Run standards first (low to high), then unknowns. Include appropriate QA/QC
solutions, as required. Prepare calibration curves and convert absorbances to
concentration. See following analytical flowchart.
CAUTION: The hydride of selenium is very toxic. Precautions must be
taken to avoid inhaling the gas.
7.7 If the method of standard additions was employed, plot the measured
concentration of the spiked samples and unspiked sample versus the spiked
concentrations. The spiked concentration axis intercept will be the method of
standard additions concentration. If the plot does not result in a straight
line, a nonlinear interference is present. This problem can sometimes be
overcome by dilution or addition of other reagents if there is some knowledge
about the waste. If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
7742-6 Revision 0
November 1992
8.0 QUALITY CONTROL
8.1 Refer to Section 8.0 of Method 7000.

9.1 The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2 ug/L in solution.
10.0 REFERENCES
2. "Evaluation of Hydride Atomic Absorption Methods for Antimony, Arsenic,
Selenium, and Tin", an EMSL-LV internal report under Contract 68-03-3249,
Job Order 70.16, prepared for T. A. Hinners by D. E. Dobb, and J. D.
Lindner of Lockheed Engineering and Sciences Co., and L. V. Beach of the
Varian Corporation.
7742-7 Revision 0
November 1992
METHOD 7742
SELENIUM (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDE)
Start
7 .1 u.. Method 7.1 u••

3050 (furnace Solid Aqueous M•thod 3010
AA option) to to digHt 100
digHt l. 0 g ml sampl•
a ample
7.1-7.4 7 Z Add urea

DJ.geat with and cone HCl to
H,O, aa aliquot;heat int+-~~~~~~~~
deacrib•d in H,O bath; bring
M•thod 3050 to volume
7 3 Prepare
7.5 Add worlung
concentrat•d alandards from
HCl standard stock
S• solution
7. 6 Do find 7 4 Use the

volurtt• Extracts method of
reduction and standard
di.lulion, aa addJ. ti on:o on
deacr1bed extracts, only
All
Other
7 4 Spilce 3 7 5-7 6 Analyze

aliquots with the sample
worlu.ng using hybrid
standard Se generation
.sol\J.l1on apparatus
Yes
7 5-7 G Analyze 7 7 Determine

7 1 furth•r the •ample Se
dilut• with uaing h.ybrl.d concentration
diluant general ion from linear
apparatus plot
7 7 Determine
Sa cone from
standard
calibration
curve
Slop
7742-8 Revision 0
November 1992
METHOD 7760
SILVER (ATOMIC ABSORPTION, DIRECT ASPIRATION)

1.1 Method 7760 is an atomic absorption procedure approved for
determining the concentration of silver (CAS Registry Number 7440-22-4) in
wastes, mobility procedure extracts, soils, and ground water. All samples must
be subjected to an appropriate dissolution step prior to analysis.
2.1 Prior to analysis by Method 7760, samples must be prepared for direct
aspiration. The method of sample preparation will vary according to the sample
matrix. Aqueous samples are subjected to the acid-digestion procedure
described in this method.
2.2 Following the appropriate dissolution of the sample, a representative
aliquot is aspirated into an air/acetylene flame. The resulting absorption of
hollow cathode radiation will be proportional to the silver concentration.
Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.01 mg/L; typical
sensitivity is 0.06 mg/L.
3.0 INTERFERENCES
3.1 Background correction is required because nonspecific absorption and
light scattering may occur at the analytical wavelength.
3.2 Silver nitrate solutions are light-sensitive and have the tendency to
plate out on container walls. Thus silver standards should be stored in brown
bottles.
3.3 Silver chloride is insoluble; therefore, hydrochloric acid should be
avoided unless the silver is already in solution as a chloride complex.
3. 4 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.1 Atomic absorption spectrophotometer: Single- or dual-channel,
single- or double-beam instrument with a grating monochromator,
photomultiplier detector, adjustable slits, and provisions for background
correction.
4.2 Silver hollow cathode lamp.
4.3 Strip-chart recorder (optional).
7760 - 1 Revision 1
December 1987
5.0 REAGENTS
determination.
5.3 Nitric Acid (concentrated), HN03.
5.4 Ammonium Hydroxide (concentrated), NH40H.
5.5 Silver Stock Standard Solution (1,000 mg/L), AgN03. Dissolve 0.7874 g
anhydrous silver nitrate in water. Add 5 ml HN03 and bring to volume in a
500-ml volumetric flask (1 ml = 1 mg Ag). Alternatively, procure a certified
aqueous standard from a supplier and verify by comparison with a second
standard.
5.6 Silver working standards - These standards should be prepared from
silver stock solution to be used as ca 1i brat ion standards at the ti me of
analysis. These standards should be prepared with nitric acid and at the same
concentrations as the analytical solution.
5.7 Iodine solution (lN). Dissolve 20 g potassium iodide (Kl), in 50 ml
of water. Add 12.7 g iodine (12) and dilute to 100 ml. Store in a brown
bottle.
5.8 Cyanogen iodide solution. Add 4.0 ml ammonium hydroxide, 6.5 g
potassium cyanide (KCN), and 5.0 ml of iodine solution to 50 ml of water. Mix
and dilute to 100 ml with water. Do not keep longer than 2 weeks.
CAUTION: This reagent cannot be mixed with any acid solutions because
toxic hydrogen cyanide will be produced.
5.9 Air.
5.10 Acetylene.
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH < 2 with nitric acid.
7760 - 2 Revision 1
December 1987
6.4 When possible, standards and samples should be stored in the dark and
in brown bottles.
7.0 PROCEDURE
7.1 Sample preparation - Aqueous samples should be prepared according to
Steps 7.2 and 7.3. The applicability of a sample preparation technique to a
new matrix type must be demonstrated by analyzing spiked samples and/or
relevant standard reference materials.
7.2 Preparation of aqueous samples
7.2.1 Transfer a representative aliquot of the well-mixed sample to
a beaker and add 3 ml of concentrated HN03. Cover the beaker with a watch
glass. Pl ace the beaker on a hot pl ate and cautiously evaporate to near
dryness, making certain that the sample does not boil. DO NOT BAKE. Cool
beaker with a watch glass and return to the hot plate. Increase the
temperature of the hot plate so that a gentle reflux action occurs.
NOTE: If the sample contains thiosulfates, this step may result in
splatter of sample out of the beaker as the sample approaches
dryness. This has been reported to occur with certain photographic
types of samples.
7.2.2 Continue heating, adding additional acid, as necessary, until
the digestion is complete (generally indicated when the digestate is light
in color or does not change in appearance with continued refluxing).
Again, evaporate to near dryness and cool the beaker. Add a small quantity
of HN03 so that the final dilution contains 0.5% (v/v) HN03 and warm the
beaker to dissolve any precipitate or residue resulting from evaporation.
7. 2. 3 Wash down the beaker wa 11 s and watch glass with water and,
when necessary, filter the sample to remove silicates and other insoluble
material that could clog the nebul izer. Adjust the volume to some
predetermined value based on the expected metal concentrations. The sample
is now ready for analysis.
7.3 If plating out of AgCl is suspected, the precipitate can be
redissolved by adding cyanogen iodide to the sample. This can be done only
after digestion and after neutralization of the sample to a pH > 7 to prevent
formation of toxic cyanide under acid conditions. In this case do not adjust
the sample volume to the predetermined value until the sample has been
neutralized to pH > 7 and cyanogen iodide has been added. If cyanogen iodide
addition to the sample is necessary, then the standards must be treated in the
same manner. Cyanogen iodide must not be added to the acidified silver
standards. New standards must be made, as directed in Steps 5.5 and 5.6,
except that the acid addition step must be omitted. For example, to obtain a
100 mg/L working standard, transfer 10 ml of stock solution to a small beaker.
Add water to make about 70 ml. Make the solution basic (pH above 7) with
7760 - 3 Revision 1
December 1987
ammonium hydroxide. Rinse the pH meter electrodes into the solution with
water. Add 1 ml cyanogen iodide and allow to stand 1 hour. Transfer
quantitatively to a 100-ml volumetric flask and bring to volume with water.
CAUTION: CNI reagent can be added only after digestion to prevent
formation of toxic cyanide under acidic conditions. CNI reagent
must not be added to the acidified silver standards.
NOTE: Once the sample or sample aliquot has been treated with the CNI
reagent and diluted per instruction, the solution has a cyanide
concentration of approximately 260 mg/l. A solution of that cyanide
concentration must be considered a potential hazardous waste and
must be disposed of using an approved safety plan in accordance
with local authority requirements. Until such time that a detailed
disposal plan can be fully documented and approved, the use of the
CNI reagent should be avoided.
7. 4 The 328. 1 nm wavelength line and background correction sha 11 be
employed.
7.5 An oxidizing air-acetylene flame shall be used.
7.6 Follow the manufacturer's operating instructions for all other
spectrophotometer parameters.
7. 7 Either ( 1) run a series of silver standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances, or (2) for the method of standard additions, plot added
concentration versus absorbance. For instruments that read directly in
concentration, set the curve corrector to read out the proper concentration.
7.8 Analyze all Extraction Procedure (EP) extracts, all samples analyzed
as part of a delisting petition, and all samples that suffer from matrix
interferences by the method of standard additions.
7.9 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. A11 dilution or concentration factors must be taken
into account.
8.0 QUALITY CONTROL
8.2 Calibration curves must be composed of a minimum of a calibration
blank and three standards. A calibration curve should be made for every hour
of continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
7760 - 4 Revision 1
December 1987
8.5 Verify calibration with an independently prepared qualtiy control
reference sample every 15 samples.
8.6 Run one spiked replicate sample for every 10 samples or per
analytical batch, whichever is more frequent. A replicate sample is a sample
brought through the entire sample preparation and analytical process.
8.7 The method of standard additions (see Method 7000, Step 8.7) shall be
used for the analysis of all EP extracts, on all analyses submitted as part of
a delisting petition, and whenever a new sample matrix is being analyzed.
8.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
9.1 Precision and accuracy data are available in Method 272.1 of "Methods
for Chemical Analysis of Water and Wastes."
9. 2 The data shown in Table 1 were obtained from records of state and
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes; U.S. Environmental
Protection Agency. Office of Research and Development. En vi ronmenta l
600/4-79-020.
2. Gaskill, A., Compliation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, December 1987.
3. Rohrbaugh, W. G.; et a1 . Reagent Chemicals, American Chemical Society
for Reagent Water"; ATSM: Philadelphia, PA, 1985; Dll93-77.
7760 - 5 Revision 1
December 1987
TABLE 1.
METHOD PERFORMANCE DATA

Wastewater treatment sludge 3050 2.3, 1.6 ug/g

Emission control dust 3050 1. 8, 4 . 2 ug/ g
7760 - 6 Revision I
December 1987
METHOD 7760
SILVER (ATOMIC ABSORPTION, DIRECT ASPIRATION)
T.S Aijaat pl vitk

aaaoaia• •ydroxide:
ri••• electrode•
iato aola wit•
water: add cyaao1••
iodide: wait 1
koar: traa1fer to
tlull: brh1 to
vol1a1 witk wat1r
Sa•ple1 coataiaia1 Slad1e-type

oil, 1r1a11, or eaaplH
vax
7.C-1 let
iutraaeat
paraHt•ra
7.2.1 Traa1f1r •••Pl•

1liq1ot to beaker:
add coac aitric acid:
7.1 Prepare •••pl• evaporate to aear 7.1 Prepare •••pl• 1. 7 Coutract
according to Metkod dryae11: cool: add accordia1 to Metllod calibratioa carve
3040 coac aitric acid: 3060
lleat 10 1•atl• reflax
actin ocean
7.2.2 Co•pleh
dilHtioa:
evaporate to •••r 1. I Aaalyze by
dryae11: cool: add aetllod of ataadard
coac aitric ecid: additioa if
wara to di11olv• ••c111ar;r
aay precipitate or
rHidu
7.2.S Filter •••pl•

if HCeH&rJ: 7.t Calcalat• aetal
adjaat volaae vitk coaceatratioa
water
Stop
7. S IHtraliza
•••ple: add cyaao1••
iodide to diaaolva
precipitate: reaall•
ataadarda oaitti•I
acid: traaaf•r ali-
qaot of atocll aola-
t ioa to beeller: add
veter:
7760 - 7 Revision 1
December 1987
METHOD 7780
STRONTIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION}

3.0 INTERFERENCES
3.2 Chemical interference caused by silicon, aluminum, and phosphate are
controlled by adding lanthanum chloride. Potassium chloride is added to
suppress the ionization of strontium. All samples and standards should contain
1 ml of lanthanum chloride/potassium chloride solution (Step 5.3) per 10 ml of
solution.
4.2 Instrument parameters (general):
4.2.1 Strontium hollow cathode lamp.
4.2.4 Oxidant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: not required.
5.0 REAGENTS
5.2 Preparation of standards
5.2.1 Stock solution: (1.0 ml= 1.0 mg Sr). Dissolve 2.415 g of
strontium nitrate, Sr(N03)2, in 10 ml of concentrated HCl and 700 ml of
water. Dilute to 1 liter with water. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
7780 - 1 Revision 0
December 1987
5.2.2 Prepare dilutions of the stock solution to be used as
should be prepared using the same type of acid as the samples and cover
the range of expected concentrations in the samples. Calibration standards
should also contain 1 ml of lanthanum chloride/potassium chloride solution
per 10 ml.
5.3 Lanthanum Chloride/Potassium Chloride Solution. Dissolve 11.73 g of
lanthanum oxide, La203, in a minimum amount of concentrated hydrochloric acid
(approximately 50 ml). Add 1.91 g of potassium chloride, KCl. Allow solution
to cool to room temperature and dilute to 100 ml with water.
CAUTION: REACTION IS VIOLENT! Add acid slowly and in small portions to
control the reaction rate upon mixing.
6.1 See Chapter Three, Step 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation - The procedures for preparation of the sample are
given in Chapter Three, Step 3.2.
7.2 See Method 7000, Step 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
9. 1 The performance characteristics for an aqueous samp 1e free of
interferences are:
Optimum concentration range: 0.3 - 5 mg/L at a wavelength of
460.7 nm.
9.1.1 Recoveries of known amounts of strontium in a series of
prepared standards were as given in Table 1.
10.0 REFERENCES
1. Annual Book of ASTM Standards; ASTM: Philadelphia, PA, 1983; 03920.
7780 - 2 Revision 0
December 1987
TABLE 1.
RECOVERY
Significant
Amount Amount (95 %
added, found, % confidence
mg/l mg/L Bias Bias level)
Reagent Water Type II

1.00 0.998 -0.002 -0.2 no
0.50 0.503 +0.003 +0.6 no
0.10 0.102 +0.002 +2 no
Water of Choice
1.00 1.03 +0.03 +3 no
0.50 0.504 +0.004 + 0.8 no
0 .10 0.086 -0.014 -14 no
Reference: Annual Book of ASTM Standards; ASTM: Philadelphia, PA, 1983;

03920.
7780 - 3 Revision 0
December 1987
METHOD 7780
STRONTIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
Start
&.2 Prepare
ataadarb
1.1 for aaaph

proparatioa, •••
C~apter 3, Step 3.2
7.2 Aaalr•• ••tac

Motko4 1000, Step
7.3
ltop
7780 - 4 Revision O
December 1987
METHOD 35108

from aqueous samples. The method al so describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described in Section 4.3 of Chapter Four.
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.

2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separatory
funnel. The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).
3.0 INTERFERENCES
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. These reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds.

4.1 Separatory funnel - 2 liter, with Teflon stopcock.
4.2 Drying column - 20 mm IO Pyrex chromatographic column with Pyrex
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
November 1992
4.3 Kuderna-Danish (K-0) apparatus.
4.3.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equi va 1ent.
equivalent).
equivalent).
temperature control (±5°C). The bath' should be used in a hood.
4.6 Vials - 2 ml, glass with Teflon lined screw-caps or crimp tops.
4.8 Erlenmeyer flask - 250 ml.
4.9 Syringe - 5 ml.
4.10 Graduated cylinder - 1 liter.
5.0 REAGENTS
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently high purity to permit its use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na 2S04 • Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precl eaned with methylene chloride,
November 1992
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H 2 SO~. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.1 Methylene chloride, CH 2Cl 2 - Pesticide quality or equivalent.
5.6.2 Hexane, C6 H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, CH 3CH(OH)CH3 - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6 H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3 CN - Pesticide quality or equivalent.

Section 4.1.
7. 0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure 1 liter (nominal) of
sample and transfer it quantitatively to the separatory funnel. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 1iter. Add 1. 0 ml of the surrogate
standards to all samples, spikes, and blanks (see Method 3500 and the
determinative method to be used, for details on the surrogate standard solution
and the matrix spike solution). For the sample in each analytical batch selected
for spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds should
result in a final concentration of 100 ng/µL of each base/neutral analyte and
200 ng/µl of each acid analyte in the extract to be analyzed (assuming a 1 µl
injection). If Method 3640, Gel-Permeation Cleanup, is to be used, add twice the
volume of surrogates and matrix spiking compounds since half the extract is lost
due to loading of the GPC column.
7. 2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.4 Seal and shake the separatory funnel vigorously for 1-2 minutes with
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. Venting of the
3510B - 3 Revision 2
November 1992
separatory funnel should be into a hood to avoid needless exposure
of the analyst to solvent vapors.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends upon
the sample and may include stirring, filtration of the emulsion through glass
wool, centrifugation, or other physical methods. Collect the solvent extract in
an Erlenmeyer flask. If the emulsion cannot be broken (recovery of< 80% of the
methylene chloride, corrected for the water solubility of methylene chloride),
transfer the sample, solvent, and emulsion into the extraction chamber of a
continuous extractor and proceed as described in Method 3520, Continuous liquid-
liquid Extraction.
7.6 Repeat the extraction two more times using fresh portions of solvent
(Sections 7.3 through 7.5). Combine the three solvent extracts.
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1. Serially extract
three times with 60 ml of methylene chloride, as outlined in Sections 7.3
through 7.5. Collect and combine the extracts and label the combined extract
appropriately. ·
7.8 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted).
7.9 Perform the concentration (if necessary) using the Kuderna-Danish
(K-D) Technique (Sections 7.10.1 through 7.10.4).
7.10 K-D Technique
7.10 .1 Assemble a Kuderna-Dani sh (K-D) concentrator by
attaching a 10 ml concentrator tube to a 500 ml evaporation flask. Dry
the extract by passing it through a drying column containing about 10 cm
of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the Erlenmeyer fl ask, which contained the sol vent
extract, with 20-30 ml of methylene chloride and add it to the column to
7.10.2 Add one or two clean boiling chips to the flask and
attach a three ball Snyder column. Prewet the Snyder column by adding
about 1 ml of methylene chloride to the top of the column. Place the K-D
apparatus on a hot water bath (l 5-20°C above the boiling point of the
solvent) so that the concentrator tube is partially immersed in the hot
water and the entire lower rounded surface of the flask is bathed with hot
vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 10-20 minutes.
At the proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume of
November 1992
liquid reaches 1 ml, remove the K-0 apparatus from the water bath and
allow it to drain and cool for at least 10 minutes.
7.10.3 If a solvent exchange is required (as indicated in Table
1), momentarily remove the Snyder co 1umn, add 50 ml of the exchange
solvent, a new boiling chip, and reattach the Snyder column. Concentrate
the extract, as described in Section 7.11, raising the temperature of the
water bath, if necessary, to maintain proper distillation.
7.10.4 Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 ml of methylene chloride
or exchange solvent. If sulfur crystals are a problem, proceed to
Method 3660 for cleanup. The extract may be further concentrated by using
the technique outlined in Section 7.11 or adjusted to 10.0 ml with the
solvent last used.
7.11 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.11.1) or nitrogen blowdown technique (7.11.2) is used
to adjust the extract to the final volume required.
7.11.l Micro-Snyder Column Technique
7.11.1.1 If further concentration is indicated in Table 1,
add another clean boiling chip to the concentrator tube and attach
a two ball micro-Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column.
Place the K-0 apparatus in a hot water bath so that the concentrator
tube is partially immersed in the hot water. Adjust the vertical
position of the apparatus and the water temperature, as required, to
complete the concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter, but the
chambers will not flood. When the apparent volume of liquid reaches
0.5 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joints into the concentrator tube
with 0.2 ml of extraction solvent. Adjust the final volume to 1.0-
7.11.2 Nitrogen Slowdown Technique
7.11.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
7.11.2.2 The internal wall of the tube must be rinsed down
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
November 1992
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.12 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Section 4.3 of this Chapter). If
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL


10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
November 1992
TABLE 1.
8040 ~2 none 2-propanol hexane 1.0 1.0, 10.0
8070 as received none methanol methylene chloride 2.0 10.0
8250bc >11 <2 none - - 1.0
8270bd <2 >11 none - - 1.0
8310 as received none acetonitrile - - 1.0
8321 as received none methanol - - 1.0
8410 as received none methylene chloride methylene chloride 10.0 0.0 (dry)
a Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also contains an optional
derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on the cleanup
procedures available if required.
c Loss of phthalate esters, organochlorine pesticides and phenols can occur under these extraction conditions {see Section 3.2).
d Extraction pH sequence may be reversed to better separate acid and neutral waste components. Excessive pH adjustments may
result in the loss of some analytes {see Section 3.2).
November 1992
METHOD 35108
Start
7 l Add 7 7 Collect
surrogate and combl.ne
stands to a 11 extracts and
samples, spl.kes label
and blanks
7 8 Combl.ne
7 2 Check Y' es base/neutral
and ad1ust pH extracts
prl.or to
concentratl.on
7 3-7 6 7 9-7 11
Extract 3 Concentrate
tl.mes extract
November 1992
METHOD 35208

from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative steps
described in Section 4.3 of Chapter Four.
water-insoluble and slightly soluble organics in preparation for a variety of
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate the
effectiveness of any such automatic extraction device before employing it in
sample extraction.

2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous l iquid-1 iquid extractor, adjusted, if necessary, to a specific pH (see
Table 1), and extracted with organic solvent for 18-24 hours. The extract is
dried, concentrated (if necessary), and, as necessary, exchanged into a solvent
compatible with the cleanup or determinative method being employed (see Table 1
for appropriate exchange solvents).
3.0 INTERFERENCES
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. These reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds.

4.1 Continuous liquid-liquid extractor - Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Kontes 584200-0000,
584500-0000, 583250-0000, or equivalent).
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
November 1992
fr its may be purchased. Use a sma 11 pad of Pyrex glass woo 1 to
4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
equivalent.
equivalent).
4.3.4 Snyder column Two ball micro (Kontes K-569001-0219 or
equivalent).
4.6 Vials - 2 ml, glass with Teflon lined screw-caps or crimp tops.
4.9 Syringe - 5 ml.
5. 0 REAGENTS
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
November 1992
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H 2 SO~. Slowly add 50 ml of H2S04
(sp. gr. 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3 ) 2CHOH - Pesticide quality or equivalent.
5.6.4 Cyclohexane, C6 H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH 3 CN - Pesticide quality or equivalent.

Section 4.1.
7. 0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure out 1 liter (nominal) of
sample and transfer it quantitatively to the continuous extractor. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter. Check the pH of the sample with wide-
range pH paper and adjust the pH, if necessary, to the pH indicated in Table 1
using 1:1 (V/V) sulfuric acid or 10 N sodium hydroxide. Pipet 1.0 ml of the
surrogate standard spiking solution into each sample into the extractor and mix
well. (See Method 3500 and the determinative method to be used, for details on
the surrogate standard solution and the matrix spike solution.) For the sample
in each analytical batch selected for spiking, add 1.0 ml of the matrix spiking
standard. For base/neutral -acid analysis, the amount of the surrogates and
matrix spiking compounds added to the sample should result in a final
concentration of 100 ng/µL of each base/neutral analyte and 200 ng/µL of each
acid analyte in the extract to be analyzed (assuming a 1 µL injection). If
Method 3640, Ge 1-Permeation Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.2 Add 300-500 ml of methylene chloride to the distilling flask. Add
several boiling chips to the flask.
November 1992
7.3 Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Section 7.7.
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to the
second pH indicated in Table 1. Attach a clean distilling flask containing
500 ml of methylene chloride to the continuous extractor. Extract for 18-24
hours, allow to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral and base compounds at low concentrations must be determined,
separate extract analyses may be warranted).
7.7 Perform concentration (if necessary) using the Kuderna-Danish (K-D)
Technique (Sections 7.8.1 through 7.8.4).
7.8 K-D Technique
7.8.1 Assemble a Kuderna-Danish (K-0) concentrator by attaching a 10
ml concentrator tube to a 500 ml evaporation flask. Dry the extract by
passing it through a drying column containing about 10 cm of anhydrous
sodium sulfate. Collect the dried extract in a K-D concentrator. Rinse
the flask which contained the solvent extract with 20-30 ml of methylene
chloride and add it to the column to complete the quantitative transfer.
7.8.2 Add one or two clean boiling chips to the flask and attach a
three ball Snyder column. Prewet the Snyder column by adding about 1 ml
of methylene chloride to the top of the column. Place the K-D apparatus
on a hot water bath (15-20°C above the boiling point of the solvent) so
that the concentrator tube is partially immersed in the hot water and the
entire lower rounded surface of the fl ask is bathed with hot vapor.
Adjust the vertical position of the apparatus and the water temperature,
as required, to complete the concentration in 10-20 minutes. At the
proper rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent vo 1ume of 1i quid
reaches 1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at 1east 10 minutes. Remove the Snyder co 1umn and
rinse the flask and its lower joints into the concentrator tube with 1-2
ml of extraction solvent.
7.8.3 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent,
a new boiling chip, and reattach the Snyder column. Concentrate the
extract, as described in Section 7.9, raising the temperature of the water
bath, if necessary, to maintain proper distillation.
7.8.4 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 ml of methylene chloride or
November 1992
exchange sol vent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
techniques outlined in Section 7.9 or adjusted to 10.0 ml with the solvent
last used.
7.9 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique (7.9.2) is used
to adjust the extract to the final volume required.
7.9.1 Micro-Snyder Column Technique
7.9.1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro-Snyder column. Prewet
the column by adding 0. 5 ml of methylene ch 1ori de or exchange
solvent to the top of the column. Place the K-D apparatus in a hot
water bath so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
5-10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the K-0
apparatus from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column, rinse the flask and its
lower joints into the concentrator tube with 0.2 ml of methylene
chloride or exchange solvent, and adjust the final volume to 1.0 to
7.9.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
7.10 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Section 4.3 of this Chapter). If
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
November 1992
8.0 QUALITY CONTROL
8.1 Any reagent blanks, matrix spike, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
Method 3500 for extraction and sample-preparation procedures.

10.0 REFERENCES
November 1992
TABLE 1.
Determ4native extraction extraction for for for for
8040 <2 none 2-propanol hexane 1.0 1.0, 10.0
8070 as received none methanol methylene chloride 2.0 10.0
8250b,c >11 <2 none - - 1.0
8270b,d <2 >11 none - - 1.0
8310 as received none acetonitrile - - 1.0
8321 as received none methanol - - 1.0
8410 as received none methylene chloride methylene chloride 10.0 0.0 (dry)
a Phenols may he anaTyzed,-by Method-8040, using a--1.0 mI 2-propanol extract by GC/FID. Method-8040also contains an optional
derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on the cleanup
procedures available if required.
c Loss of phthalate esters, organochlorine pesticides and phenols can occur under these extraction conditions (see Section 3.2).
d If further separation of major acid and neutral components is required, Method 3650, Acid-Base Partition Cleanup, is
recommended. Reversal of the Method 8270 pH sequence is not recommended as analyte losses are more severe under the base first
continuous extraction (see Section 3.2).
November 1992
METHOD 35208
Start
l Add appropr•at•
•urrogate and 7 7-7 8 Conc•ntrat•
matr1• •plk1ng ••tract
solulJ.ona
7 2 Add m•thyl•n• 7 8 3 Add ••chang•

chlori.d• lo sa,l.'l•nt
d•sl•ll•n9 flask concentrate extract
7 l Add rH9•nl 7 9 fudhu

water to ••tractor, concentrala ••tract
••tract for 18-24 i.f neceaa.ary,
hour• ad1uat final volume
7 5 Adiust pH of
aquaou• ph•••. 1 10 Anal1t• uo1n9
••tract for 18-24 organic technique•
hour• with clean
flask
7 6 Comb•n• ac•d
and bas•/n•utral
ealracta prior to
concenlratJ.on
November 1992
METHOD 35408
SOXHLET EXTRACTION

1.1 Method 3540 is a procedure for extracting nonvolatile and semi-
vo lat i le organic compounds from solids such as soils, sludges, and wastes. The
Soxhlet extraction process ensures intimate contact of the sample matrix with the
extraction solvent.
1.2 This method is applicable to the isolation and concentration of water
insoluble and slightly water soluble organics in preparation for a variety of

2.1 The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using an
appropriate solvent in a Soxhlet extractor. The extract is then dried,
concentrated (if necessary), and, as necessary, exchanged into a solvent
compatible with the cleanup or determinative step being employed.
3.0 INTERFERENCES

4.1 Soxhlet extractor - 40 mm ID, with 500 ml round bottom flask.
glass wool at bottom.
fri ts may be purchased. Use a sma 11 pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass woo 1 pad with 50 ml of
extracts.
equivalent.
November 1992
equivalent).
equivalent).
4.6 Vials - Glass, 2 ml capacity, with Teflon lined screw or crimp top.
4.7 Glass or paper thimble or glass wool - Contaminant free.
4.9 Disposable glass pasteur pipet and bulb.
4.10 Apparatus for determining percent dry weight.
4.10.2 Desiccator.
4.10.3 Crucibles - Porcelain or disposable aluminum.
4.11 Apparatus for grinding
4.12 Analytical balance - 0.0001 g.
5.0 REAGENTS
5 .1 Reagent grade chemicals sha 11 be used in a11 tests. Unless otherwise
such specifications are available. Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.
5.2 Organic-free reagent water. All references to water in this method
the sodium sulfate.
November 1992
5.4 Extraction solvents
5.4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems:
5. 4. 1. 1 Acetone/Hexane ( 1: 1) ( v/v) , CH 3COCHJCH 6 H14 •
NOTE: This solvent system has lower disposal cost and lower
toxicity.
5.4.1.2 Methylene chloride/Acetone ( 1: 1 v/v),
CH 2Cl 2/CH3COCH 3 . Pesticide quality or equivalent.
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH 2Cl 2 • Pesticide quality or
equivalent.
5. 4. 2. 2 Toluene/Methanol (10: 1) (v/v), C6 H5 CH3/CH 30H.
5.5 Exchange solvents
5.5.1 Hexane, C6 H14 • Pesticide quality or equivalent.
5.5.2 2-Propanol, (CH3 ) 2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6 H12 • Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH 3 CN. Pesticide quality or equivalent.

6.1 See the introductory material to this chapter, Organic Analysis,
Section 4.1.
7. 0 PROCEDURE
7.1 Sample Handling
7.1.2 Waste samples - Samples consisting of multiphases must be
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a I mm sieve or can
November 1992
be extruded through a 1 mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.1.4 Gummy, fibrous or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling these difficult matrixes.
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination.
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay overdrying of the weighed-out portion until other analytical
results are available.
7.2.1 Immediately after weighing the sample for extraction, weigh 5-
10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight = g of dry sample x 100
g of sample
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely for
the duration of the extraction period. A glass wool plug above and below the
sample in the Soxhlet extractor is an acceptable alternative for the thimble.
Add 1.0 ml of the surrogate standard spiking solution onto the sample (see Method
3500 for details on the surrogate standard and matrix spiking solutions}. For
the sample in each analytical batch selected for spiking, add 1.0 ml of the
matrix spiking standard. For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final concentration
of 100 ng/µL of each base/neutral analyte and 200 ng/µL of each acid analyte in
the extract to be analyzed (assuming a 1 µL injection). If Method 3640, Gel
Permeation Chromatography Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.4 Place approximately 300 ml of the extraction solvent (Section 5.4)
into a 500 ml round bottom flask containing one or two clean boiling chips.
Attach the flask to the extractor and extract the sample for 16-24 hours at 4-6
cycles/hr.
7.5 Allow the extract to cool after the extraction is complete.
November 1992
7.6 Assemble a Kuderna-Danish (K-0) concentrator (if necessary) by
attaching a 10 ml concentrator tube to a 500 ml evaporation flask.
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-0
concentrator. Wash the extractor flask and sodium sulfate column with 100 to 125
ml of extraction solvent to complete the quantitative transfer.
ball Snyder column. Prewet the Snyder column by adding about 1 ml of methylene
chloride to the top of the column. Place the K-0 apparatus on a hot water bath
(15-20°C above the boiling point of the solvent) so that the concentrator tube
is partially immersed in the hot water and the entire lower rounded surface of
the flask is bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the concentration
in 10-20 minutes. At the proper rate of distillation the balls of the column
will actively chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 1-2 ml, remove the K-0 apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
momentarily remove the Snyder column, add approximately 50 ml of the exchange
solvent and a new boiling chip, and reattach the Snyder column. Concentrate the
extract as described in Section 7.8, raising the temperature of the water bath,
if necessary, to maintain proper distillation. When the apparent volume again
reaches 1-2 ml, remove the K-0 apparatus from the water batch and allow it to
drain and cool for at least 10 minutes.
into the concentrator tube with 1-2 ml of methylene chloride or exchange solvent.
If sulfur crystals are a problem, proceed to Method 3660 for cleanup. The
extract may be further concentrated by using the techniques described in Section
7.11 or adjusted to 10.0 ml with the solvent last used.
7.11 If further concentration is indicated in Table 1, either micro Snyder
column technique (Section 7.11.1) or nitrogen blowdown technique (Section 7.11.2)
is used to adjust the extract to the final volume required.
7.11.l Micro Snyder Column Technique
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of methylene chloride or exchange
solvent to the top of the column. Place the K-0 apparatus in a hot
water bath so that the concentrator tube is partially immersed in
the hot water. Adjust the vertical position of the apparatus and
5-10 minutes. At the proper rate of distillation the balls of the
column will actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the K-0
apparatus from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column and rinse the flask and
its 1ower joints with about 0. 2 ml of sol vent and add to the
November 1992
concentrator tube. Adjust the final volume to 1.0-2.0 ml, as
indicated in Table 1, with solvent.
7.11.2.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
{filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
7.12 The extracts obtained may now be analyzed for the target analytes
using the appropriate organic technique(s) (see Section 4.3 of this Chapter).
If analysis of the extract will not be performed immediately, stopper the
concentrator tube and store in a refrigerator. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined screw
cap or crimp top, and labeled appropriately.
8.0 QUALITY CONTROL


10.0 REFERENCES
November 1992
TABLE 1.
Exchange Exchange Volume Fina 1

8040 8 as received 2-propanol hexane 1.0 1.0, 10.0b
8070 as received methanol methylene chloride 2.0 10.0
8100 as received none cyclohexane 2.0 1.0
8250a,c as received none -- -- 1.0
8270c as received none -- -- 1.0
8310 as received acetonitril e -- -- 1.0
8321 as received methanol -- -- 1.0
8410 as received methylene chloride methylene chloride 10.0 0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD.
c The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance
METHOD 35406
SOXHLET EXTRACTION
Start
7.12
7.1 7.6
Use appropriate Assemble K-0
No Analyze using
sample handling ooncenlrator
organic techniques
technique
7.7 8000
7.2
Ory and coiled Series
Determine sample o/o Methods
dry weight extract in K-0
ooncenlrator
7.3 7.8
Add appropriale Concentrate using
surrogate and matrix Snyder cch.mn
spiking standards and K-0 apparatus
7.4
Add extraction
solvent ID flask:
extract for 16-24
hours
7.9
7.5
Add exchange
Cool extract solvent,
reconoentrate extract
November 1992
METHOD 3541
AUTOMATED SOXHLET EXTRACTION

1.1 Method 3541 describes the extraction of organic analytes from soil,
sediment, sludges, and waste solids. The method uses a commercially available,
unique, three stage extraction system to achieve analyte recovery comparable to
Method 3540, but in a much shorter time. There are two differences between this
extraction method and Method 3540. In the initial extraction stage of Method
3541, the sample-loaded extraction thimble is immersed into the boiling solvent.
This ensures very rapid intimate contact between the specimen and solvent and
rapid extraction of the organic analytes. In the second stage the thimble is
elevated above the solvent, and is rinse-extracted as in Method 3540. In the
third stage, the solvent is evaporated, as would occur in the Kuderna-Danish
(K-0) concentration step in Method 3540. The concentrated extract is then ready
for cleanup (Method 3600) followed by measurement of the organic analytes.
1.2 The method is applicable to the extraction and concentration of water
insoluble or slightly water soluble polychlorinated biphenyls (PCBs) in
preparation for gas chromatographic determination using either Method 8080 or
8081. This method is applicable to soils, clays, solid wastes and sediments
containing from 1 to 50 ~g of PCBs {measured as Arochlors) per gram of sample.
It has been statistically evaluated at 5 and 50 ~g/g of Arochlors 1254 and 1260,
and found to be equivalent to Method 3540 (Soxhlet Extraction). Higher
concentrations of PCBs are measured following volumetric dilution with hexane.
1.3 The method is also applicable the extraction and concentration of
organochlorine pesticides and semivolatile organics in preparation for GC/MS
analysis by Method 8270 or by analysis using specific GC or HPLC methods.

2.1 Organochlorine pesticides and semivolatile organics: A 10-g solid
sample (the sample is pre-mixed with anhydrous sodium sulfate for certain
matrices) is placed in an extraction thimble and usually extracted with 50 ml of
1:1 (v/v) acetone/hexane for 60 minutes in the boiling extraction solvent. The
thimble with sample is then raised into the rinse position and extracted for an
additional 60 minutes. Following the extraction steps, the extraction solvent
is concentrated to I to 2 ml.
2.2 PCBs: Moist solid samples {e.g., soil/sediment samples) may be air-
dried and ground prior to extraction or chemically dried with anhydrous sodium
sulfate. The prepared sample is extracted using 1:1 (v/v) acetone:hexane in the
automated Soxhlet following the same procedure as outlined for semivolatile
organics in Section 2.1. The extract is then concentrated and exchanged into
pure hexane prior to final gas chromatographic PCB measurement.
3541 - 1 Revision 0
November 1992
3.0 INTERFERENCES
3.2 The extraction thimble and the o-rings used to seal the extraction
cup are both a source of interference. Both should be checked by including a
method blank and following the extraction procedure as written. Solvent rinsing
or extraction, prior to use, may be necessary to eliminate or reduce
interferences. Vi ton seals contributed least to the interference prob 1em,
however, even they contributed some interference peaks when the extraction
solvent was analyzed by the electron capture detector. Use of butyl or EPDM
rings are not recommended since they were found to contribute significant
background when the extraction solvent was 1:1 v/v hexane/acetone or 1:1 v/v
methylene chloride/acetone.

4.1 Automated Soxh let Extraction System - with temperature-contra 11 ed oil
bath (Soxtec, or equivalent). Tecator bath oil (catalog number 1000-1886) should
be used with the Soxtec. Silicone oil must not be used because it destroys the
rubber parts. See Figure 1. The apparatus is used in a hood.
4.2 Accessories and consumables for the automated Soxhlet system. (The
catalog numbers are Fisher Scientific based on the use of the Soxtec HT-6,
however, other sources that are equivalent are acceptable.)
4.2.1 Cellulose extraction thimbles 26 mm ID x 60 mm
contamination free, catalog number 1522-0034, or equivalent.
4.2.2 Glass extraction cups (80 ml) - (set of six required for the
HT-6), catalog number 1000-1820.
4.2.3 Thimble adapters - (set of six required for the HT-6),
catalog number 1000-1466.
4.2.4 Viton seals - catalog number 1000-2516.
4.3 Syringes - 100 and 1000 ~L and 5 ml.
4.4 Apparatus for Determining Percent Ory Weight
4.4.1 Drying Oven.
4.4.2 Desiccator.
4.4.3 Crucibles, porcelain.
4.4.4 Balance, analytical.
4.5 Apparatus for grinding - Fisher Cyclotec, Fisher Scientific catalog
number 1093, or equivalent.
4.6 Spatula
3541 - 2 Revision 0
November 1992
4.7 Graduated cylinder - 100 ml.
4.8 Aluminum weighing dish - VWR Scientific catalog number 25433-008 or
equivalent.
4.9 Graduated, conical-bottom glass tubes - 15 ml, Kimble catalog number
45166 or equivalent, or 10 ml KD concentrator tube.
5.0 REAGENTS
without lessening the accuracy of the determination.
5.3 Sodium sulfate (granular, anhydrous), Na 2 S04 • Purify by heating at
methylene chloride. A method blank must be analyzed, demonstrating that there
is no interference from the sodium sulfate.
5.4 Extraction solvents:
5.4.1 Organochlorine pesticides/PCB extraction:
5.4.1.1 Acetone/hexane ( 1: 1 v/v),
5.4.2 Semivolatile organics extraction:
5.4.2.1 Acetone/hexane (1:1 v/v),
5.4.2.2 Acetone/methylene chloride (1: 1 v/v),
CH3 COCH3/CH 2Cl 2 • Pesticide quality or equivalent.
5.5 Hexane, C6 H14 • Pesticide quality or equivalent.

Section 4.1.
3541 - 3 Revision 0
November 1992
7.0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - Decant and discard any water layer
on a sediment sample. Mix sample thoroughly, especially composited
samples. Discard any foreign objects such as sticks, leaves, and rocks.
7.1.1.1 PCBs or high-boiling organochlorine pesticides -
Air-dry the sample at room temperature for 48 hours in a glass tray
or on hexane-cleaned aluminum foil, or dry the sample by mixing with
anhydrous sodium sulfate until a free-flowing powder is obtained
(see Section 7.2).
NOTE: Dry, finely ground soil/sediment allows the best
extraction efficiency for non-volatile, non-polar
organics, e.g., PCBs, 4,4'-DDT, etc. Air-drying
is not appropriate for the analysis of the more
volatile organochlorine pesticides (e.g. the
BHCs) or the more volatile of the semivolatile
organics because of losses during the drying
process.
7.1.2 Dried sediment/soil and dry waste samples amenable to
grinding - Grind or otherwise subdivide the waste so that it either passes
through a 1 mm sieve or can be extruded through a 1 mm hole. Introduce
sufficient sample into the grinding apparatus to yield at least 20 g after
grinding. Disassemble grinder between samples, according to
manufacturer's instructions, and clean with soap and water, followed by
acetone and hexane rinses.
NOTE: The same warning on loss of volatile analytes applies to the
grinding process. Grinding should only be performed when
analyzing for non-volatile organics.
7.1.3 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. If grinding of
these materials is preferred, the addition and mixing of anhydrous sodium
sulfate with the sample (1:1) may improve grinding efficiency. The
professional judgment of the analyst is required for handling such
difficult matrices.
7.1.4 Multiple phase waste samples - Samples consisting of multiple
phases must be prepared by the phase separation method in Chapter Two
before extraction. This procedure is for solids only.
7.2 For sediment/soil (especially gummy clay) that is moist and cannot
be air-dried because of loss of volatile analytes - Mix 5 g of sample with 5 g
of anhydrous sodium sulfate in a small beaker using a spatula. Use this approach
for any solid sample that requires dispersion of the sample particles to ensure
greater solvent contact throughout the sample mass.
3541 - 4 Revision 0
November 1992
7.3 Determination of sample percent dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination.
Significant laboratory contamination may result from the
drying of a heavily contaminated hazardous waste sample.
7.3.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the% dry weight of
before weighing:
g of sample
7.4 Check the heating oil level in the automated Soxhlet unit and add oil
if needed. See service manual for details. Set the temperature on the service
unit at 140°C when using hexane-acetone (1:1, v/v) as the extraction solvent.
7.5 Press the "MAINS" button; observe that the switch lamp is now "ON".
7.6 Open the cold water tap for the reflux condensers. Adjust the flow
to 2 L/min to prevent solvent loss through the condensers.
7.7 Weigh 10 g of sample into extraction thimbles. For samples mixed
with anhydrous sodium sulfate, transfer the entire contents of the beaker
(Section 7.2) to the thimble. Add surrogate spikes to each sample and the matrix
spike/matrix spike duplicate to the selected sample.
NOTE: When surrogate spikes and/or matrix spikes contain relatively
volatile compounds (e.g., trichlorobenzenes, BHCs, etc.), steps 7.8,
7.9, and 7.10 must be performed quickly to avoid evaporation losses
of these compounds. As the spike is added to the sample in each
thimble, the thimble should immediately be transferred to the
condenser and lowered into the extraction solvent.
7.8 Immediately transfer the thimbles containing the weighed samples into
the condensers. Raise the knob to the "BOILING" position. The magnet will now
fasten to the thimble. Lower the knob to the "RINSING" position. The thimble
will now hang just below the condenser valve.
7.9 Insert the extraction cups containing boiling chips, and load each
with 50 ml of extraction solvent (normally 1:1 (v/v) hexane:acetone, see Section
5.4). Using the cup holder, lower the locking handle, ensuring that the safety
catch engages. The cups are now clamped into position. (The seals must be pre-
rinsed or pre-extracted with extraction solvent prior to initial use.)
7.10 Move the extraction knobs to the "BOILING" position. The thimbles
are now immersed in solvent. Set the timer for 60 minutes. The condenser valves
must be in the "OPEN" position. Extract for the preset time.
3541 - 5 Revision 0
November 1992
7.11 Move the extraction knobs to the "RINSING" position. The thimbles
will now hang above the solvent surface. Set timer for 60 minutes. Condenser
valves are still open. Extract for the preset time.
7.12 After rinse time has elapsed, close the condenser valves by turning
each a quarter-turn, clockwise.
7.13 When a11 but 2 to 5 ml of sol vent have been co 11 ected, open the
system and remove the cups.
7.14 Transfer the contents of the cups to 15 ml graduated, conical-bottom
glass tubes. Rinse the cups using hexane (methylene chloride if 1:1 methylene
chloride-acetone was used for extraction and analysis is by GC/MS) and add the
rinsates to the glass tubes. Concentrate the extracts to l to 10 ml. The final
volume is dependent on the determinative method and the quantitation limit
required. Transfer a portion to a GC vial and store at 4°C until analyses are
performed.
NOTE: The recovery solvent volume can be adjusted by adding
sol vent at the top of the condensers. For more details
concerning use of the extractor, see the operating manual
for the automated extraction system.
7.15 Shutdown
7.15.l Turn "OFF" main switch.
7.15.2 Turn "OFF" cold water tap.
7.15.3 Ensure that all condensers are free of solvent. Empty
the solvent that is recovered in the evaporation step into an appropriate
storage container.
7.16 The extract is now ready for cleanup or analysis, depending on the
extent of interfering co-extractives. See Method 3600 for guidance on cleanup
methods and Method 8000 for guidance on determinative methods. Certain cleanup
and/or determinative methods may require a solvent exchange prior to cleanup
and/or determination.
8.0 QUALITY CONTROL

8.1 Refer to Chapter One for general quality control procedures and to
Method 3500 for specific extraction and sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free solid matrix (e.g., reagent sand) method blank
that a11 glassware and reagents are interference-free. Each ti me a set of
samples is extracted, or when there is a change in reagents, a method blank
should be processed as a safeguard against chronic laboratory contamination. The
blank samples should be carried through all stages of the sample preparation and
measurement. This is especially important because of the possibility of
interferences being extracted from the extraction cup seal.
3541 - 6 Revision 0
November 1992
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or less samples must contain: a method
blank, either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis, and a laboratory control sample, unless the
determinative method provides other guidance. Also, routinely check the
integrity of the instrument seals.
8.4 Surrogate standards must be added to all samples when specified in
the appropriate determinative method.

9.1 Mu1ti-1aboratory accuracy and precision data were obtained for PCBs
in soil. Eight laboratories spiked Arochlors 1254 and 1260 into three portions
of 10 g of Fuller's Earth on three non-consecutive days followed by immediate
extraction using Method 3541. Six of the laboratories spiked each Arochlor at
5 and 50 mg/kg and two laboratories spiked each Arochlor at 50 and 500 mg/kg.
All extracts were analyzed by Oak Ridge National Laboratory, Oak Ridge, TN, using
Method 8080. These data are listed in a table found in Methods 8080 and 8081,
and were taken from Reference 1.
9.2 Single-laboratory accuracy data were obtained for chlorinated
hydrocarbons, nitroaromatics, haloethers, and organochlorine pesticides in a clay
soil. The spiking concentrations ranged from 500 to 5000 µg/kg, depending on the
sensitivity of the analyte to the electron capture detector. The spiking
solution was mixed into the soil during addition and then immediately transferred
to the extraction device and immersed in the extraction solvent. The data
represents a single determination. Analysis was by capillary column gas
chromatography/electron capture detector following Methods 8081 for the
organochlorine pesticides, 8091 for the nitroaromatics, 8111 for the
hydrocarbons, and 8121 for the chlorinated hydrocarbons. These data are listed
in a table located in their respective methods and were taken from Reference 2.
9.3 Single-laboratory accuracy and precision data were obtained for
semivolatile organics in soil by spiking at a concentration of 6 mg/kg for each
compound. The spiking solution was mixed into the soil during addition and then
allowed to equilibrate for approximately 1 hr prior to extraction. Three
determinations were performed and each extract was analyzed by gas
chromatography/mass spectrometry following Method 8270. The low recovery of the
more volatile compounds is probably due to volatilization losses during
equilibration. These data are listed in a Table located in Method 8270 and were
taken from Reference 2.
10.0 REFERENCES
I. Stewart, J. "Intra-Laboratory Recovery Data for the PCB Extraction
Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6138;
October 1989.
3541 - 7 Revision 0
November 1992
2. Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
Extraction Procedure for Extracting Organic Compounds from Soi 1 s and
Sediments", EPA 600/X-91/140, US EPA, Environmental Monitoring Systems
Laboratory-Las Vegas, October 1991.
3541 - 8 Revision 0
November 1992
Figure 1
Automated Soxhlet Extraction System
Condenser •
Thimble
Sample
~ Aluminum beaker (cup)

~~!:I
.______ Hot plate _____-.
3541 - 9 Revision 0
November 1992
METHOD 3541
AUTOMATED SOXHLET EXTRACTION
7.1 7.5 7.11

Use appropriate Press "Mains· Move extraction
sample handling button. knobs to
technique. "Rinsing" for
60 mins.
7.6
Open Cold water
7.2 tap. Adjust flow.
7.12
Add anhydrous
Close
Na 2 S04 if
condenser valves.
necessary 7.7
Weigh sample into
extraction thimbles.
Add surrogate 7.13
7.3 spike. Remove cups.
Determine percent
dry weight.
7.8 7.14
Transfer samples
Transfer contents
7.4 into condensers.
Adjust position of to collection
Check oil vials, dilute or
magnet and thimble.
level in concentrate to
Soxhlet unit.
volume.
7.9
Insert extraction
cups and load 7.15
with solvent. Shutdown
7.10 Stop
Move extraction
knobs to
"Boiling" for
60 mins.
November 1992
METHOD 3550A
ULTRASONIC EXTRACTION
iee DISCLAIMER-I. See manufacturer's specifications for operational settings .
.. 0 SCOPE AND APPLICATION

1.1 Method 3550 is a procedure for extracting nonvo 1at il e and semi -
1olatile organic compounds from solids such as soils, sludges, and wastes. The
Jltrasonic process ensures intimate contact of the sample matrix with the
~xtraction solvent.
1. 2 The method is divided into two sections, based on the expected

:oncentration of organics in the sample. The low concentration method
'.individual organic components of~ 20 mg/kg) uses a larger sample size and a
ore rigorous extraction procedure (lower concentrations are more difficult to
~xtract). The medium/high concentration method (individual organic components
Jf > 20 mg/kg) is much simpler and therefore faster.
1.3 It is highly recommended that the extracts be cleaned up prior to
analysis. See Chapter Four (Cleanup), Section 4.2.2, for applicable methods.

2.1 Low concentration method - A 30 g sample is mixed with anhydrous
sodium sulfate to form a free flowing powder. This is solvent extracted three
times using ultrasonic extraction. A portion of the extract is removed for
cleanup and/or analysis.
2.2 Medium/high concentration method - A 2 g sample is mixed with
anhydrous sodium sulfate. This mixture is solvent extracted three times using
ultrasonic extraction. The extract is separated from the sample by vacuum
filtration or centrifugation. The extract is ready for cleanup and/or analysis
following concentration.
3.0 INTERFERENCES

4.1 Apparatus for grinding dry waste samples.
4.2 Ultrasonic preparation - A horn type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.
November 1992
4.2.1 Ultrasonic Disrupter - The disrupter must have a minimum power
wattage of 300 watts, with pulsing capability. A device designed tc
reduce the cavitation sound is recommended. Follow the manufacturers
instructions for preparing the disrupter for extraction of samples witt
low and medium/high concentration.
Use a 3/4" horn for the low concentration method and a 1/8" taperec
microtip attached to a 1/2" horn for the medium/high concentration method.
4.3 Sonabox - Recommended with above disrupters for decreasing cavitatior
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).
4.4 Apparatus for determining percent dry weight.
4.4.2 Desiccator.
4.4.3 Crucibles - Porcelain or disposable aluminum.
4.5 Pasteur glass pipets - 1 ml, disposable.
4.6 Beakers - 400 ml.
4.7 Vacuum or pressure filtration apparatus.
4.7.1 Buchner funnel.
4.7.2 Filter paper - Whatman No. 41 or equivalent.
4.8 Kuderna-Danish (K-D) apparatus.
extracts.
4.8.2 Evaporation flask 500 ml (Kontes K-570001-500 or
equivalent.
equivalent).
equivalent).
temperature control (± 5°C). The batch should be used in a hood.
November 1992
4.11 Balance - Top loading, capable of accurately weighing to the nearest
0.01 g.
4.12 Vials - 2 ml, for GC autosampler, with Teflon lined screw caps or
crimp tops.
4.13 Glass scintillation vials - 20 ml, with Teflon lined screw caps.
4.14 Spatula - Stainless steel or Teflon.
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after
highly contaminated extracts have been passed through.
Columns without frits may be purchased. Use a small pad of
Pyrex glass wool to retain the adsorbent. Prewash the glass
wool pad with 50 ml of acetone followed by 50 ml of elution
solvent prior to packing the column with adsorbent.
4.16 Syringe - 5 ml.
5.0 REAGENTS
otherwise specified, it is intended that all inorganic reagents shall conform to
the specifications of the Committee on Analytical Reagents of the American
used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
400 °C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
the sodium sulfate.
5.4 Extraction solvents.
5.4.1 Low concentration soil/sediment and aqueous sludge samples
shall be extracted using a solvent system that gives optimum, reproducible
recovery for the matrix/analyte combination to be measured. Suitable
solvent choices are given in Table 1.
5.4.2 Methylene chloride:Acetone, CH 2Cl 2 :CH3COCH 3 (1:1, v:v).
5.4.3 Methylene chloride, CH 2Cl 2 • Pesticide quality or equivalent.
November 1992
5.5 Exchange solvents.
5.5.2 2-Propanol, {CH3 ) 2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6 H12 • Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH 3CN. Pesticide quality or equivalent.
5.5.5 Methanol, CH30H. Pesticide quality or equivalent.

6.1 See the introductory material to this Chapter, Organic Analytes,
Section 4.1.
7. 0 PROCEDURE
7.1 Sample handling
7.1.1.2 Determine the dry weight of the sample (Section
7.2) remaining after decanting. Measurement of soil pH may be
required.
7.1.2 Waste samples - Samples consisting of multiphases must be
7.1.3 Ory waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1 mm sieve or can
be extruded through a 1 mm hole. Introduce sufficient sample into the
grinder to yield at least 100 g after grinding.
7.1.4 Gummy, fibrous or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to a11 ow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling of these difficult
matrices.
7.2 Determination of percent dry weight - In certain cases, sample
results are desired based on a dry weight basis. When such data are desired,
or required, a portion of sample for this determination should be weighed out at
the same time as the portion used for analytical determination.
November 1992
Significant laboratory contamination may result from drying a
heavily contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay overdrying of the weighed-out portion until other analytical
results are available.
7.2.1 Immediately after weighing the sample for extraction, weigh 5-
10 g of the sample into a tared crucible. Determine the % dry weight of
before weighing:
g of sample
7.3 Extraction method for samples expected to contain low concentrations
of organics and pesticides (~ 20 mg/kg):
7.3.1 The following step should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of sample
into a 400 ml beaker. Record the weigh to the nearest 0.1 g. Nonporous
or wet samples (gummy or clay type) that do not have a free-flowing sandy
texture must be mixed with 60 g of anhydrous sodium sulfate, using a
spatula. If required, more sodium sulfate may be added. After addition
of sodium sulfate, the sample should be free flowing. Add 1 ml of
surrogate standards to a11 samples, spikes, standards, and bl an ks (see
Method 3500 for details on the surrogate standard solution and the matrix
spike solution). For the sample in each analytical batch selected for
should result in a final concentration of 100 ng/µL of each base/neutral
analyte and 200 ng/µL of each acid analyte in the extract to be analyzed
(assuming a 1 µL injection). If Method 3640, Gel-Permeation Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half of the extract is lost due to loading of the GPC
column. Immediately add 100 ml of 1:1 methylene chloride:acetone.
7.3.2 Place the bottom surface of the tip of the #207 3/4 in.
disrupter horn about 1/2 in. below the surface of the solvent, but above
the sediment layer.
7.3.3 Extract ultrasonically for 3 minutes, with output control knob
set at 10 (full power) and with mode switch on Pulse (pulsing energy
rather than continuous energy) and percent-duty cycle knob set at 50%
(energy on 50% of time and off 50% of time). Do not use microtip probe.
7.3.4 Decant and filter extracts through Whatman No. 41 filter paper
(or equivalent) using vacuum filtration or centrifuge, and decant
extraction solvent.
November 1992
7.3.5 Repeat the extraction two or more times with two additional
100 ml portions of solvent. Decant off the solvent after each ultrasonic
extraction. On the final ultrasonic extraction, pour the entire sample
into the Buchner funnel and rinse with extraction solvent.
7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 ml concentrator tube to a 500 ml evaporator flask.
Transfer filtered extract to a 500 ml evaporator flask and proceed to the
next section.
7.3.7 Add one to two clean boiling chips to the evaporation flask,
and attach a three ball Snyder column. Prewet the Snyder column by adding
about 1 ml methylene chloride to the top. Place the K-D apparatus on a
hot water bath (80-90 °C) so that the concentrator tube is partially
immersed in the hot water and the entire lower rounded surface of the
flask is bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 10-15 min. At the proper rate of distillation the balls
of the column will actively chatter, but the chambers will not flood with
condensed solvent. When the apparent volume of liquid reaches 1 ml,
remove the K-D apparatus and allow it to drain and cool for at least 10
min.
7.3.8 If a solvent exchange is required (as indicated in Table I),
momentarily remove the Snyder column, add 50 ml of the exchange solvent
and a new boiling chip, and re-attach the Snyder column. Concentrate the
extract as described in Section 7.3.8, raising the temperature of the
water bath, if necessary, to maintain proper distillation. When the
apparent volume again reaches 1-2 ml, remove the K-D apparatus and allow
it to drain and cool for at least 10 minutes.
joints into the concentrator tube with 1-2 ml of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
technique outlined in Section 7.3.11 or adjusted to 10.0 ml with the
solvent last used.
7.3.10 If further concentration is indicated in Table 1, either
micro Snyder column technique (Section 7.3.11.1) or nitrogen blow down
technique (Section 7.3.11.2) is used to adjust the extract to the final
volume required.
7.3.10.1 Micro Snyder Column Technique
7.3.10.1.1 Add a clean boiling chip and attach a
two ball micro Snyder column to the concentrator tube. Prewet
the column by adding approximately 0.5 ml of methylene
ch 1ori de or exchange so 1vent through the top. Pl ace the
apparatus in the hot water bath. Adjust the vertical position
and the water temperature, as required, to comp 1ete the
concentration in 5-10 minutes. At the proper rate of
distillation the balls of the column will actively chatter,
November 1992
but the chambers will not flood. When the liquid reaches an
apparent volume of approximately 0.5 ml, remove the apparatus
from the water bath and allow to drain and cool for at least
10 minutes. Remove the micro Snyder column and rinse its
lower joint with approximately 0.2 ml of appropriate solvent
and add to the concentrator tube. Adjust the final volume to
the volume required for cleanup or for the determinative
method (see Table 1).
7.3.10.2 Nitrogen Blowdown Technique
7.3.10.2.1 Place the concentrator tube in a warm
water bath (approximately 35 °C) and evaporate the solvent
volume to the required level using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the
carbon trap and the sample.
7.3.10.2.2 The internal wall of the tube must be
rinsed down several times with the appropriate solvent during
the operation. During evaporation, the solvent level in the
tube must be positioned to prevent water from condensing into
the sample (i.e., the solvent level should be below the level
of the water bath). Under normal operating conditions, the
extract should not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below
1 ml, semivolatile analytes may be lost.
7.4 If analysis of the extract will not be performed immediately, stopper
the concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined cap
and labeled appropriately.
7.5 Extraction method for samples expected to contain high concentrations
of organics (> 20 mg/kg):
7.5.1 Transfer approximately 2 g (record weight to the nearest 0.1
g) of sample to a 20 ml vial. Wipe the mouth of the vial with a tissue to
remove any sample material. Record the exact weight of sample taken. Cap
the vial before proceeding with the next sample to avoid any cross
contamination.
7.5.2 Add 2 g of anhydrous sodium sulfate to sample in the 20 ml
vial and mix well.
7.5.3 Surrogate standards are added to all samples, spikes, and
blanks (see Method 3500 for details on the surrogate standard solution and
on the matrix spike solution). Add 2.0 ml of surrogate spiking solution
to sample mixture. For the sample in each analytical batch selected for
November 1992
should result in a final concentration of 200 ng/µL of each base/neutral
analyte and 400 ng/µL of each acid analyte in the extract to be analyzed
(assuming a 1 µL injection). If Method 3640, Gel-Permeation Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half the extract is lost due to loading of the GPC column.
7.5.4 Immediately add whatever volume of solvent is necessary to
bring the final volume to' 10.0 ml considering the added volume of
surrogates and matrix spikes. Disrupt the sample with the 1/8 in. tapered
microtip ultrasonic probe for 2 minutes at output control setting 5 and
with mode switch on pulse and percent duty cycle at 50%. Extraction
solvents are:
I. Nonpol ar compounds (i.e., organochl ori ne pesticides and PCBs),
hexane or appropriate solvent.
2. Extractable priority pollutants, methylene chloride.
7.5.5 Loosely pack disposable Pasteur pipets with 2 to 3 cm Pyrex
glass wool plugs. Filter the extract through the glass wool and collect
5. 0 ml in a concentrator tube if further con cent ration is required.
Follow Section 7.3.11 for details on concentration. Normally, the 5.0 ml
extract is concentrated to approximately 1.0 ml or less.
7.5.6 The extract is ready for cleanup or analysis, depending on the
extent of interfering co-extractives.
8.0 QUALITY CONTROL

8.1 Any reagent blanks or matrix spike samples should be subject to

9.1 Refer to the determinative method for performance data.
10.0 REFERENCES
2. U.S. EPA, Interlaboratory Comparison Study: Methods for Volatile and
Semi-Volatile Compounds, Environmental Monitoring Systems Laboratory,
Office of Research and Development, Las Vegas, NV, EPA 600/4-84-027, 1984.
November 1992
3. Christopher S. Hein, Paul J. Marsden, Arthur S. Shurtleff, "Evaluation of
Methods 3540 (Soxhlet) and 3550 (Sonication) for Evaluation of Appendix IX
Analytes form Solid Samples", S-CUBED, Report for EPA Contract 68-03-33-
75, Work Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
3550A - 9 Revision l
November 1992
TABLE 1.
EFFICIENCY OF EXTRACTION SOLVENT SYSTEMS 8
Solvent Systemd
A B c 0 E
Compound CAS No.b ABNC %R SD %R SD %R SD %R SD %R SD
4-Bromophenyl phenyl ether 101-55-3 N 64.2 6.5 56.4 0.5 86.7 1. 9 84.5 0.4 73.4 1.0
4-Chloro-3-methylphenol 59-50-7 A 66.7 6.4 74.3 2.8 97.4 3.4 89.4 3.8 84.1 1.6
bis(2-Chloroethoxy)methane 111-91-1 N 71. 2 4.5 58.3 5.4 69.3 2.4 74.8 4.3 37.5 5.8
bis(2-Chloroethyl) ether 111-44-4 N 42.0 4.8 17.2 3 .1 41.2 8.4 61.3 11. 7 4.8 1.0
2-Chloronaphthalene 91-58-7 N 86.4 8.8 78.9 3.2 100.8 3.2 83.0 4.6 57.0 2.2
4-Chlorophenyl phenyl ether 7005-72-3 N 68.2 8.1 63.0 2.5 96.6 2.5 80.7 1.0 67.8 1.0
1,2-Dichlorobenzene 95-50-1 N 33.3 4.5 15.8 2.0 27.8 6.5 53.2 10 .1 2.0 1. 2
1,3-Dichlorobenzene 541-73-1 N 29.3 4.8 12.7 1. 7 20.5 6.2 46.8 10.5 0.6 0.6
Diethyl phthalate 84-66-2 N 24.8 1.6 23.3 0.3 121.1 3.3 99.0 4.5 94.8 2.9
4,6-Dinitro-o-cresol 534-52-1 A 66 .1 8.0 63.8 2.5 74.2 3.5 55.2 5.6 63.4 2.0
2,4-Dinitrotoluene 121-14-2 N 68.9 1.6 65.6 4.9 85.6 1. 7 68.4 3.0 64.9 2.3
2,6-Dinitrotoluene 606-20-2 N 70.0 7.6 68.3 0.7 88.3 4.0 65.2 2.0 59.8 0.8
Heptachlor epoxide 1024-57-3 N 65.5 7.8 58.7 1.0 86.7 1.0 84.8 2.5 77 .0 0.7
Hexachlorobenzene 118-74-1 N 62.1 8.8 56.5 I. 2 95.8 2.5 89.3 1. 2 78.1 4.4
Hexachlorobutadiene 87-68-3 N 55.8 8.3 41.0 2.7 63.4 4.1 76.9 8.4 12.5 4.6
Hexachlorocyclopentadiene 77-47-4 N 26.8 3.3 19.3 1.8 35.5 6.5 46.6 4.7 9.2 1. 7
Hexachloroethane 67-72-1 N 28.4 3.8 15.5 1.6 31.1 7.4 57.9 10.4 1.4 1.2
5-Nitro-o-toluidine 99-55-8 B 52.6 26.7 64.6 4.7 74.7 4.7 27.9 4.0 34.0 4.0
Nitrobenzene 98-95-3 N 59.8 7.0 38.7 5.5 46.9 6.3 60.6 6.3 13.6 3.2
Phenol 108-95-2 A 51.6 2.4 52.0 3.3 65.6 3.4 65.5 2.1 50.0 8.1
1,2,4-Trichlorobenzene 120-82-1 N 66.7 5.5 49.9 4.0 73.4 3.6 84.0 7.0 20.0 3.2
- Percent recovery of analytes spiked at 200 mg/kg
a into NIST sediment SRM 1645
b Chemical Abstracts Service Registry Number
c Compound Type: A = Acid, B = Base, N = neutral
d A = Methylene chloride
B = Methylene chloride/Acetone (1/1)
C = Hexane/Acetone (1/1}
D = Methyl t-butyl ether
E = Methyl t-butyl ether/Methanol (2/1)
TABLE 2.
Exchange Exchange Volume Fina 1

8040 8 as received 2-propanol hexane 1.0 1.0, 10.0b
8070 as received methanol methylene chloride 2.0 10.0
8100 as received none cyclohexane 2.0 1.0
8250a,c as received none -- -- 1.0
8270c as received none -- -- 1.0
8310 as received acetonitrile -- -- 1.0
8321 as received methanol -- -- 1.0
8410 as received methylene chloride methylene chloride 10.0 0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD.
c The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance
Revision 1
3550A - 11 November 1992
METHOD 3550A
ULTRASONIC EXTRACTION
START
7 1 Pr•p•re sample•
using appropri•l•
method for the
w•ste m•lrix
7 2 Del•rm1ne the
percent dry weight
of the saampl•
7 3 l Add surrogate
7 S 2 Add annydrou• sl•ndards to all
sodium sulfate lo s.amples, spikes,
saampl• and bl.anks
7 S 3 Add surrog•l•
stand&rds to all 732-735
s.ampl•• spi1C•• Son1c•l• s•mple at
and blanlu least 3 limes
7 S 4 Adiu•t
volume disrupt 7 3 7 Dry •nd
sample with l•p•red collect ••lraact in
microt1p ultrasonic K·D coneenlr•tor
probe
7 5 5 rd ler 7 3 8 Concentraate
through gl••• wool extract and collect
in K·D concenlraalor
November 1992
METHOD 3550A
continued
7 3.9 Add exchange

solvent;
concentrate extract
7 3.10 Use Method

3660 for cleanup
7 3.11 Further
concentrate and/or
adJust volume
November 1992
METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST):
GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE

1.1 Method 5040 was formerly Method 3720 in the Second Edition of this
manual.
1.2 This method covers the determination of volatile principal organic
hazardous constituents (POHCs), collected on Tenax and Tenax/charcoal sorbent
cartridges using a volatile organic sampling train, VOST (1). Much of the
description for purge-and-trap GC/MS analysis is described in Method 8240 of this
chapter. Because the majority of gas streams sampled using VOST will contain a
high concentration of water, the analytical method is based on the quantitative
thermal desorption of volatile POHCs from the Tenax and Tenax/charcoal traps and
analysis by purge-and-trap GC/MS. For the purposes of definition, volatile POHCs
are those POHCs with boiling points less than 100°C.
1.3 This method is applicable to the analysis of Tenax and Tenax/
charcoal cartridges used to collect volatile POHCs from wet stack gas effluents
from hazardous waste incinerators.
1.4 The sensitivity of the analytical method for a particular volatile
POHC depends on the level of interferences and the presence of detectable levels
of volatile POHCs in blanks. The desired target detection limit of the
analytical method is 0.1 ng/L (20 ng on a single pair of traps) for a particular
volatile POHC desorbed from either a single pair of Tenax and Tenax/charcoal
cartridges or by thermal desorption of up to six pairs of traps onto a single
pair of Tenax and Tenax/charcoal traps. The resulting single pair of traps is
then thermally desorbed and analyzed by purge-and-trap GC/MS.
1.5 This method is recommended for use only by experienced mass
spectroscopists or under the close supervision of such qualified persons.

2.1 A schematic diagram of the analytical system is shown in Figure 1.
The contents of the sorbent cartridges are spiked with an internal standard and
thermally desorbed for 10 min at 180°C with organic-free nitrogen or helium gas
(at a flow rate of 40 ml/min), bubbled through 5 ml of organic-free reagent
water, and trapped on an analytical adsorbent trap. After the 10 min.
desorption, the analytical adsorbent trap is rapidly heated to 180°C, with the
carrier gas flow reversed so that the effluent flow from the analytical trap is
directed into the GC/MS. The volatile POHCs are separated by temperature
programmed gas chromatography and detected by low-resolution mass spectrometry.
The concentrations of volatile POHCs are calculated using the internal standard
technique.
November 1992
3.0 INTERFERENCES
3.1 Refer to Methods 3500 and 8240.

4.1 Thermal desorption unit:
4.1.1 The thermal desorption unit (for Inside/Inside VOST
cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user-fabricated unit is required) should be capable of
thermally desorbing the sorbent resin tubes. It should also be capable of
heating the tubes to 180 ± 10°C with flow of organic-free nitrogen or
helium through the tubes.
4.2 Purge-and-trap unit:
4.2.1 The purge-and-trap unit consists of three separate pieces of
equipment: the sample purger, trap, and the desorber. It should be
capable of meeting a11 requirements of Method 5030 for analysis of
purgeable organic compounds fr~m water.
4.3 GC/MS system: As described in Method 8240.
5.0 REAGENTS
5.2 Methanol, CH 30H - Pesticide grade, or equivalent.
5.3 Analytical trap reagents:
5.3.1 2,6-Diphenylene oxide polymer: Tenax (60/80 mesh), chromato-
graphic grade or equivalent.
5.3.2 Methyl silicone packing: 3% OV-1 on Chromosorb W(60/80 mesh)
or equivalent.
5.3.3 Silica gel: Davison Chemical (35/00 mesh), Grade 15, or
equivalent.
5.3.4 Charcoal: Petroleum-based (SKC Lot 104 or equivalent).
5.4 Stock standard solution:
5.4.1 Stock standard solutions will be prepared from pure standard
materials or purchased as certified solutions. The stock standards should
be prepared in methanol using assayed liquids or gases, as appropriate.
Because of the toxicity of some of the organohalides, primary dilutions of
these materials should be prepared in a hood. A NIOSH/MESA approved toxic
November 1992
gas respirator should be used when the analyst handles high concentrations
of such materials.
5.4.2 Fresh stock standards should be prepared weekly for volatile
POHCs with boiling points of <35°C. All other standards must be replaced
monthly, or sooner if comparison with check standards indicates a problem.
5.5 Secondary dilution standards:
5.5.1 Using stock standard solutions, prepare, in methanol,
secondary dilution standards that contain the compounds of interest,
either singly or mixed together. The secondary dilution standards should
be prepared at concentrations such that the desorbed calibration standards
will bracket the working range of the analytical system.
5.6 4-Bromofluorobenzene (BFB) standard:
5.6.1 Prepare a 25 ng/µL solution of BFB in methanol.
5.7 Deuterated benzene:
5.7.1 Prepare a 25 ng/µL solution of benzene-d6 in methanol.

6.1 Refer to Method 0030, Chapter Ten.
6.2 Sample trains obtained from the VOST should be analyzed within 2-6
weeks of sample collection.
7. 0 PROCEDURE
7.1 Assembly of PTO device:
7.1.1 Assemble a purge-and-trap desorption device (PTO) that meets
all the requirements of Method 5030 (refer to Figure 1).
7 .1. 2 Connect the therma 1 desorption device to the PTO device.
Calibrate the PTD-GC/MS system using the internal standard technique.
7.2 Internal standard calibration procedure:
7.2.1 This approach requires the use of deuterated benzene as the
i nterna 1 standard for these ana 1yses. Other i nterna 1 standards may be
proposed for use in certain situations. The important criteria for
choosing a particular compound as an internal standard are that it be
similar in analytical behavior to the compounds of interest and that it
can be demonstrated that the measurement of the internal standard be
unaffected by method or matrix interferences. Other internal standards
that have been used are d10 -ethylbenzene and d4 -1,2-dichloroethane. One
adds 50 ng of BFB to all sorbent cartridges (in addition to one or more
November 1992
internal standards) to provide continuous monitoring of the GC/MS
performance relative to BFB.
7.2.2 Prepare calibration standards at a minimum of three
concentration levels for each analyte of interest.
7.2.3 The calibration standards are prepared by spiking a blank
Tenax or Tenax/charcoal trap with a methanolic solution of the calibration
standards (including 50 ng of the internal standard, such as deuterated
benzene), using the flash evaporation technique. The flash evaporation
technique requires filling the needle of a 5.0 µl syringe with clean
methanol and drawing air into the syringe to the 1.0 µl mark. This is
followed by drawing a methanolic solution of the calibration standards
(containing 25 µg/µl of the internal standard) to the 2.0 µl mark. The
glass traps should be attached to the injection port of a gas
chromatograph while maintaining the injector temperature at 160°C. The
carrier gas flow through the traps should be maintained at about 50
ml/min.
7.2.4 After directing the gas flow through the trap, the contents of
the syringe should be slowly expelled through the gas chromatograph
injection port over about 15 sec. After 25 sec have elapsed, the gas flow
through the trap should be shut off, the syringe removed, and the trap
analyzed by the PTD-GC/MS procedure outlined in Method 8240. The total
flow of gas through the traps during addition of calibration standards to
blank cartridges, or internal standards to sample cartridges, should be 25
ml or less.
7.2.5 Analyze each calibration standard for both Tenax and Tenax/
charcoal cartridges according to Section 7.3. Tabulate the area response
of the characteristic ions of each analyte against the concentration of
the internal standard and calculate the response factor (RF) for each
compound, using Equation 1.
( 1)
where:
As Area of the characteristic ion for the analyte to be
measured.
Ais Area of the characteristic ion for the internal
standard.
cis = Amount (ng) of the internal standard.
cs = Amount (ng) of the volatile POHC in calibration
standard.
If the RF value over the working range is a constant (<10% RSD), the
RF can be assumed to be invariant, and the average RF can be used for
calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais versus RF.
November 1992
7.2.6 The working calibration curve or RF must be verified on each
working day by the measurement of one or more of the calibration
standards. If the response varies by more than ±25% for any analyte, a
new calibration standard must be prepared and analyzed for that analyte.
7. 3 The schematic of the PTD-GC/MS system is shown in Figure 1. The
sample cartridge is placed in the thermal desorption apparatus (for Inside/
Inside VOST cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated unit is required) and desorbed in the purge-and-trap
system by heating to 180°C for 10 min at a flow rate of 40 ml/min. The desorbed
components pass into the bottom of the water column, are purged from the water,
and collected on the analytical adsorbent trap. After the 10 min desorption
period, the compounds are desorbed from the analytical adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.
7.4 Qualitative analysis
7 .4.1 The qualitative identification of compounds determined by this
method is based on retention time, and on comparison of the sample mass
spectrum, after background correction, with characteristic ions in a
reference mass spectrum. The reference mass spectrum must be generated by
the laboratory using the conditions of this method. The characteristic
ions from the reference mass spectrum are defined to be the three ions of
greatest relative intensity, or any ions over 30% relative intensity if
less than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.4.1.1 The intensities of the characteristic ions of a
compound maximize in the same scan or within one scan of each other.
Selection of a peak by a data system target compound search routine,
where the search is based on the presence of a target
chromatographic peak containing ions specific for the target
compound at a compound-specific retention time, will be accepted as
meeting this criterion.
7.4.1.2 The RRT of the sample component is within± 0.06
RRT units of the RRT of the standard component.
7.4.1.3 The relative intensities of the characteristic
ions agree within 30% of the relative intensities of these ions in
the reference spectrum. (Example: For an ion with an abundance of
50% in the reference spectrum, the corresponding abundance in a
sample spectrum can range between 20% and 80%.)
7.4.1.4 Structural isomers that produce very similar mass
spectra should be identified as individual isomers if they have
sufficiently different GC retention times. Sufficient GC resolution
is achieved if the height of the valley between two isomer peaks is
less than 25% of the sum of the two peak heights. Otherwise,
structural isomers are identified as isomeric pairs.
7.4.1.5 Identification is hampered when sample components
are not resolved chromatographically and produce mass spectra
containing ions contributed by more than one analyte. When gas
November 1992
chromatographic peaks obviously represent more than one sample
component (i.e., a broadened peak with shoulder(s) or a valley
between two or more maxima), appropriate selection of analyte
spectra and background spectra is important. Examination of
extracted ion current profiles of appropriate ions can aid in the
selection of spectra, and in qualitative identification of
compounds. When analytes coelute (i.e., only one chromatographic
peak is apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by the
coeluting compound.
7.4.2 For samples containing components not associated with the
calibration standards, a library search may be made for the purpose of
tentative identification. The necessity to perform this type of
identification will be determined by the type of analyses being conducted.
Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference spectrum
(ions > 103 of the most abundant ion) should be present in the sample
spectrum.
(2) The relative intensities of the major ions should agree within
± 20%. (Example: For an ion 'with an abundance of 50% in the standard
spectrum, the corresponding sample ion abundance must be between 30 and
70%).
(3) Molecular ions present in the reference spectrum should be
present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background contamination or
presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coeluting peaks. Data
system library reduction programs can sometimes create these
discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of the
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.5 Quantitative analysis
7.5.l When an analyte has been qualitatively identified,
quantitation should be based on the integrated abundance from the EICP of
the primary characteristic ion chosen for that analyte. If the sample
produces an interference for the primary characteristic ion, a secondary
characteristic ion should be used.
November 1992
7.5.1.1 Using the internal standard calibration procedure,
the amount of analyte in the sample cartridge is calculated using
the response factor (RF) determined in Section 7.2.5 and Equation 2.
(2)
where:
Area of the characteristic ion for the analyte to
be measured.
Area for the characteristic ion of the internal
standard.
Amount (ng) of internal standard.
7.5.1.2 The choice of methods for evaluating data
collected using VOST for incinerator trial burns is a regulatory
decision. The procedures used extensively by one user are outlined
below.
7.5.1.3 The total amount of the POHCs of interest
collected on a pair of traps should be summed.
7.5.1.4 The observation of high concentrations of POHCs of
interest in blank cartridges indicates possible residual
contamination of the sorbent cartridges prior to shipment to and use
at the site. Data that fall in this category (especially data
indicating high concentrations of POHCs in blank sorbent cartridges)
should be qualified with regard to validity, and blank data should
be reported separately. The applicability of data of this type to
the determination of DRE is a regulatory decision. Continued
observation of high concentrations of POHCs in blank sorbent
cartridges indicates that procedures for cleanup, monitoring,
shipment, and storage of sorbent cartridges by a particular user be
investigated to eliminate this problem.
7.5.1.5 If any internal standard recoveries fall outside
the control limits established in Section 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation.
8.0 QUALITY CONTROL

Method 0030 for sample preparation procedures.
8. 2 Each 1aboratory that uses this method is required to operate a forma 1
quality control program. The minimum requirements of this program consist of an
initial demonstration of laboratory capability and the analysis of blank Tenax
and Tenax/charcoal cartridges spiked with the ana lytes of interest. The
laboratory is required to maintain performance records to define the quality of
data that are generated. Ongoing performance checks must be compared with
November 1992
established performance criteria to determine if results are within the expected
precision and accuracy limits of the method.
8.2.1 Before performing any analyses, the analyst must demonstrate
the ability to generate acceptable precision and accuracy with this
method. This ability is established as described in Section 7.2.
8.2.2 The laboratory must spike all Tenax and Tenax/charcoal
cartridges with the internal standard(s) to monitor continuing laboratory
performance. This procedure is described in Section 7.2.
8.3 To establish the ability to generate acceptable accuracy and
precision, the analyst must spike blank Tenax and Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.
8.3.l The average response factor (R) and the standard deviation (S)
for each must be calculated.
8.3.2 The average recovery and standard deviation must fall within
the expected range for determination of volatile POHCs using this method.
The expected range for recovery of volatile POHCs using this method is 50-
150%.
8.4 The analyst must calculate method performance criteria for the
internal standard(s).
8.4.1 Calculate upper and lower control limits for method
performances using the average area response (A) and standard deviation(s)
for internal standard:
Upper Control Limit (UCL) =A+ 3S
Lower Control Limit (LCL) =A - 3S
The UCL and LCL can be used to construct control charts that are
useful in observing trends in performance. The control limits must be
replaced by method performance criteria as they become available from the
U.S. EPA.
8.5 The laboratory is required to spike all sample cartridges (Tenax and
Tenax/charcoal) with internal standard.
8.6 Each day, the analyst must demonstrate through analysis of blank
Tenax and Tenax/charcoal cartridges and organic-free reagent water that
interferences from the analytical system are under control.
8.7 The daily GC/MS performance tests required for this method are
described in Method 8240.

November 1992
10. 0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHC's Using VOST.
EPA/600/8-84-007, March 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014a, January 1986.
November 1992
METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST)·
GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
Stai.t
'·'·'
purge
•••••bl•
and trap '·'·'
content•
lxpel
of
,_, •l•o•
aamole
7.1.l.I
a11ount of POHCa
....
deaorptton ~ aytina• thi:ough ~ carti:tdge in ~ of int•r••t for
device GC injection d••ozp. appaz:.; eacb paii. of
port deaoi:b io P·T trap a
" ' '

7. 1. 2 Connect 7. 2. t Analyse De•orD
7. 1 7. 5. l . ' Analyse
thez11al
deaoz:ption
devle•1
calib. eyatem
tzap by P-T-D
GC/NO
prooedura
(Method 12•0)
into GC/MS
ayatem
Clletbod ...., blank•
•ivn•
reai4••1
contamination.
fO<
Of
' v
7. 2. 5Analyze 7.'. l 7 5. l . 5 co11pare
...
7. 2. l select each calib. ouantatively int •td.
internal atandard for identify recovet:iea to
atanda:z:d botb cartridgea volatile POHCa aection
{aee 7. 1) (Wet hod a 24 o) control limita.
I' I< v v
7. 2. 3 Pxepare 7. 2. 5 Tabulate 7.5 1 u ..
calibi-ation a:z:ea ieaponae p1i11a:z:y
1taadard• ••h• aad calc.,.tlate ollaz:aoteriatic •top I
flaah evaporat. response factoi ion for
technique quantification
II •ii 'II
7. 2.' verify 7. s. 1. 1
7. 2. t Direct re•pon•• calculate
gao flow .--- factor each
1---
a11ount of
1---
tbrough tr•p• day &D&lyto in

aun.ple
5040A 10 Revision 1
November 1992
METHOD 5040A
continued
........,
7 . S. 1. 3
POKC• of
aua
!--·-·-·-~
7.s.1.• cual.
••••.. :::~::,"·•
repo.1:t blank
date ••P•Z•t•lY
7 , 9, 1.. 7 guel.1 fy
7 5.1.> Blank Yoo acevraey of th•
co1:1:ect u•iDtl I----;~ cl..ata tos all
Paia::•d analYt.•• l'&om
thac cert.1:td9•
7 S.l..3 Uae
• •t&Dcl.&J:d Ci•ld bla.a.k
devtatton of
combined field value
and trip blank•
Daterain• it
aaapl• i •
'"''·····
:tro111 bl a nit
'1 .I .a .I V•• ., .a.a.• •l••k

••a•u&•d •••Pl•
valu• aftlli••ion valu•
calculate of a particular
••iaa1oa
5040A 11 Revision 1
November 1992
METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN: WIDE-BORE CAPILLARY COLUMN TECHNIQUE

1.1 This method describes the analysis of volatile principal organic
hazardous constituents {POHCs) collected from the stack gas effluents of
hazardous waste incinerators using the VOST methodology {l). For a comprehensive
description of the VOST sampling methodology see Method 0030. The following
compounds may be determined by this method:
Compound Name CAS No. 8

Acetone 67-64-1
Acrylonitri1e 107-13-1
Benzene 71-43-2
Bromodichloromethane 75-27-4
Bromoformb 75-25-2
Bromomethanec 74-83-9
Carbon disulfide 75-15-0
Carbon tetrachloride 56-23-5
Chlorobenzene 108-90-7
Chlorodibromomethane 124-48-1
Chloroethanec 75-00-3
Chloroform 67-66-3
Chloromethanec 74-87-3
Dibromomethane 74-95-3
1,1-Dichloroethane 75-35-3
1,2-Dichloroethane 107-06-2
1,1-Dichloroethene 75-35-4
trans-1,2-Dichloroethene 156-60-5
1,2-Dichloropropane 78-87-5
cis-1,3-Dichloropropene 10061-01-5
trans-1,3-Dichloropropene 10061-02-6
Ethyl benzeneb 100-41-4
Iodomethane 74-88-4
Methylene chloride 75-09-2
Styreneb 100-42-5
1,1,2,2-Tetrachloroethaneb 79-34-5
Tetrachloroethene 127-18-4
Toluene 108-88-3
1,1,1-Trichloroethane 71-55-6
1,1,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
1,2,3-Trichloropropaneb 96-18-4
Vinyl chloridec 75-01-4
Xylenesb
5041 - 1 Revision 0
November 1992
a Chemical Abstract Services Registry Number.
b Bo i1 i ng point of this compound is above 132°C. Method 0030 is not
appropriate for quantitative sampling of this analyte.
c Boiling point of this compound is below 30°C. Special precautions must
be taken when sampling for this analyte by Method 0030. Refer to Section 1.3 for
discussion.
1.2 This method is most successfully applied to the analysis of non-polar
organic compounds with boiling points between 30°C and l00°C. Data are applied
to the calculation of destruction and removal efficiency (DRE), with limitations
discussed below.
1.3 This method may be applied to analysis of many compounds which boil
above 100°C, but Method 0030 is always inappropriate for collection of compounds
with boiling points above 132°C. All target analytes with boiling points greater
than 132°C are so noted in the target analyte list presented in Section 1.1. Use
of Method 0030 for collection of compounds boiling between 100°C and 132°C is
often possible, and must be decided based on case by case inspection of
information such as sampling method collection efficiency, tube desorption
efficiency, and analytical methoq precision and bias. An organic compound with
a boiling point below 30°C may break through the sorbent under the conditions
used for sample collection. Quantitative values obtained for compounds with
boiling points below 30°C must be qualified, since the value obtained represents
a minimum value for the compound if breakthrough has occurred. In certain cases,
additional QC measures may have been taken during sampling very low boilers with
Method 0030. This information should be considered during the data
interpretation stage.
When Method 5041 is used for survey analyses, values for compounds boiling
above 132°C may be reported and qualified since the quantity obtained represents
a minimum value for the compound. These minimum values should not be used for
trial burn DRE calculations or to prove insignificant risk.
1.4 The VOST analytical methodology can be used to quantitate volatile
organic compounds that are insoluble or slightly soluble in water. When
volatile, water soluble compounds are included in the VOST organic compound
analyte list, quantitation limits can be expected to be approximately ten times
higher than quantitation limits for water insoluble compounds (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®) is poor.
1.5 Overall sensitivity of the method is dependent upon the level of
interferences encountered in the sample and the presence of detectable
concentrations of ~olatile POHCs in blanks. The target detection limit of this
method is 0.1 µg/m (ng/L) of flue gas, to permit calculation of a DRE equal to
or greater than 99.99% for volatile POHCs which may be present in the waste
stream at 100 ppm. The upper end of the range of applicability of this method
is limited by the dynamic range of the analytical instrumentation, the overall
1oad i ng of organic compounds on the exposed tubes, and breakthrough of the
volatile POHCs on the sorbent traps used to collect the sample. Table 1 presents
5041 - 2 Revision 0
November 1992
retention times and characteristic ions for volatile compounds which can be
determined by this method. Table 2 presents method detection limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.
1.6 The wide-bore VOST analytical methodology is restricted to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems, and gas chromatograph/mass spectrometers, and skilled in
the interpretation of mass spectra and their use as a quantitative tool.

2.1 The sorbent tubes are thermally desorbed by heating and purging with
organic-free helium. The gaseous effluent from the tubes is bubbled through
pre-purged organic-free reagent water and trapped on an analytical sorbent trap
in a purge-and-trap unit (Figure 2). After desorption, the analytical sorbent
trap is heated rapidly and the gas flow from the analytical trap is directed to
the head of a wide-bore column under subambient conditions. The volatile organic
compounds desorbed from the analytical trap are separated by temperature
programmed high re solution gas chromatography and detected by continuously
scanning low resolution mass spectrometry (Figure 3). Concentrations of volatile
organic compounds are calculated from a multi-point calibration curve, using the
method of response factors.
3.0 INTERFERENCES
3.1 Sorbent tubes which are to be analyzed for volatile organic compounds
can be contaminated by diffusion of volatile organic compounds (particularly
Freon® refrigerants and common organic solvents) through the external container
(even through a Teflon® lined screw cap on a glass container) and the Swagelok®
sorbent tube caps during shipment and storage. The sorbent tubes can also be
contaminated if organic solvents are present in the analytical laboratory. The
use of blanks is essential to assess the extent of any contamination. Field
blanks must be prepared and taken to the field. The end caps of the tubes are
removed for the period of time required to exchange two pairs of traps on the
VOST sampling apparatus. The tubes are recapped and shipped and handled exactly
as the actual field samples are shipped and handled. At least one pair of field
blanks is included with each six pairs of sample cartridges collected.
3.2 At least one pair of blank cartridges (one Tenax-GC®, one
Tenax-GC®/charcoal) shall be included with shipment of cartridges to a hazardous
waste incinerator site as trip blanks. These trip blanks will be treated like
field blanks except that the end c~ps will not be removed during storage at the
site. This pair of traps will be analyzed to monitor potential contamination
which may occur during storage and shipment.
3.3 Analytical system blanks are required to demonstrate that
contamination of the purge-and-trap unit and the gas chromatograph/mass
spectrometer has not occurred or that, in the event of analysis of sorbent tubes
with very high concentrations of organic compounds, no compound carryover is
occurring. Tenax® from the same preparation batch as the Tenax® used for field
5041 - 3 Revision 0
November 1992
sampling should be used in the preparation of the method (laboratory) blanks.
A sufficient number of cleaned Tenax® tubes from the same batch as the field
samples should be reserved in the laboratory for use as blanks.
3.4 Cross contamination can occur whenever low-concentration samples are
analyzed after high-concentration samples, or when several high-concentration
samples are analyzed sequentially. When an unusually concentrated sample is
analyzed, this analysis should be followed by a method blank to establish that
the analytical system is free of contamination. If analysis of a blank
demonstrates that the system is contaminated, an additional bake cycle should be
used. If the analytical system is still contaminated after additional baking,
routine system maintenance should be performed: the analytical trap should be
changed and conditioned, routine column maintenance should be performed (or
replacement of the column and conditioning of the new column, if necessary), and
bakeout of the ion source (or cleaning of the ion source and rods, if required).
After system maintenance has been performed, analysis of a blank is required to
demonstrate that the cleanliness of the system is acceptable.
3.5 Impurities in the purge gas and from organic compounds out-gassing
in tubing account for the majority of contamination problems. The analytical
system must be demonstrated to be free from contamination under the conditions
of the analysis by analyzing two ~ets of clean, blank sorbent tubes with organic-
free reagent purge water as system blanks. The analytical system is acceptably
clean when these two sets of blank tubes show values for the analytes which are
within one standard deviation of the normal system blank. Use of plastic
coatings, non-Teflon® thread sealants, or flow controllers with rubber
components should be avoided.
3.6 VOST tubes are handled in the laboratory to spike standards and to
position the tubes within the desorption apparatus. When sorbent media are
handled in the laboratory atmosphere, contamination is possible if there are
organic solvents in use anywhere in the laboratory. It is therefore necessary
to make daily use of system blanks to monitor the cleanliness of the sorbents and
the absence of contamination from the analytical system. A single set of system
blank tubes shall be exposed to normal 1aboratory handling procedures and
analyzed as a sample. This sample should be within one standard deviation of
normal VOST tube blanks to demonstrate lack of contamination of the sorbent
media.
3.7 If the emission source has a high concentration of non-target organic
compounds (for example, hydrocarbons at concentrations of hundreds of ppm), the
presence of these non-target compounds will interfere with the performance of the
VOST analytical methodology. If one or more of the compounds of interest
saturates the chromatographic and mass spectrometric instrumentation, no
quantitative calculations can be made and the tubes which have been sampled under
the same conditions will yield no valid data for any of the saturated compounds.
In the presence of a very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is so saturated that the linear range has
been surpassed. When instrument saturation occurs, it is possible that compounds
of interest cannot even be i dent ifi ed correctly because a saturated mass
spectrometer may mis-assign masses. Even if compounds of interest can be
identified, accurate quantitative calculations are impossible at detector
saturation. No determination can be made at detector saturation, even if the
target compound itself is not saturated. At detector saturation, a negative bias
5041 - 4 Revision 0
November 1992
will be encountered in analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.
3.8 The recoveries of the surrogate compounds, which are spiked on the
VOST tubes immediately before analysis, should be monitored carefully as an
overall indicator of the performance of the methodology. Since the matrix of
stack emissions is so variable, only a general guideline for recovery of 50-150%
can be used for surrogates. The analyst cannot use the surrogate recoveries as
a guide for correction of compound recoveries. The surrogates are valuable only
as a general indicator of correct operation of the methodology. If surrogates
are not observed or if recovery of one or more of the surrogates is outside the
50-150% range, the VOST methodology is not operating correctly. The cause of the
failure in the methodology is not obvious. The matrix of stack emissions
contains large amounts of water, may be highly acidic, and may contain large
amounts of target and non-target organic compounds. Chemical and surface
interactions may be occurring on the tubes. If recoveries of surrogate compounds
are extremely low or surrogate compounds cannot even be identified in the
analytical process, then failure to observe an analyte may or may not imply that
the compound of interest has been removed from the emissions with a high degree
of efficiency (that is, the Destruction and Removal Efficiency for that analyte
is high).

4 .1 Tube desorption apparatus: Acceptable performance of the methodology
requires: 1) temperature regulation to ensure that tube temperature during
desorption is regulated to 180°C ± 10°; 2) good contact between tubes and the
heating apparatus to ensure that the sorbent bed is thoroughly and uniformly
heated to facilitate desorption of organic compounds; and 3) gas-tight
connections to the ends of the tubes to ensure flow of desorption gas through the
tubes without leakage during the heating/desorption process. A simple clamshell
heater which wi 11 hold tubes which are 3/ 4" in outer diameter wi 11 perform
acceptably as a desorption apparatus.
4.2 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: a sample purge vessel, an analytical trap, and a
desorber. Complete devices are commercially available from a variety of sources,
or the separate components may be assembled. The cartridge thermal desorption
apparatus is connected to the sample purge vessel by 1/8" Teflon® tubing
(unheated transfer line). The tubing which connects the desorption chamber to
the sample purge vessel should be as short as is practical.
4.2.1 The sample purge vessel is required to hold 5 ml of organic-
free reagent water, through which the gaseous effluent from the VOST tubes
is routed. The water column should be at least 3 cm deep. The gaseous
headspace between the water column and the analytical trap must have a
total volume of less than 15 ml. The purge gas must pass through the
water column as finely divided bubbles with a diameter of less than 3 mm
at the origin. The sample purger shown in Figure 4 meets these
requirements. Alternate sample purging vessels may be used if equivalent
performance is demonstrated.
5041 - 5 Revision 0
November 1992
4.2.2 The analytical trap must be at least 25 cm and have an
internal diameter of at least 0.105 in. The analytical trap must contain
the following components:
2,6-diphenylene oxide polymer: 60/80 mesh, chromatograph grade
(Tenax-GC®, or equivalent)
methyl silicone packing: OV-1 (3%) on Chromosorb-W 60/80
mesh, or equivalent
silica gel: 35/60 mesh, Davison grade 15 or
equivalent
coconut charcoal: prepare from Barneby Cheney,
CA-580-26, or equivalent, by
crushing through 26 mesh
screen.
The proportions are: 1/3 Tenax-GC®, 1/3 silica gel, and 1/3
charcoal, with approximately 1.0 cm of methyl silicone packing. The
analytical trap should be conditioned for four hours at 180°C with gas flow
(10 ml/min) prior to use ~n sample analysis. During conditioning, the
effluent of the trap should not be vented to the analytical column. The
thermal desorption apparatus is connected to the injection system of the
mass spectrometer by a transfer line which is heated to 100°C.
4.2.3 The desorber must be capable of rapidly heating the analytical
trap to 180°C for desorption. The polymer section of the trap should not
exceed l80°C, and the remaining sections should not exceed 220°C, during
bake-out mode.
4.3 Gas chromatograph/mass spectrometer/data system:
4.3.1 Gas chromatograph: An analytical system complete with a
temperature programmable oven with sub-ambient temperature capabilities
and all required accessories, including syringes, analytical columns, and
gases.
4.3.2 Chromatographic column: 30 m x 0.53 mm ID wide-bore fused
silica capillary column, 3 2m film thickness, DB-624 or equivalent.
4.3.3 Mass spectrometer: capable of scanning from 35-260 amu every
second or less, using 70 eV (nominal) electron energy in the electron
ionization mode and producing a mass spectrum that meets all of the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) is injected
into the water in the purge vessel.
4.3.4 Gas chromatograph/mass spectrometer interface: Any gas
chromatograph to mass spectrometer interface that gives acceptable
calibration points at 50 ng or less per injection of each of the analytes,
and achieves the performance criteria for 4-bromofluorobenzene shown in
Table 3, may be used. If a glass jet separator is used with the wide-bore
5041 - 6 Revision 0
November 1992
column, a helium make-up flow of approximately 15 ml, introduced after the
end of the column and prior to the entrance of the effluent to the
separator, will be required for optimum performance.
4. 3. 5 Data system: A computer system that a11 ows the continuous
acquisition and storage on machine readable media of all mass spectra
obtained throughout the duration of the chromatographic program must be
interfaced to the mass spectrometer. The computer must have software that
allows searching any gas chromatographic/mass spectrometric data file for
ions of a specified mass and plotting such ion abundances versus time or
scan number. This type of plot is defined as an Extracted Ion Current
Profile (EICP). Software must also be available that allows the
integration of the ion abundances in any EICP between specified time or
scan number limits. The most recent version of the EPA/NIST Mass Spectral
Library should also be available.
4.4 Wrenches: 9/16", 1/2", 7/16", and 5/16".
4.5 Teflon® tubing: 1/8" diameter.
4.6 Syringes: 25 µL syringes (2), 10 µL syringes (2).
4.7 Fittings: 1/4" nuts, 1/8" nuts, 1/16" nuts, 1/4" to 1/8" union, 1/4"
to 1/4" union, 1/4" to 1/16" union.
4.8 Adjustable stand to raise the level of the desorption unit, if
required.
4.9 Volumetric flasks: 5 ml, class A with ground glass stopper.
4.10 Injector port or equivalent, heated to 180°C for loading standards
onto VOST tubes prior to analysis.
4.11 Vials: 2 ml, with Teflon® lined screw caps or crimp tops.
4.12 Syringe: 5 ml, gas-tight with shutoff valve.
5.0 REAGENTS
5.2.1 It is advisable to maintain the stock of organic-free reagent
water generated for use in the purge-and-trap apparatus with a continuous
5041 - 7 Revision 0
November 1992
stream of inert gas bubbled through the water. Continuous bubbling of the
inert gas maintains a positive pressure of inert gas above the water as a
safeguard against contamination.
5.3 Methanol, CH30H. Pesticide quality or equivalent. To avoid
contamination with other laboratory solvents, it is advisable to maintain a
separate stock of methanol for the preparation of standards for VOST analysis and
to regulate the use of this methanol very carefully.
5. 4 Stock standard solutions - Can be prepared from pure standard
materials or can be purchased as certified solutions. Commerc i a11 y prepared
stock standards can be used if they are verified against EPA standards. If EPA
standards are not available for verification, then standards certified by the
manufacturer and verified against a standard made from pure material is
acceptable. Stock standard solutions must be prepared in high purity methanol.
All preparation of standards should take place in a hood, both to avoid
contamination and to ensure safety of the analyst preparing the standards.
5.4.1 Place about 4 ml of high purity methanol in a 5 ml volumetric
flask. Allow the flask to stand, unstoppered, for about 10 min, or until
all alcohol wetted surfaces have dried.
5.4.1.1 Add appropriate volumes of neat liquid chemicals
or certified solutions, using a syringe of the appropriate volume.
Liquid which is added to the volumetric flask must fall directly
into the alcohol without contacting the neck of the flask. Gaseous
standards can be purchased as methanol solutions from several
commercial vendors.
5.4.1.2 Dilute to volume with high purity methanol,
stopper, and then mix by inverting the flask several times. Calcu-
1ate concentration by the dilution of certified solutions or neat
chemicals.
5.4.2 Transfer the stock standard solution into a Teflon® sealed
screw cap bottle. An amber bottle may be used. Store, with minimal
headspace, at -10°C to -20°C, and protect from light.
5.4.3 Prepare fresh standards every two months for gases. Reactive
compounds such as styrene may need to be prepared more frequently. All
other standards must be replaced after six months, or sooner if comparison
with check standards indicates a problem.
5.5 Secondary dilution standards: Using stock standard solutions,
prepare, in high purity methanol, secondary dilution standards containing the
compounds of interest, either singly or mixed together. Secondary di 1ut ion
standards must be stored with minimal headspace and should be checked frequently
for signs of degradation or evaporation, especially just prior to preparing
calibration standards from them.
5. 6 Surrogate standards: The recommended surrogates are to l uene-d 8 ,
4-bromofluorobenzene, and 1,2-dichloroethane-d4 . Other compounds may be used as
surrogate compounds, depending upon the requirements of the analysis. Surrogate
compounds are selected to span the elution range of the compounds of interest.
5041 - 8 Revision 0
November 1992
Isotopically labeled compounds are selected to preclude the observation of the
same compounds in the stack emissions. More than one surrogate is used so that
surrogate measurements can still be made even if analytical interferences with
one or more of the surrogate compounds are encountered. However, at least three
surrogate compounds should be used to monitor the performance of the methodology.
A stock surrogate compound solution in high purity methanol should be prepared
as described in Section 5.4, and a surrogate standard spiking solution should be
prepared from the stock at a concentration of 250 µg/10 ml in high purity
methanol. Each pair of VOST tubes (or each individual VOST tube, if the tubes
are analyzed separately) must be spiked with 10 µL of the surrogate spiking
solution prior to GC/MS analysis.
5.7 Internal standards: The recommended internal standards are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d5 • Other compounds
may be used as internal standards as long as they have retention times similar
to the compounds being analyzed by GC/MS. The internal standards should be
distributed through the chromatographic elution range. Prepare internal standard
stock and secondary dilution standards in high purity methanol using the
procedures described in Sections 5.2 and 5.3. The secondary dilution standard
should be prepared at a concentration of 25 mg/L of each of the internal standard
compounds. Addition of 10 µL of this internal standard solution to each pair
of VOST tubes (or to each VOST tube, if the tubes are analyzed individually) is
the equivalent of 250 ng total.
5.8 4-Bromofluorobenzene (BFB) standard: A standard solution containing
25 ng/µL of BFB in high purity methanol should be prepared for use as a tuning
standard.
5.9 Calibration standards: Calibration standards at a minimum of five
concentrations will be required from the secondary dilution of stock standards
(see Sections 5.2 and 5.3). A range of concentrations for calibration can be
obtained by use of different volumes of a 50 mg/L methanol so 1ut ion of the
calibration standards. One of the concentrations used should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in field samples but should not exceed the linear range of the GC/MS analytical
system (a typical range for a calibration would be 10, 50, 100, 350, and 500 ng,
for example). Each calibration standard should contain each analyte for
detection by this method. Store calibration standards for one week only in a
vial with no headspace.
5.10 Great care must be taken to maintain the integrity of all standard
solutions. All standards of volatile compounds in methanol must be stored at
-10° to -20°C in amber bottles with Teflon® lined screw caps or crimp tops. In
addition, careful attention must be paid to the use of syringes designated for
a specific purpose or for use with only a single standard solution since cross
contamination of volatile organic standards can occurs very readily.

6.1 See Method 0030 for the VOST Sampling Methodology.
5041 - 9 Revision 0
November 1992
6.2 VOST samples are collected on paired cartridges. The first of the
pair of sorbent cartridges is packed with approximately 1.6 g of Tenax-GC®
resin. The second cartridge of the pair is packed with Tenax-GC® and petroleum
based charcoal (3:1 by volume; approximately 1 g of each). In sampling, the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal layer. The Tenax-GC® is cleaned and reused; charcoal is not reused
when tubes are prepared. Sorbent is cleaned and the tubes are packed. The tubes
are desorbed and subjected to a blank check prior to being sent to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile Organic Sampling Train (VOST)), cooling water is circulated to the
condensers and the temperature of the cooling water is maintained near 0°C. The
end caps of the sorbent cartridges are placed in a clean, screw capped glass
container during sample collection.
6.3 After the apparatus is leak checked, sample collection is
accomplished by opening the valve to the first condenser, turning on the pump,
and sampling at a rate of I liter/min for 20 minutes. The volume of sample for
any pair of traps should not exceed 20 liters. An alternative set of conditions
for sample collection requires sampling at a reduced flow rate, where the overall
volume of sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period is required for collecting an integrated sample.
6.4 Following collection' of 20 liters of sample, the train is leak
checked a second time at the highest pressure drop encountered during the run to
minimize the chance of vacuum desorption of organics from the Tenax®.
6.5 The train is returned to atmospheric pressure and the two sorbent
cartridges are removed. The end caps are replaced and the cartridges are placed
in a suitable environment for storage and transport until analysis. The sample
is considered invalid if the leak test does not meet specifications.
6.6 A new pair of cartridges is placed in the VOST, the VOST is leak
checked, and the sample collection process is repeated until six pairs of traps
have been exposed.
6.7 All sample cartridges are kept in coolers on cold packs after
exposure and during shipment. Upon receipt at the laboratory, the cartridges are
stored in a refrigerator at 4°C until analysis.
7. 0 PROCEDURE
7.1 Recommended operating conditions for cartridge desorber,
purge-and-trap unit, and gas chromatograph/mass spectrometer using the wide-bore
column are:
Cartridge Desorption Oven
Desorb Temperature 180°C
Desorb Time 11 minutes
Desorption Gas Flow 40 ml/min
Desorption/Carrier Gas Helium, Grade 5.0
November 1992
Purge-and-Trap Concentrator
Analytical Trap Desorption Flow 2.5 ml/min helium
Purge Temperature Ambient
Purge Time 11 minutes
Analytical Trap Desorb Temperature 180°C
Analytical Trap Desorb Time 5 minutes
Gas Chromatograph
Column DB-624, 0.53 mm ID x 30 m thick
film (3 µm) fused silica capillary,
or equivalent
Carrier Gas Flow 15 ml/min
Makeup Gas Flow 15 ml/min
Injector Temperature 200°c
Transfer Oven Temperature 240°C
Initial Temperature 5°C
Initial Hold Time 2 minutes
Program Rate 6°C/min
Final Temperature 240°C
Final Hold Time 1 minute, or until elution ceases
Mass Spectrometer
Manifold Temperature 105°C
Scan Rate I sec/cycle
Mass Range 35-260 amu
Electron Energy 70 eV (nominal)
Source Temperature According to manufacturer's
specifications
7.2 Each GC/MS system must be hardware tuned to meet the criteria in
Table 3 for a 50 ng injection of 4-bromofluorobenzene (2 µl injection of the BFB
standard solution into the water of the purge vessel). No analyses may be
initiated until the criteria presented in Table 3 are met.
7.3 Assemble a purge-and-trap device that meets the specifications in
Method 5030. Condition the analytical trap overnight at 180°C in the purge mode,
with an inert gas flow of at least 20 ml/min. Prior to use each day, condition
the trap for 10 minutes by backflushing at 180°C, with the column at 220°C.
7.4 Connect the purge-and-trap device to a gas chromatograph.
7.5 Assemble a VOST tube desorption apparatus which meets the
requirements of Section 4.1.
7.6 Connect the VOST tube desorption apparatus to the purge-and-trap
unit.
7.7 Calibrate the instrument using the internal standard procedure, with
standards and calibration compounds spiked onto cleaned VOST tubes for
calibration.
7.7.1 Compounds in methanolic solution are spiked onto VOST tubes
using the flash evaporation technique. To perform flash evaporation, the
November 1992
injector of a gas chromatograph or an equivalent piece of equipment is
required.
7.7.1.1 Prepare a syringe with the appropriate volume of
methanolic standard solution (either surrogates, internal standards,
or calibration compounds}.
7.7.1.2 With the injector port heated to 180°C, and with
an inert gas flow of 10 ml/min through the injector port, connect
the paired VOST tubes (connected as in Figure 1, with gas flow in
the same direction as the sampling gas flow) to the injector port;
tighten with a wrench so that there is no leakage of gas. If
separate tubes are being analyzed, an individual Tenax® or
Tenax®/charcoal tube is connected to the injector.
7.7.1.3 After directing the gas flow through the VOST
tubes, slowly inject the first standard solution over a period of 25
seconds. Wait for 5 sec before withdrawing the syringe from the
injector port.
7.7.1.4 Inject a second standard (if required} over a
period of 25 second;S and wait for 5 sec before withdrawing the
syringe from the injector port.
7.7.1.5 Repeat the sequence above as required until all of
the necessary compounds are spiked onto the VOST tubes.
7. 7 .1. 6 Wait for 30 seconds, with gas fl ow, after the last
spike before disconnecting the tubes. The total time the tubes are
connected to the injector port with gas flow should not exceed 2.5
minutes. Total gas flow through the tubes during the spiking
process should not exceed 25 ml to prevent break through of adsorbed
compounds during the spiking process. To allow more time for
connecting and disconnecting tubes, an on/off valve may be installed
in the gas line to the injector port so that gas is not flowing
through the tubes during the connection/disconnection process.
7.8 Prepare the purge-and-trap unit with 5 ml of organic-free reagent
water in the purge vessel.
7. 9 Connect the paired VOST tubes to the gas 1i nes in the tube desorption
unit. The tubes must be connected so that the gas flow during desorption will
be opposite to the flow of gas during sampling: i.e., the tube desorption gas
passes through the charcoal portion of the tube first. An on/off valve may be
installed in the gas line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during the connection process.
7.10 Initiate tube desorption/purge and heating of the VOST tubes in the
desorption apparatus.
7.11 Set the oven of the gas chromatograph to subambient temperatures by
cooling with liquid nitrogen.
7.12 Prepare the GC/MS system for data acquisition.
5041 - 12 Revision O
November 1992
7.13 At the conclusion of the tube/water purge time, attach the analytical
trap to the gas chromatograph, adjust the purge-and-trap device to the desorb
mode, and initiate the gas chromatographic program and the GC/MS data
acquisition. Concurrently, introduce the trapped materials to the gas
chromatographic column by rapidly heating the analytical trap to 180°C while
backflushing the trap with inert gas at 2.5 ml/min for 5 min. Initiate the
program for the gas chromatograph and simultaneously initiate data acquisition
on the GC/MS system.
7.14 While the analytical trap is being desorbed into the gas
chromatograph, empty the purging vessel. Wash the purging vessel with a minimum
of two 5 ml fl us hes of organic-free reagent water (or methanol foll owed by
organic-free reagent water} to avoid carryover of analytes into subsequent
analyses.
7.15 After the sample has been desorbed, recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit. The analytical trap may
be baked at temperatures up to 220°C. However, extensive use of high
temperatures to recondition the trap wi 11 shorten the useful life of the
analytical trap. After approximately 11 minutes, terminate the trap bake and
cool the trap to ambient temperatures in preparation for the next sample. This
procedure is a convention for reasonable samples and should be adequate if the
concentration of contamination does not saturate the analytical system. If the
organic compound concentration is so high that the analytical system is saturated
beyond the point where even extended system bakeout is not sufficient to clean
the system, a more extensive system maintenance must be performed. To perform
extensive system maintenance, the analytical trap is replaced and the new trap
is conditioned. Maintenance is performed on the GC column by removing at least
one foot from the front end of the co 1umn. If the chromatography does not
recover after column maintenance, the chromatographic column must be replaced.
The ion source should be baked out and, if the bakeout is not sufficient to
restore mass spectrometric peak shape and sensitivity, the ion source and the
quadrupole rods must be cleaned.
7.16 Initial calibration for the analysis of VOST tubes: It is essential
that calibration be performed in the mode in which analysis will be performed.
If tubes are being analyzed as pairs, calibration standards should be prepared
on paired tubes. If tubes are being analyzed individually, a calibration should
be performed on individual Tenax® only tubes and Tenax®/charcoal tubes.
7.16.l Prepare the calibration standards by spiking VOST tubes
using the procedure described in Section 7.7.1. Spike each pair of VOST
tubes (or each of the individual tubes} immediately before analysis.
Perform the calibration analyses in order from low concentration to high
to minimize the compound carryover. Add 5.0 ml of organic-free reagent
water to the purging vessel. Initiate tube desorb/purge according to the
procedure described above.
7 .16. 2 Tabulate the area response of the characteristic primary
ions (Table 1) against concentration for each target compound, each
surrogate compound, and each internal standard. The first criterion for
quantitative analysis is correct identification of compounds. The
compounds must elute within ± 0.06 retention time units of the elution
time of the standard analyzed on the same analytical system on the day of
November 1992
the analysis. The analytes should be quantitated relative to the closest
eluting internal standard, according to the scheme shown in Table 4.
Calculate response factors {RF) for each compound relative to the internal
standard shown in Table 4. The internal standard selected for the
calculation of RF is the internal standard that has a retention time
closest to the compound being measured. The RF is calculated as follows:
where:
Ax = area of the characteristic ion for the compound being
measured.
A.15 = area of the characteristic ion for the specific internal
standard.
C; 5 = concentration of the specific internal standard.
Cx = concentration of the compound being measured.
7.16.3 The average RF must be calculated for each compound. A
system performance check should be made before the calibration curve is
used. Five compounds {the System Performance Check Compounds, or SPCCs)
are checked for a minimum average response factor. These compounds are
chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have RFs
of 0.4 - 0.6, and are used to check compound instability and check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.16.3.1 Chloromethane: This compound is the most likely
compound to be lost if the purge flow is too fast.
7.16.3.2 Bromoform: This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in transfer lines may adversely
affect response. Response of the primary quantitation ion (m/z 173)
is directly affected by the tuning for 4-bromofluorobenzene at the
ions of masses 174 and 176. Increasing the ratio of ions 174 and 176
to mass 95 (the base peak of the mass spectrum of
bromofluorobenzene) may improve bromoform response.
7.16. 3. 3 1, 1, 2, 2-Tetrachl oroethane and I, I-di chl oroethane:
These compounds are degraded by contaminated transfer 1ines in
purge-and-trap systems and/or active sites in trapping materials.
7.16.4 Using the response factors from the initial calibration,
calculate the percent relative standard deviation (%RSD) for the
Calibration Check Compounds (CCCs).
%RSD = (SD/X} x 100
November 1992
where:
%RSD percent relative standard deviation
individual RF measurement
= mean of 5 initial RFs for a compound (the 5 points
over the calibration range)
SD standard deviation of average RFs for a compound,
where SD is calculated:
N (RF; - RF) 2
so = E
1
N-1
The %RSD for each individual CCC should be less than 30 percent.
This criterion must be met in order for the individual calibration to be
valid. The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane,
toluene, ethylbenzene, and vinyl chloride.
7.17 Daily GC/MS Calibration
7.17.1 Prior to the analysis of samples, purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectrum for the BFB
must meet all of the criteria given in Table 3 before sample analysis
begins. These criteria must be demonstrated every twe 1ve hours of
operation.
7.17.2 The initial calibration curve (Section 7.16) for each
compound of interest must be checked and verified once every twelve hours
of analysis time. This verification is accomplished by analyzing a
calibration standard that is at a concentration near the midpoint
concentration for the working range of the GC/MS and checking the SPCC
(Section 7.16.3) and CCC (Section 7.16.4).
7.17. 3 System Performance Check Compounds (SPCCs) : A system
performance check must be made each twelve hours of analysis. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration. If the minimum response factors are not achieved, the system
must be evaluated, and corrective action must be taken before analysis is
allowed to begin. The minimum response factor for volatile SPCCs is 0.300
(0.250 for bromoform). If these minimum response factors are not
achieved, some possible problems may be degradation of the standard
mixture, contamination of the injector port, contamination at the front
end of the analytical column, and active sites in the column or
chromatographic system. If the problem is active sites at the front end
of the analytical column, column maintenance (removal of approximately 1
foot from the front end of the column) may remedy the problem.
November 1992
7.17.4 Calibration Check Compounds: After the system performance
check has been met, CCCs listed in Section 7.16.4 are used to check the
validity of the initial calibration. Calculate the percent difference
using the following equation:
(RF; - RFC) x 100
% Difference =
RF;
where:
RFi = average response factor from initial calibration
RFc = response factor from current calibration check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. Benzene, toluene, and
styrene will have problems with response factors if Tenax® decomposition
occurs (either as a result of sampling exposure or temperature
degradation), since these compounds are decomposition products of Tenax®.
If the percent difference for each CCC is less than 25%, the initial
calibration is assumed to be valid. If the criterion of percent
difference less than 25% is not met for any one CCC, corrective action
MUST be taken. Problems similar to those listed under SPCCs could affect
this criterion. If a source of the problem cannot be determined after
corrective action is taken, a new five-point calibration curve MUST be
generated. The criteria for the CCCs MUST be met before quantitative
analysis can begin.
7.17.5 Internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last check calibration (12 hr), the
chromatographic system must be inspected for malfunctions and corrections
must be made, as required. A factor which may influence the retention
times of the internal standards on sample tubes is the level of overall
organic compound loading on the VOST tubes. If the VOST tubes are very
highly loaded with either a single compound or with multiple organic
compounds, retention times for standards and compounds of interest will be
affected. If the area for the primary ion of any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check, the gas chromatograph and mass spectrometer should be
inspected for malfunctions and corrections must be made, as appropriate.
If the level of organic loading of samples is high, areas for the primary
ions of both compounds of interest and standards will be adversely
affected. Calibration check standards should not be subject to variation,
since the concentrations of organic compounds on these samples are set to
be within the linear range of the instrumentation. If instrument
malfunction has occurred, analyses of samples performed under conditions
of malfunction may be invalidated.
November 1992
7.18 GC/MS Analysis of Samples
7.18.1 Set up the cartridge desorption unit, purge-and-trap
unit, and GC/MS as described above.
7.18.2 BFB tuning criteria and daily GC/MS calibration check
criteria must be met before analyzing samples.
7.18.3 Adjust the helium purge gas flow rate (through the
cartridges and purge vessel) to approximately 40 ml/min. Optimize the
flow rate to provide the best response for chloromethane and bromoform, if
these compounds are analytes. A flow rate which is too high reduces the
recovery of chloromethane, and an insufficient gas flow rate reduces the
recovery of bromoform.
7.18.4 The first analysis performed after the tuning check and
the calibration or daily calibration check is a method blank. The method
blank consists of clean VOST tubes (both Tenax® and Tenax®/charcoal) which
are spiked with surrogate compounds and internal standards according to
the procedure described in Section 7.7.1. The tubes which are used for
the method blanks should be from the same batch of sorbent as the sorbent
used for the field samples. After the tubes are cleaned and prepared for
shipment to the field, sufficient pairs of tubes should be retained from
the same batch in the laboratory to provide method blanks during the
analysis.
7.18.5 The organic-free reagent water for the purge vessel for
the analysis of each of the VOST samples should be supplied from the
laboratory inventory which is maintained with constant bubbling of inert
gas to avoid contamination.
7.18.6 If the analysis of a pair of VOST tubes has a
concentration of analytes that exceeds the initial calibration range, no
reanalysis of desorbed VOST tubes is possible. An additional calibration
point can be added to bracket the higher concentration encountered in the
samples so that the calibration database encompasses six or more points.
Alternatively, the data may be flagged in the report as "extrapolated
beyond the upper range of the calibration." The use of the secondary ions
shown in Table 1 is permissible only in the case of interference with the
primary quant itat ion ion. Use of secondary ions to calculate compound
concentration in the case of saturation of the primary ion is not an
acceptable procedure, since a negative bias of an unpredictable magnitude
is introduced into the quantitative data when saturation of the mass
spectrum of a compound is encountered. If high organic loadings, either
of a single compound or of multiple compounds, are encountered, it is
vital that a method blank be analyzed prior to the analysis of another
sample to demonstrate that no compound carryover is occurring. If
concentrations of organic compounds are sufficiently high that carryover
problems are profound, extensive bakeout of the purge-and-trap unit will
be required. Complete replacement of the contaminated analytical trap,
with the associated requirement for conditioning the new trap, may also be
required for VOST samples which show excessive concentrations of organic
compounds. Other measures which might be required for decontamination of
the analytical system include bakeout of the mass spectrometer,
November 1992
replacement of the filament of the mass spectrometer, cleaning of the ion
source of the mass spectrometer, and/or (depending on the nature of the
contamination) maintenance of the chromatographic column or replacement of
the chromatographic column, with the associated requirement for
conditioning the new chromatographic column.
7.19 Data Interpretation
7.19.l Qualitative analysis:
7.19.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.19.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Se 1ect ion of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound specific
retention time will be accepted as meeting this criterion.
7.19.1.1.2 The RRT of the sample component is within±
0.06 RRT units of the RRT of the standard component.
7.19.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Ex amp 1e: For an ion with an abundance of 50% in the
reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.)
7.19.1.1.4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum of
the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
7.19.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
November 1992
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the select ion of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.19.l.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification
are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within ± 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample with the nearest library searches will the mass
spectral interpretation specialist assign a tentative
identification.
7.19.2 Quantitative analysis:
7. 19. 2. 1 When a compound has been identified, the
quantitative analysis of that compound will be based on the
integrated abundance from the extracted ion current profile of the
primary characteristic ion for that compound (Table 1). In the
event that there is interference with the primary ion so that
quantitative measurements cannot be made, a secondary ion may be
used.
November 1992
NOTE: Use of a secondary ion to perform quantitative
calculations in the event of the saturation of the
primary ion is not an acceptable procedure because of
the unpredictable extent of the negative bias which is
introduced. Quantitative calculations are performed
using the internal standard technique. The internal
standard used to perform quantitative ca lcul at i ans sha 11
be the internal standard nearest the retention time of
a given analyte (see Table 4).
7.19.2.2 Calculate the amount of each identified analyte
from the VOST tubes as follows:
Amount (ng)
where:
As = area of the characteristic ion for the analyte to be
measured.
Ais = area of the characteristic ion of the internal standard.

cis amount (ng) of the internal standard.
7.19.2.3 The choice of methods for evaluating data
collected using the VOST methodology for incinerator trial burns is
a regulatory decision. Various procedures are used to decide
whether blank correction should be, performed and how blank
correction should be performed. Regulatory agencies to which VOST
data are submitted also vary in their preferences for data which are
or which are not blank corrected.
7.19.2.4 The total amount of the POHCs of interest
collected on a pair of traps should be summed.
7.19.2.5 The occurrence of high concentrations of analytes
on method blank cartridges indicates possible residual contamination
of sorbent cartridges prior to shipment and use at the sampling
site. Data with high associated blank values must be qualified with
respect to validity, and all blank data should be reported
separately. No blank corrections should be made in this case.
Whether or not data of this type can be applied to the determination
of Destruction and Removal Efficiency is a regulatory decision.
Continued observation of high concentrations of analytes on blank
sorbent cartridges indicates that procedures for cleanup and quality
control for the ~ampling tubes are inadequate. Corrective action
MUST be applied to tube preparation and monitoring procedures to
maintain method blank concentrations below detection limits for
analytes.
7.19.2.6 Where applicable, an estimate of concentration for
noncalibrated components in the sample may be made. The formulae
for quantitative calculations presented above should be used with
the following modifications: The areas Ax and Ais should be from the
November 1992
tot a1 ion chromatograms, and the Response Factor for the
non ca 1i brated compound should be assumed to be 1. The nearest
eluting internal standard free from interferences in the total ion
chromatogram should be used to determine the concentration. The
concentration which is obtained should be reported indicating: (1)
that the value is an estimate; and (2) which internal standard was
used.
7.19.2.7 If any internal standard recoveries fall outside
the control limits established in Section 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation. Report results without correction for surrogate
compound recovery data. When duplicates are analyzed, report the
data obtained with the sample results.
8.0 QUALITY CONTROL

8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum Quality Control requirements of are
specified in Chapter One. In addition, this program should consist of an initial
demonstration of laboratory capability and an ongoing analysis of check samples
to evaluate and document data quality. The laboratory must maintain records to
document the quality of the data generated. Ongoing data quality checks are
compared with established performance criteria to determine if the results of
analyses meet the performance characteristics of the method. When sample
analyses indicate atypical method performance, a quality control check standard
(spiked method blank) must be analyzed to confirm that the measurements were
performed in an in-control mode of instrument operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a method blank (laboratory blank sorbent tubes, reagent
water purge) that interferences from the analytical system, glassware, sorbent
tube preparation, and reagents are under control. Each time a new batch of
sorbent tubes is analyzed, a method blank should be processed as a safeguard
against chronic laboratory contamination. Blank tubes which have been carried
through all the stages of sorbent preparation and handling should be used in the
analysis.
8.3 The experience of the analyst performing the GC/MS analyses is
invaluable to the success of the analytical methods. Each day that the analysis
is performed, the daily calibration check standard should be evaluated to
determine if the chromatographic and tube desorption systems are operating
properly. Questions that should be asked are: Do the peaks look normal? Is the
system response obtained comparable to the response from previous calibrations?
Careful examination of the chromatogram of the calibration standard can indicate
whether column maintenance is required or whether the column is still usable,
whether there are leaks in the system, whether the injector septum requires
replacing, etc. If changes are made to the system (such as change of a column),
a calibration check must be carried out and a new multipoint calibration must be
generated.
November 1992
8.4 Required instrument quality control is found in the following
sections:
8.4.1 The mass spectrometer must be tuned to meet the specifications
for 4-bromofluorobenzene in Section 7.2 (Table 3).
8.4.2An initial calibration of the tube
desorption/purge-and-trap/GC/MS must be performed as specified in Section
7.7.
8.4.3 The GC/MS system must meet the SPCC criteria specified in
Section 7.16.3 and the CCC criteria in Section 7.16.4 each twelve hours of
instrument operation.
precision, the analyst must perform the following operations.
8.5.l A quality control (QC) check sample concentrate is required
containing each analyte at a concentration of 10 mg/L in high purity
methanol. The QC check sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If the QC check
sample concentrate is prepared by the 1aboratory, the QC check sample
concentrate must be prepared using stock standards prepared independently
from the stock standards used for calibration.
8.5.2 Spike four pairs of cleaned, prepared VOST tubes with 10 µL
of the QC check sample concentrate and analyze these spiked VOST tubes
according to the method beginning in Section 7.0.
8.5.3 Calculate the average recovery (X) in ng and the standard
deviation of the recovery (s) in ng for each analyte using the results of
the four analyses.
8.5.4 The average recovery and standard deviation must fall within
the expected range for determination of volatile organic compounds using
the VOST anal yt i cal methodology. The expected range for recovery of
volatile organic compounds using this method is 50-150%. Standard
deviation will be compound dependent, but should, in general, range from
15 to 30 ng. More detailed method performance criteria must be generated
from historical records in the laboratory or from interlaboratory studies
coordinated by the Environmental Protection Agency. Since the additional
steps of sorbent tube spiking and desorption are superimposed upon the
methodology of Method 8240, direct transposition of Method 8240 criteria
is questionable. If the recovery and standard deviation for all analytes
meet the acceptance criteria, the system performance is acceptable and the
analysis of field samples may begin. If any individual standard deviation
exceeds the precision limit or any individual recovery falls outside the
range for accuracy, then the system performance is unacceptable for that
analyte.
NOTE: The large number of analytes listed in Table 1 presents a
substant i a1 probabi 1ity that one or more wi 11 fail at least
one of the acceptance criteria when a11 ana 1ytes for this
method are determined.
November 1992
8.5.5 When one or more of the analytes tested fails at least one of
the acceptance criteria, the analyst must proceed according to one of the
alternatives below.
8.5.5.1 Locate and correct the source of any problem with
the methodology and repeat the test for all the analytes beginning
with Section 8.5.2.
8.5.5.2 Beginning with Section 8.5.2, repeat the test only
for those analytes that have failed to meet acceptance criteria.
Repeated failure, however, will confirm a general problem either
with the measurement system or with the applicability of the
methodology to the particular analyte (especially if the analyte in
question is not listed in Table 1). If the problem is identified as
originating in the measurement system, locate and correct the source
of the problem and repeat the test for all compounds of interest
beginning with Section 8.5.2.
8.6 To determine acceptable accuracy and precision limits for surrogate
standards, the following procedure should be performed.
8.6.1 For each sample analyzed, calculate the percent recovery of
each surrogate compound in the sample.
8.6.2 Once a minimum of thirty samples has been analyzed, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (s) for each of the surrogate compounds.
8.6.3 Calculate the upper and lower control limits for method
performance for each surrogate standard. This calculation is performed as
follows:
Upper Control Limit (UCL) = p + 3s
Lower Control Limit (LCL) = p - 3s
For reference, the comparable control limits for recovery of the
surrogate compounds from water and soil in Method 8240 are:
4-Bromofluorobenzene Water: 86-115% Soil: 74-121%
1,2-Dichloroethane-d4 Water: 76-114% Soi 1: 70-121%
Toluene-d 8 Water: 88-110% Soi 1: 81-117%
The control limits for the VOST methodology would be expected to be
similar, but exact data are not presently available. Individual laboratory
control limits can be established by the analysis of replicate samples.
8.6.4 If surrogate recovery is not within the limits established by
the laboratory, the fo 11 owing procedures are required: ( 1) Verify that
there are no errors in calculations, preparation of surrogate spiking
solutions, and preparation of internal standard spiking solutions. Also,
verify that instrument performance criteria have been met. (2) Recalculate
the data and/or analyze a replicate sample, if replicates are available.
November 1992
(3) If all instrument performance criteria are met and recovery of
surrogates from spiked blank VOST tubes (analysis of a method blank) i5
acceptable, the problem is due to the matrix. Emissions samples may be
highly acidic and may be highly loaded with target and non target organic
compounds. Both of these conditions will affect the ability to recover
surrogate compounds which are spiked on the field samples. The surrogate
compound recovery is thus a valuable indicator of the interactions of
sampled compounds with the matrix. If surrogates spiked immediatel)
before analysis cannot be observed with acceptable recovery, the
implications for target organic analytes which have been sampled in the
field must be assessed very carefully. If chemical or other interactions
are occurring on the exposed tubes, the failure to observe an analyte may
not necessarily imply that the Destruction and Removal Efficiency for that
analyte is high.
8.7 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples analyzed. Field duplicates may be analyzed to assess the precision of
the environmental measurements. When doubt exists over the identification of c
peak on the chromatogram, confirmatory techniques such as gas chromatography with
a dissimilar column or a different ionization mode using a mass spectrometer may
be used, if replicate samples showing the same compound are available. Whenever
possible, the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.

9.1 The method detection limit (MDL) is defined in Chapter One. The MDL
concentrations listed in Table 2 were obtained using cleaned blanked VOST tubes
and reagent water. Similar results have been achieved with field samples. The
MDL actually achieved in a given analysis will vary depending upon instrument
sensitivity and the effects of the matrix. Preliminary spiking studies indicate
that under these conditions, the method detection limit for spiked compounds in
extremely complex matrices may be larger by a factor of 500-1000.
10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHCs Using VOST.
EPA/600/8-84-007, March, 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014A, January, 1986.
3. U. S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
4. Bellar, T. A., and J. J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
November 1992
5. Bellar, T. A., and J. J. Lichtenberg, "Semi-Automated Headspace Analysis
of Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp 108-129, 1979.
November 1992
TABLE 1.
RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
WHICH CAN BE ANALYZED BY METHOD 5041
Retention Primary Ion Secondary Ion ( s)

Compound Time (min) Mass Mass(es)
Acetone 7.1 43 58
Acryl onitri le 8.6 53 52' 51
Benzene 13.3 78 52' 77
Bromochloromethane 12.0 128 49, 130, 51
Bromodichloromethane 16.0 83 85, 129
4-Bromofluorobenzene 23.4 95 174, 176
Bromoform 22.5 173 171, 175, 252
Bromomethane 4.1 94 96, 79
Carbon disulfide 7.1 76 78
Carbon tetrachloride 12.6 117 119, 121
Chlorobenzene 20.5 112 114, 77
Chlorodibromomethane 19.3 129 208, 206
Chloroethane 4.2 64 66, 49
Chloroform 12.2 83 85, 47
Chloromethane 3.0 50 52, 49
Dibromomethane 15.4 93 174, 95
1,1-Dichloroethane 10.0 63 65, 83
1,2-Dichloroethane 13.3 62 64, 98
1,1-Dichloroethene 6.4 96 61, 98
trans-1,2-Dichloroethene 8.6 96 61, 98
1,2-Dichloropropane 15.2 63 62, 41
cis-1,3-Dichloropropene 17.0 75 77' 39
trans-1,3-Dichloropropene 18.2 75 77, 39
1,4-Difluorobenzene 14.2 114 63, 88
Ethyl benzene 21.1 106 91
Iodomethane 7.0 142 127' 141
Methylene chloride 8.1 84 49, 51, 86
Styrene 22.3 104 78, 103
1,1,2,2-Tetrachloroethane 24.0 83 85, 131, 133
Tetrachloroethene 18.6 164 129, 131, 166
Toluene 17.4 92 91, 65
1,1,1-Trichloroethane 12.4 97 99, 117
1,1,2-Trichloroethane 18.4 97 83, 85, 99
Trichloroethene 14.5 130 95, 97' 132
Trichlorofluoromethane 5.1 101 103, 66
1,2,3-Trichloropropane 24.0 75 110, 77' 61
Vinyl chloride 3.2 62 64, 61
Xylenes* 22.2 106 91
* The retention time given is for m- and p-xylene, which coelute on the Megabor
column. a-Xylene elutes approximately 50 seconds later.
November 1992
TABLE 2.
PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Detection Boiling
Compound CAS Number Limit, ng Point, °C
Chloromethane 74-87-3 58 -24

Bromomethane 74-83-9 26 4
Vinyl chloride 75-01-4 14 -13
Chloroethane 75-00-3 21 13
Methylene chloride 75-09-2 9 40
Acetone 67-64-1 35 56
Carbon disulfide 75-15-0 11 46
1,1-Dichloroethene 75-35-4 14 32
1,1-Dichloroethane 75-35-3 12 57
trans-1,2-Dichloroethene 156-60-5 11 48
Chloroform 67-66-3 11 62
1,2-Dichloroethane 107-06-2 13 83
1,1,1-Trichloroethane 71-55-6 8 74
Carbon tetrachloride 56-23-5 8 77
Bromodichloromethane 75-27-4 11 88
1,1,2,2-Tetrachloroethane** 79-34-5 23 146
1,2-0ichloropropane 78-87-5 12 95
trans-1,3-Dichloropropene 10061-02-6 17 112
Trichloroethene 79-01-6 11 87
Dibromochloromethane 124-48-1 21 122
1,1,2-Trichloroethane 79-00-5 26 114
Benzene 71-43-2 26 80
cis-1,3-Dichloropropene 10061-01-5 27 112
Bromoform** 75-25-2 26 150
Tetrachloroethene 127-18-4 11 121
Toluene 108-88-3 15 111
Chlorobenzene** 108-90-7 15 132
Ethyl benzene 100-41-4 21 136
Styrene** 100-42-5 46 145
Trichlorofluoromethane 75-69-4 17 24
lodomethane 74-88-4 9 43
Acryl onitril e 107-13-1 13 78
Dibromomethane 74-95-3 14 97
1,2,3-Trichlorppropane** 96-18-4 37 157
total Xylenes 22 138-144
* The method detection limit (MDL) is defined as the minimum concentration of a
substance that can be measured and reported with 99% confidence that the analyte
concentration is greater than zero and is determined from analysis of a sample in
a given matrix containing the analyte. The detection limits cited above were
determined according to Title 40 CFR, Part 136, Appendix B, using standards spiked
onto clean VOST tubes. Since clean VOST tubes were used, the values cited above
represent the best that the methodology can achieve. The presence of an emissions
matrix will affect the ability of the methodology to perform at its optimum level.
**Not appropriate for quantitative sampling by Method 0030.
November 1992
TABLE 3.
KEY ION ABUNDANCE CRITERIA FOR 4-BROMOFLUOROBENZENE
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95%, but less than 101% of mass 174
177 5 to 9% of mass 176
November 1992
TABLE 4.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANTITATION
3romochloromethane 1,4-Difluorobenzene
ketone Benzene
kryl onitril e Bromodichloromethane
Bromomethane Bromoform
Carbon disulfide Carbon tetrachloride
Chloroethane Chlorodibromomethane
Chloroform Dibromomethane
Chloromethane 1,2-Dichloropropane
1,1-Dichloroethane cis-1,3-Dichloropropene
1,2-Dichloroethane trans-1,3-Dichloropropene
1,2-Dichloroethane-d4 (surrogate) 1,1,1-Trichloroethane
1,1-Dichloroethene 1,1,2-Trichloroethane
Trichloroethene
trans-1,2-Dichloroethene
Iodomethane
Methylene chloride
Trichlorofluoromethane
Vinyl chloride
Chlorobenzene-d5
4-Bromofluorobenzene (surrogate)
Chlorobenzene
Ethyl benzene
Styrene
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
Toluene-d8 (surrogate)
1,2,3-Trichloropropane
Xylenes
November 1992
"'c
...4"
c
.2
...•
c:
0
·;:
:;)
ID
'---
~
0
c:
...•
D
0
c:
...
•
3c: 3
c: c:
0
·;: • :.,. Co
::i
io
.::"
•
;"'
.......
-
.......
'
~
a. 0 e
:.,.
v
'
v
Figure 1. Cartridge Desorption Flow
November 1992
w
...J
a..
~
<(
V1
c:
:J
a.
0
I..
I-
~1
.S?
0..
....
0
"'v
0
v
O'l
~
....
:;
u
Figure 2. Cartridge Desorption Unit with Purge and Trap Unit
November 1992
-E
(/1
(/1
- I..
Q)
E
0
Q)
-
-Q)
(/1
>- -
0
,, Q)
·-
>
Q) · -
~..c:
Q) I..
u
0 I.. (11
~-
u
CJ\<
0 0 I..
Q)
a. 0 o_0
I..
(/') a U1
....._
'l
_.._
Q)
u
- 0
-
I ..
Q)
c
....--:...
ll
..c:
a.
0
I..
01
(/1 0
o-
<..:> 0
E
0
I..
..c:
u
'l
a.
0
I.. (/1
.... :I
~-
c~
oo
Q) a.
°'a.
1..<
:I
Cl..
c
0
Q):.;:_
~a:-
:::i'-C
I- O=>
(/1
Q)
0
Figure 3. Schematic Diagram of Overall Analytical System
November 1992
0
Sintered Glass frit Gas flow
Figure 4. Sample Purge Vessel
November 1992
_....._ ___ ;;
<..:)
0
~
i...----..iJi
..
,.. ...
: ig'
1:a.
,___ __..: '-' .§
Figure 5. Schematic of Volatile Organic Sampling Train (VOST)
November 1992
METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN: WIDE-BORE CAPILLARY COLUMN TECHNIQUE
7 10 Initiate 7 16 2
tube Tabulate the
( Start ,._- desorption/ ...... area responae
purge and of all cm pd a
heat1ng of lnterest
7 1 Cond1 tions for

Cartr1dge 7 11 Set the GC 7 16 3
Desorption Oven, oven to subam· Calculate the
Purge & Trap bient tempera- average Rf for
Concentrator, GC, ture with each compound
and MS liqu1d n1trogan of lntarest
7 2 Daily. tune 7 12 Prep the 7 16 4 Cal cu-

the CC/MS with CC/MS tystem ht• the %RSD
BIB and check for data for the CCCa
ca lib curve aqu1s1t1on The %RSD must
See sect 7 17 be <30%
7 13 After the
tube/water purge
7 3 -7 6 time, at ta ch th• 7 18 GC/MS
Assemble th• analytical trap to analysis of
system the GC/MS for samples
desorption
7 7 l Calibrate the
instrument system us·
ing the lnternal std 7 14 Waah purg- 7 19 l Qualita-
procedure Stds and ing vessel w1th tiv• analysis
call.bral1on cmpdt are two Sml flush•• of data and
•piked lnlo cleaned of organic-free ident guide-
VOST tube• using the reagent water line• of cmpds
flash evaporation
technique
7 15 Recond1 ti on the
analytical trap by
7 8 Prep the baking it out at 7 19 2 Quanll-
purge & trap t•mp• up to 220 C for tative analysis
unll w1th Sml 11 min Trap replace- of data for the
organic-fr•• ment may be necessary compounds of
r ea gent water if the analytical interest
trap lt saturated
beyond cleanup
7 9 Connect 7 16 l Prep
paired VOST
tubes to the
gas lines for
desorpt1on
- ca lib stds as
ln 7 7 l Add
waler to vessel
and detorb
i---
( Stop
November 1992
METHOD 5100
DETERMINATION OF THE VOLATILE ORGANIC CONCENTRATION OF WASTE SAMPLES

1.1 This method is applicable to the determination of the volatile
organic concentration of hazardous wastes.
1. 2 Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID) or a Hall
electrolytic conductivity detector (HECD), because knowledge beyond the scope of
this presentation is required.

2.1 A sample of waste is collected from a source as close to the point
of generation as practical. The sample is then heated and purged with nitrogen
to separate the volatile organic compounds. Part of the sample is analyzed for
carbon concentration, as methane, with an FID, and part of the sample is analyzed
for chlorine concentration, as chloride, with an HECD. The volatile organic
concentration is the sum of the measured carbon and chlorine concentrations of
the sample.
3.0 INTERFERENCES
(particularly chlorofluorocarbons and methylene chloride) through the sample
container septum during shipment and storage. A field blank prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.

4.1 Sampling. The following equipment is required:
4.1.1 Static Mixer. Installed in-line or as a by-pass loop, sized so
that the drop size of the dispersed phase is no greater than 1,000 µm.
If the installation of the mixer is in a by-pass loop, then the entire
waste stream must be diverted through the mixer.
4.1.2 Tap. Installed no further than two pipe diameters downstream
of the static mixer outlet.
4.1.3 Sampling Tube. Flexible Teflon, 0.25 in. ID.
4.1.4 Sample Container. Borosilicate glass or Teflon, 15 to 50 ml,
and a Teflon lined screw cap capable of forming an air tight seal.
5100 - 1 Revision 0
November 1992
4.1.5 Cooling Coil. Fabricated from 0.25 in. ID 304 stainless steel
tubing with a thermocouple at the coil outlet.
4.2 Analysis. The following equipment is required:
4.2.1 Purging Apparatus. For separating the volatile organics from
the waste sample. A schematic of the system is shown in Figure 1. The
purging apparatus consists of the following major components:
4.2.1.1 Purging Chamber. A glass container to hold the
sample while it is heated and purged with dry nitrogen. Exact
dimensions are shown in Figure 3.
The cap of the purging chamber is equipped with three
fittings: one for a mechanical stirrer (fitted with the #11 Ace
thread), one for a thermometer (top fitting), and one for the Teflon
exit tubing (side fitting) as shown in Figure 3.
The base of the purging chamber is a 50 mm inside diameter
(ID) cylindrical glass tube. One end of the tube is fitted with a
50 mm Ace-thread fitting, while the other end is sealed. Near the
sealed end in the side w~ll is a fitting for a glass purging lance.
4.2.1.2 Purging Lance. Glass tube, 6 mm ID by 15.25 cm
long, bent into an "L" shape. The "L" end of the tube is sealed,
and then pierced with fifteen holes, each 1 mm in diameter.
4.2.1.3 Mechanical Stirrer. Stainless steel or Teflon
stirring rod driven by an electric motor.
4.2.1.4 Coalescing Filter. Porous fritted disc
incorporated into a container with the same dimensions as the
purging chamber. The details of the design are shown in Figure 3.
4.2.1.5 Constant Temperature Bath. Capable of maintaining
a temperature around the purging chamber and coalescing filter of 75
± 5°C.
4.2.1.6 Three-way Valves. Two, manually operated,

stainless steel.
4.2.1.7 Flow Controller. Capable of maintaining a purge
gas flow rate of 6 ± 0.006 L/min.
4.2.1.8 Rotameters. Two for monitoring the air flow
through the purging system (0-20 L/min).
4.2.1.9 Sample Splitters. Two heated flow restrictors.
At a purge rate of up to 6 L/min, one will supply a constant flow of
70 to 100 ml/min to the analyzers. The second will split the
analytical flow between the FID and the HECD. The approximate flow
to the FID will be 40 ml/min and to the HECD will be 15 ml/min, but
the exact flow must be adjusted to be compatible with the individual
detector and to meet its linearity requirement.
5100 - 2 Revision O
November 1992
4.2.1.10 Adsorbent Tube. To hold 10 g of activated
charcoal. Excess purge gas is vented through the adsorbent tube to
prevent any potentially hazardous materials from entering the
laboratory.
4.2.2 Volatile Organic Measurement System. Consisting of an FID to
measure the carbon concentration of the sample, and an HECD to measure the
chlorine concentration (as chloride).
4.2.2.1 FID. An FID meeting the following specifications
is required:
4.2.2.1.1 Linearity. A linear response (± 5 percent)
over the operating range as demonstrated by the procedures
established in Section 8.1.1.
4.2.2.1.2 Range. A full scale range of 50 pg
carbon/sec to 50 µg carbon/sec. Signal attenuators shall be
available to produce a minimum signal response of 10 percent
of full scale.
4.2.2.1.3 Data Recording System. Analog strip chart
recorder or digital integration system compatible with the FID
for permanently recording the output of the detector.
4.2.2.2 HECD. An HECD meeting the following
specifications is required:
4.2.2.2.1 Linearity. A linear response(± 10 percent)
over the response range as demonstrated by the procedures in
Section 8.1.2.
4.2.2.2.2 Range. A full scale range of 5.0 pg/sec to
500 ng/sec chloride. Signal attenuators shall be available to
produce a minimum signal response of 10 percent of full scale.
4.2.2.2.3 Data Recording System. Analog strip chart
recorder or digital integration system compatible with the
output voltage range of HECD.
5.0 REAGENTS
use without adversely impacting the accuracy of the determination.
refer to organic-free reagent water as defined in Chapter One.
5100 - 3 Revision 0
November 1992
5.3 Sampling.
5.3.l Polyethylene glycol (PEG), 98 percent pure with an average
molecular weight of 400. Remove any organic compounds that may be
detected as volatile organics already present in the polyethylene glycol
before it is used, by heating it to 250°C and purging it with nitrogen at
a flow rate of 1 to 2 L/min for 2 hours. Waste PEG must be disposed of
properly (consult local, State and Federal guidelines and regulations).
5.4 Analysis.
5.4.1 Sample Separation. The following are required for the sample
purging step:
5.4.1.1 Polyethylene glycol. Same as Section 5.3.1.
5.4.1.2 Silicone, Mineral, or Peanut Oil. For use as the
heat dispersing medium in the constant temperature bath.
5.4.1.3 Purging Gas. Zero grade nitrogen (Nz), containing
less than 1 ppm carbon.
5.4.2 Volatile Organics Measurement. The following are required for
measuring the volatile organic concentrations:
5.4.2.1 Hydrogen (Hz). Zero grade Hz, 99.999 percent pure.
5. 4. 2. 2 Combustion Gas. Zero grade air or oxygen, as
required by the FID.
5.4.2.3 FID Calibration Gases.
5.4.2.3.1 Low-level Calibration Gas. Gas mixture
standard with a nominal concentration of 35 ppm (v/v) propane
in Nz.
5.4.2.3.2 Mid-level Calibration Gas. Gas mixture
in Nz.
5.4.2.3.3 High-level Calibration Gas. Gas mixture
in Nz.
5.4.2.4 HECD Calibration Gases.
5.4.2.4.1 Low-level Ca'fibration Gas. Gas mixture
standard with a nominal concentration of 20 ppm (v/v) 1,1-
dichloroethene in Nz.
5.4.2.4.2 Mid- level Calibration Gas. Gas mixture
dichloroethene in Nz.
5100 - 4 Revision 0
November 1992
5.4.2.4.3 High-level Calibration Gas. Gas mixture
dichloroethene in N2 •
5.4.2.5 n-Propanol, CH3CH 2CH 20H. ACS grade or better.
5.4.2.6 Electrolyte Solution. For use in the conductivity
detector. Mix together 500 ml of water and 500 ml of n-propanol and
store in a glass container.
5.4.2.7 Charcoal. Activated coconut, 12 to 30 mesh.

6.1 See Volume One, Section B, Chapter Four, "Organic Analytes,"
Section 4. 1.
6.2 Sampling Plan Design and Development. Use the procedures given in
Volume Two, Part III, Chapter Nine, "Sampling Plan."
6.3 Waste in Enclosed Pipes. Sample as close as practical to the point
of waste generation in order to minimize the loss of organics. Assemble the
sampling apparatus as shown in Figure 4. Install the static mixer in the process
line or in a by-pass line. Locate the tap within two pipe diameters of the
static mixer outlet.
6.4 Prepare the sampling containers as follows: Pour into the container
an amount of PEG equal to the total volume of the sample container, less 10 ml.
PEG will reduce, but not eliminate, the loss of volatile organic compounds during
sample collection. Weigh the sample container with the screw cap, the PEG and
any labels to the nearest 0.01 g, and record the weight (m ). Before sampling,
store the containers in an ice bath until the temperature of the PEG is less than
4°C.
6.5 Begin sampling by purging the sample lines and cooling coil with at
least four volumes of waste. Collect the purged material in a separate container
and dispose of it properly.
6.6 After purging, stop the sample flow and direct the sampling tube to
a preweighed sample container, prepared as described in Section 6.4. Keep the
tip of the tube below the surface of the PEG during sampling to minimize contact
with the atmosphere. Sample at a flow rate such that the temperature of the
waste is less than 10°C. Fill the sample container and immediately cap it
(within 5 seconds) so that a minimum headspace exists in the container. Store
immediately in a cooler and cover with ice .
•
6.7 Alternative sampling techniques may be used upon the approval of the
Administrator.
5100 - 5 Revision 0
November 1992
7. 0 PROCEDURE
7.1 Sample Recovery. Remove the sample container from the cooler, and
wipe the exterior of the container to remove any extraneous ice, water, or other
debris. Reweigh the sample container and sample to the nearest 0. 01 g, and
record the weight (m5 f). Pour the contents of the sample container into the
purging flask. Rinse the sample container three times with PEG, transferring the
rinsings to the purging flask after each rinse. The total volume of PEG in the
purging flask shall be approximately 50 ml. Add approximately 50 ml of water.
7. 2 Apparatus Assembly. Assemble the purging apparatus as shown in
Figure 2, leaving the purging chamber out of the constant temperature bath.
Adjust the stirring rod so that it nearly reaches the bottom of the chamber.
Position the sparger so that it is within 1 cm of the bottom, but does not
interfere with the stirring rod. Lower the thermometer so that it extends into
the liquid.
7.3 Sample Analysis. Turn on the constant temperature bath and allow the
temperature to equilibrate at 75 ± 5°C. Turn the bypass valve so that the purge
gas bypasses the purging chamber. Turn on the purge gas. Allow both the FIO and
the HECO to warm up until a stable baseline is achieved on each detector. Pack
the adsorbent tube with 10 g of charcoal. Replace the charcoal after each run
and dispose of the spent charcoal properly. Place the assembled chamber in the
constant temperature bath. When the temperature of the PEG reaches 75 ± 5°C,
turn the bypass valve so that the purge gas flows through the purging chamber.
Begin recording the response of the FID and the HECD. Compare the readings
between the two rotameters in the system. If the readings differ by more than
five percent, stop the purging and determine the source of the discrepancy before
resuming.
As purging continues, monitor the output of the FID to make certain that
the separation is proceeding correctly, and that the results are being properly
recorded. Every 10 minutes, read and record the purge flow rate and the liquid
temperature. Continue purging for 30 minutes.
7.4 Initial Performance Check of Purging System. Before placing the
system in operation, after a shutdown of greater than six months, and after any
major modification, conduct the linearity checks described in Sections 7.4.1 and
7.4.2. Install all calibration gases at the three-way calibration gas valve.
See Figure 1.
7.4.l FID Linearity Check and Calibration. With the purging system
operating as in Section 7.3, allow the FID to establish a stable baseline.
Set the secondary pressure regulator of the calibration gas cylinder to
the same pressure as the purge gas cylinder, and inject the calibration
gas by turning the calibration gas valve to switch flow from the purge gas
to the calibration gas. Continue the calibration gas flow for
approximately two minutes before switching to the purge gas. Make
triplicate injections of each calibration gas (Section 5.4.2.3), and then
calculate the average response factor for each concentration (Rt), as well
as the overall mean of the response factor values, R9 • The instrument
linearity is acceptable if each Ri is within 5 percent of R and if the
relative standard deviation (Section 7.7.10) for each set o~ triplicate
5100 - 6 Revision 0
November 1992
injections is less than 5 percent. Record the overall mean value of the
propane response factor values as the FID calibration response factor, R0 •
7.4.2 HECD Linearity Check and Calibration. With the purging system
operating as in Section 7.3, allow the HECD to establish a stable
baseline. Set the secondary pressure regulator of the calibration gas
cylinder to the same pressure as the purge gas cylinder, and inject the
calibration gas by turning the calibration gas valve to switch flow from
the purge gas to the calibration gas. Continue the calibration gas flow
for about two minutes before switching to the purge gas. Make triplicate
injections of each calibration gas (Section 5.4.2.4), and then calculate
the average response factor for each concentration, Rth' as well as the
overall mean of the response factors, R~. The instrument linearity is
acceptable if each Rth (Section 7.7.5) is within 10 percent of R0 h and if
the relative standard deviation (Section 7.7.10) for each set of
triplicate injections is less than 10 percent. Record the overall mean
value of the chlorine response factors as the HECD response factor, R0 h.
7.5 Daily Calibrations.
7.5.1 FID Daily Calibration. Inject duplicate samples from the mid-
level FID calibration gas (Section 5.4.2.3.2) as described in Section
7.4.1, and calculate the average daily response factor (DRt). System
operation is adequate if the DRt is within 5 percent of the R0 calculated
during the initial performance test (Section 7. 4.1) . Use the DRt for
calculation of carbon content in the samples.
7.5.2 HECD Daily Calibration. Inject duplicate samples from the
mid-level HECD calibration gas (Section 5.4.2.4.2) as described in Section
7.4.2, and calculate the average daily response factor DRth' The system
operation is adequate if the DRth is within 10 percent of the R0 h
calculated during the initial performance test (Section 7.4.2). Use the
DRth for calculation of chlorine in the samples.
7.6 Water Blank. Transfer about 60 ml of organic-free reagent water into
the purging chamber. Add 50 ml of PEG to the purging chamber. Treat the blank
as described in Sections 7.2 and 7.3.
7.7 Calculations
7.7.1 Nomenclature.
Area under the water blank response curve, counts.
= Area under the sample response curve, counts.
c = Concentration of volatile organic in the sample,
ppm(w/w).
Concentration of FID calibration gas, ppm(v/v).
Concentration of HECD calibration gas, ppm(v/v).
Average daily response factor of the FID, µg C/counts.
5100 - 7 Revision 0
November 1992
Average daily response factor of the HECD detector, µg
Cl "/counts.
= Mass of carbon, as methane, in the FID calibration
standard, µg.
= Mass of chloride in the HECD calibration standard, µg.
= Mass of the waste sample, g.
Mass of carbon, as methane, in the sample, µg.
= Mass of sample container and waste sample, g.
Mass of chloride in the sample, µg.
= Mass of sample container prior to sampling, g.
= Mass of volatile organic in the sample, µg.
Ambient barometric pressure in the laboratory, Torr.
Flowrate of calibration gas, L/min.
Length of time standard gas is delivered to the
analyzer, min.
= Ambient temperature in the laboratory, °K.
7.7.2 Mass of Carbon, as Methane in the FID Calibration Gas.

mco = kz Cc tc Qc (P/Ta) Eq. 1
where k2 = 0.5773 µg C-°K/µl-Torr
7.7.3 Mass of Chloride in the HECD Detector Calibration Gas.
mch = k3 ch tc QC (P/Ta) Eq. 2
where k3 = 1.1371 µg Cl-°K/µl-Torr
7.7.4 FID Response Factor.
Rt = mcjA Eq. 3
7.7.5 HECD Response Factor.
Rth = mch/A Eq. 4
7.7.6 Mass of Carbon in the Sample.
msc = DRt (As - Ab) Eq. 5
5100 - 8 Revision 0
November 1992
7.7.7 Mass of Chloride in the Sample.
Eq. 6
7.7.8 Mass of Volatile Organic in the Sample.
Eq. 7
7.7.9 Standard Deviation.
n
SD= lOOx [ ~(xi-x) 2/(n-1)] 112 Eq. 8
i=l
7.7.10 Relative Standard Deviation.
RSD = SD/x Eq. 9
7.7.11 Mass of Sample.
Eq. 10
7.7.12 Concentration of Volatile Organic in Waste.
8.0 QUALITY CONTROL

8.1 Refer to Chapter One for specific Quality Control procedures.
8.2 Maintain a record of performance of all system checks and
calibrations.
8.3 Calibrate analytical balance against standard weights.

9.1 Performance data are not currently available.
10.0 REFERENCES
1. "Determination of the Volatile Organic Content of Waste Samples" Method
25D; Proposed Amendment to 40 CFR Part 60, Appendix A, January 1989.
5100 - 9 Revision 0
November 1992
FIGURE 1
Purging Apparatus
FLOW Vent
COALESCING METER
CALIBRATION GAS PURGINO , FILTER
VALVE Ol'\MDER
~ FID
__
I FLOW
~~-
I
I MIITER
VALVE•I• _..._ .. ~. SPLITIER
I
HECD
'4 't
VALVll
\
\
\
\
CONSTANTTEMPERATURE
BATH
' I ''BYl'ASS VALVE

' I
NITROOEN FLOW II...... I I
CALlDRATION
REGULATOR GAS
November 1992
FIGURE 2
ROl'AMlifBR
TO DETECTORS
OATH JIBATER/
CON1ROLl..f.R
/OU.. DATii
AUT
PURGINO CHAMBER COALESCING FILTER
November 1992
FIGURE 3
Purging Chamber
#11 ACETHR.ED -
l
I
• " # 7 ACETHRED
TRUBORE
STIRRER
GLASS
In I
#7 ACE THR.ED~--....1
SPAROER.
5100 - 12 Revision o
November 1992
FIGURE 4
WASTBUHI!
FROMSOURCB
t
VALVF.S
' REDUCER ( 1/4 • ruon FIITING)
omONALPUMP
November 1992
METHOD 5100
DETERMINATION OF THE VOLATILE ORGANIC CONCENTRATION OF WASTE SAMPLES
Start
7.1 7.2
Pour sample contents Direct pwge gas
in purge flask through pwge chamber
7.1
Rinse sample container
3 limes with DOP
7.2
Record response of
FIDand HECD
7.1
Assemble purging
apparatus as shown
in Figure 1
7.2 7.2
Yes
Equilibrate Stop operations
the system and readjust
No
Stop
November 1992
METHOD 5110
DETERMINATION OF ORGANIC PHASE VAPOR PRESSURE IN WASTE SAMPLES

1.1 This method is applicable for determining the organic phase vapor
pressure of waste samples from treatment, storage, and disposal facilities
(TSDF).
1. 2 Performance of this method should not be attempted by persons
unfamiliar with the operation of a Flame Ionization Detector (FID) nor by those
who are unfamiliar with source sampling, because knowledge beyond the scope of
this presentation is required.

2.1 A waste sample is collected from a source as close to the point of
generation as pr act i cal . The head space vapor of the sample is analyzed for
carbon content by a headspace analyzer, which uses an FID.
3.0 INTERFERENCES
container septum during shipment and storage. A field sample blank prepared from
3.2 Contamination by carryover can occur whenever a low-concentration
sample is analyzed after a high-concentration sample. To reduce carryover, the
sample syringe must be rinsed out between samples with organic-free reagent
water. Whenever an unusually concentrated sample is encountered, it should be
followed by an analysis of organic-free reagent water. It may be necessary to
wash out the syringe with detergent, rinse with distilled water, and dry in a
150°C oven between analyses.
3.3 Before processing daily samples, the analyst should demonstrate that
the entire analytical system is free from interference by the analysis of an
organic-free reagent water or solvent blank.

4.1 Sampling. The following equipment is required:
4.1.1 Sample Containers. Vials, glass, with butyl rubber septa,
Perkin-Elmer Corporation Part Numbers 0105-0129 (glass vials), 8001-0728
(gray butyl rubber septa, plug style), 0105-0131 (butyl rubber septa), or
equivalent. The seal must be made from butyl rubber. Silicone rubber
seals are not acceptable.
5110 - 1 Revision 0
November 1992
4.1.2 Vial Sealer. Perkin-Elmer Number 105-0106, or equivalent.
4.1.3 Gas-Tight Syringe. Perkin-Elmer Number 00230117, or
equivalent.
4.2 The following equipment is required if sampling from an enclosed
pipe:
4.2.1 Static Mixer. Installed in-line or as a by-pass loop, sized
so that the drop size of the dispersed phase is not greater that 1,000 µm.
If the installation of the mixer is in a by-pass loop, then the entire
waste stream must be diverted through the mixer.
4.2.2 Tap.
4.2.3 Tubing, Teflon, 0.25 in. ID.
4.2.4 Cooling Coil. Stainless steel (304), 0.25 in. ID, equipped
with a thermocouple at the coil outlet.
4.3 Analysis. The following equipment is required:
4.3.l Balanced Pressure Headspace Sampler. Perkin-Elmer HS-6, HS-
100, or equivalent, equipped with a glass bead column instead of a
chromatographic column.
4.3.2 Flame Ionization Detector. An FID meeting the following
specifications is required:
4.3.2.1 Linearity. A linear response (±5 percent) over
the operating range, as demonstrated by the procedures established
in Sections 7.2.2 and 8.1.1.
4.3.2.2 Range. A full scale range of 1 to 10,000 ppm CH4 .
Signal attenuators should be available to produce a minimum signal
response of 10 percent of full scale.
4.3.3 Data Recording System. Analog strip chart recorder or digital
integration system compatible with the FID for permanently recording the
output of the detector.
4.3.4 Thermometer. Capable of reading temperatures in the range of
30° to 60°C with an accuracy of ±0.1°C.
5.0 REAGENTS
5.1 Analysis. The following reagents are required for analysis:
5.1.l Hydrogen (H 2 ). Zero grade.
5.1.2 Carrier Gas. Zero grade nitrogen, containing less than 1 ppm
carbon and less than 1 ppm carbon dioxide.
5110 - 2 Revision 0
November 1992
5.1.3 Combustion Gas. Zero grade air or oxygen, as required by the
FID.
5.2 Calibration and Linearity Check.
5. 2.1 Stock Cylinder Gas Standard. 100 percent propane. The
manufacturer shall (a) certify the gas composition to be accurate to ±3
percent or better (see Section 5.2.1.1); (b) recommend a maximum shelf
life over which the gas concentration does not change by greater than ±5
percent from the certified value; and (c) affix the date of gas cylinder
preparation, certified propane concentration, and recommended maximum
shelf life to the cylinder before shipment to the buyer.
5. 2 .1.1 Cylinder Standards Cert ifi cation. The
manufacturer shall certify the concentration of the calibration gas
in the cylinder by (a) directly analyzing the cylinder and (b)
calibrating his analytical procedure on the day of cylinder
analysis. To calibrate his analytical procedure, the manufacturer
shall use, as a minimum, a three-point calibration curve.
5.2.1.2 Verification of Manufacturer's Calibration
Standards. Before using, the manufacturer shall verify the
concentration of each calibration standard by (a) comparing it to
gas mixtures prepared in accordance with the procedure described in
Section 7.1 of Method 106 of 40 CFR Part 61, Appendix B, or by (b)
calibrating it against Standard Reference Materials (SRMs), prepared
by the National Institute of Science and Technology, if such SRMs
are available. The agreement between the in it i a11 y determined
concentration value and the verification concentration value must be
within ±5 percent. The manufacturer must reverify all calibration
standards on a time interval that is consistent with the shelf life
of the cylinder standards sold.
5. 3 Bl an ks
5.3.1 Organic-free reagent water. All references to water in this
method refer to organic-free reagent water as defined in Chapter One.

Section 4.1.
6.2 Sampling Plan Design and Development. Use the procedures given in
Chapter Nine, "Sampling Plan."
6.3 Collect samples according to the procedures in Chapter 9, or, if it
is necessary to sample from an enclosed pipe, sample according to the procedures
described below.
6.3.1 The apparatus designed to sample from an enclosed pipe is
shown in Figure 1. The apparatus consists of an in-line static mixer, a
tap, a cooling coil immersed in an ice bath, a flexible Teflon tube
. 5110 - 3 Revision 0
November 1992
connected to the outlet of the cooling coil, and sample container. Locate
the tap within two pipe diameters of the static mixer outlet. Install the
static mixer in the process line or in a by-pass line.
6.3.2 Begin sample collection by purging the sample 1ines and
cooling coil with at least four volumes of waste. Collect the purged
material in a separate container.
6.3.3 After purging, stop the sample flow and transfer the Teflon
sampling tube to a sample container. Sample at a flow rate such that the
temperature of the waste is <10°C. Fill the sample container halfway (±5
percent) and cap immediately (within 5 seconds).
6.3.4 Store the collected samples on ice or in a refrigerator until
analysis.
6.3.5 Alternative sampling techniques may be used upon the approval
of the Administrator.
7. 0 PROCEDURE
7.1 Calibration
7.1.1 Maintain a record of each item.
7.1.2 Use the procedures in Section 7.1.3 to calibrate the headspace
analyzer and FID, and to check for linearity before the system is first
placed in operation, after any shutdown that is longer than 6 months, and
after any modification of the system.
7.1. 3 Ca 1 i brat ion and Linearity. Use the procedures in Section
6.2.1 of Method 18 of 40 CFR Part 60, Appendix A, to prepare the standards
and calibrate the flowmeters, using propane as the standard gas. Fill the
calibration standard vials halfway (±5 percent) with organic-free reagent
water. Prepare a minimum of three concentrations that will bracket the
applicable cutoff. For a cutoff of 5.2 kPa (0.75 psi), prepare nominal
concentrations of 30,000, 50,000, and 70,000 ppm as propane. For a cutoff
of 27.6 kPa (4.0 psi), prepare nominal concentrations of 200,000, 300,000,
and 400,000 ppm as propane.
7.1. 3. 1 Use the procedures in Section 7. 2. 3 to measure the
FID response of each standard. Use a linear regression analysis to
calculate the values for the slope (k) and they-intercept (b). Use
the procedures in Section 7.2 and 7.3 to test the calibration and
the linearity.
7.1.4 Daily FID Calibration Check. Check the calibration at the
beginning and at the end of the daily runs by using the following
procedures. Prepare two ca 1 i brat ion standards at the nomi na 1 cutoff
concentrations using the procedures in Section 7.1.3 Place one at the
beginning and end of the daily run. Measure the FID response of the daily
calibration standard. Use the values fork and b obtained from the most
recent calibration and use Equation 4 to calculate the concentration of
5110 - 4 Revision 0
November 1992
the daily standard. Use an equation similar to Equation 2 to calculate
the percent difference between the daily standard and Cs. If the percent
difference is within five, then the previous values for k and b can be
used. Otherwise, use the procedures in Section 7.1.3 to recalibrate the
FID.
7.2 Analysis.
7.2.l Allow one hour for the headspace vials to equilibrate at the
temperature specified in the regulation. Allow the FID to warm until a
stable baseline is achieved on the detector.
7.2.2 Check the calibration of the FID daily, using the procedures
in Section 7.1.4.
7.2.3 Follow the manufacturer's recommended procedures for the
normal operation of the headspace sampler and FID.
7.2.4 Use the procedures in Sections 7.3.4 and 7.3.5 to calculate
the organic vapor pressure in the samples.
7.2.5 Monitor the output of the detector to make certain that the
results are being properly recorded.
7.3 Calculations
7.3.1 Nomenclature
A = Measurement of the area under the response curve,
counts.
b = y-intercept of the linear regression line.
ca Measured vapor phase organic concentration of sample,

ppm as propane.
c~ Average 'measured vapor phase organic concentration of
standard, ppm as propane.
cm Measured vapor phase organic concentration of standard,

ppm as propane.
cs Calculated standard concentration, ppm as propane.
k Slope of the linear regression line.
pbar Atmosphere pressure at analysis conditions, mm Hg (in.
Hg).
p* Organic vapor pressure in the sample, kPa (psi).
B 1.333 x 10- 6 kPa/[(mm Hg)(ppm)], 4.91 x 10- 7 psi/
[(in.Hg)(ppm)])
5110 - 5 Revision 0
November 1992
7.3.2 Linearity. Use Equation 1 to calculate the measured standard
concentration for each standard vial.
cm = k A + b Eq. 1
7.3.2.1 Calculate the average measured standard
concentration (Clj18) for each set of triplicate standards, and use
Equation 2 to Calculate the percent difference between cma and cs.
c_s_-_cma X 100
Percent Difference = Eq. 2
cs
The instrument linearity is acceptable if the percent
difference is less than or equal to five for each standard.
7.3.3 Relative standard Deviation (RSD). Use Equation 3 to
calculate the RSD for each triplicate set of standards.
100 n (Cm - Cma)2
%RSD = E
, =1 (n - 1)
Eq. 3
The calibration is acceptable if the RSD is within five percent for

each standard concentration.
7.3.4 Concentration of Organics in the Headspace. Use Equation 4 to
calculate the concentration of vapor phase organics in each sample.
Ca = k A+ b Eq. 4
7.3.5 Vapor Pressure of Organics in the Headspace. Use Equation 5
to calculate the vapor pressure of organics in the sample.
p* = B pbar Ca Eq. 5
8.0 QUALITY CONTROL

8.1 Refer to Chapter One for specific Quality Control procedures.
8.2 Maintain a record of performance of all system checks and
calibrations.

9.1 No performance data are currently available.
5110 - 6 Revision 0
November 1992
10. 0 REFERENCES
1. "Determination of Vapor Phase Organic Concentrations in Waste Samples,"
Method 25E; Proposed Amendment to 40 CFR Part 60, Appendix A, January
1989.
2. "Headspace," Method 3810; U.S. Environmental Protection Agency, SW-846,
3rd Ed . , 1986.
5110 - 7 Revision 0
November 1992
FIGURE 1
WASTBUNI!
FROMSOURCB
t
VALVES
STATICMIXER J """'REDUCER (1/4 ·ruon FllTING)
OPTIONAL PUMP
5110 - 8 Revision O
November 1992
METHOD 5110
DETERMINATION OF ORGANIC PHASE VAPOR PRESSURE IN WASTE SAMPLES
St::.a:rt
l
7 2 1 A1.1.o'W' .., 3 2 ca.icul..&te

system to 1.inea.rit:.y
equ::L1i.bYa.t.e aoc:orc:t.~n.g to
~o:c :1. hou:c eq'l..l.a.t.:t..ona
wi...,.en
7 2 2 Do d.a.1.1.y 7 3 :3 Ca1.c:u.1e.te
FID cal..1b:rat.1.o:n. :r•l..a.t:l."V•
oneok u.•:Lng •l:.&Dcl&Zcl.
p:o:ooeclu:o:e• ~:o:om clev:Lau:Lon o~
aec::t:.ion 7 :L 4 ata.ncla.:d.e
'/
7
2 3 Ope.rate 7 3 4 caicu.1.a.t.e
head.epac::• c:on.c::antrat:i.on
&&n\p1.•:r a.:n.d. F:LD o:r oxga.:n.ic::a :l.n
a.ccorclin.g t:.o head•pace
ma.n-u.facture:r
7 2 4 Mori..:1..to::c 7 3 5 Ca..1.c'U.l..ate
clel:.eCll:.OZ' l:.he V&Jl»O:O:
~'\...l.tput to prel!l•ure th•
aea'-..1.ra p:roper orga.nice: .:1.n Che
:reco:r:cl:l.ng l";a.e a . d & p - . c e
'/
Stop I
5110 9 Revision 0
November 1992
METHOD 36008
CLEANUP

1.1 Method 3600 provides general guidance on selection of cleanup methods
that are appropriate for the target analytes of interest. Cleanup methods are
applied to the extracts prepared by one of the extraction methods, to eliminate
sample interferences. The following table lists the cleanup methods and provides
a brief description of the type of cleanup.
SW~846 CLEANUP METHODS
Method # Method Name Cleanup Tvpe
3610 Alumina Cleanup Adsorption

3611 Alumina Cleanup &Separation Adsorption
for Petroleum Waste
3620 Florisil Cleanup Adsorption
3630 Silica Gel Cleanup Adsorption
3640 Gel-Permeation Cleanup Size-Separation
3650 Acid-Base Partition Cleanup Acid-Base Partitioning
3660 Sulfur Cleanup Oxidation/Reduction
3665 Sulfuric Acid/Permanganate Oxidation/Reduction
Cleanup
1.2 The purpose of applying a cleanup method to an extract is to remove

interferences and high boiling material that may result in: (1) errors in
quantitation (data may be biased low because of analyte adsorption in the
injection port or front of the GC column or biased high because of overlap with
an interference peak}; (2) false positives because of interference peaks falling
within the analyte retention time window; (3) false negatives caused by shifting
the analyte outside the retention time window; (4) rapid deterioration of
expensive capillary columns; and, (5) instrument downtime caused by cleaning and
rebuilding of detectors and ion sources. Most extracts of soil and waste require
some degree of cleanup, whereas, cleanup for water extracts may be unnecessary.
Highly contaminated extracts (e.g. sample extracts of oily waste or soil
containing oily residue) often require a combination of cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC}, to eliminate the high
boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
November 1992
1.3 The following techniques have been applied to extract purification:
adsorption chromatography; partitioning between immiscible solvents; gel
permeation chromatography; oxidation of interfering substances with acid, alkali,
or oxidizing agents. These techniques may be used individually or in various
combinations, depending on the extent and nature of the co-extractives.
1.3.1 Adsorption column chromatography - Alumina {Methods 3610
and 3611), Florisil (Method 3620), and silica gel (Method 3630) are useful
for separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity. These are
primarily used for cleanup of a specific chemical group of relatively
non-polar analytes, i.e., organochlorine pesticides, polynuclear aromatic
hydrocarbons (PAHs), nitrosamines, etc.. Solid phase extraction
cartridges have been added as an option.
1.3.2 Acid-base partitioning (Method 3650) - Useful for
separating acidic or basic organics from neutral organics. It has been
applied to analytes such as the chlorophenoxy herbicides and phenols. It
is very useful for separating the neutral PAHs from the acidic phenols
when analyzing a site contaminated with creosote and pentachlorophenol.
1.3.3 Gel permeation chromatography (GPC) (Method 3640) - The
most universal cleanup technique for a broad range of semivolatile
organics and pesticides. It is capable of separating high
molecular-weight, high boiling material from the sample analytes. It has
been used successfully for all the semivolatile base, neutral, and acid
compounds associated with the EPA Priority Pollutant and the Superfund
Target Compound list prior to GC/MS analysis for semivolatiles and
pesticides. GPC may not be applicable to elimination of extraneous peaks
on a chromatogram which interfere with the analytes of interest. It is,
however, useful for the removal of high boiling materials which would
contaminate injection ports and column heads, prolonging column life,
stabilizing the instrument, and reducing column reactivity.
1.3.4 Sulfur cleanup (Method 3660) - Useful in eliminating
sulfur from sample extracts, which may cause chromatographic interference
with analytes of interest.
1.4 Several of the methods are also useful for fractionation of complex
mixtures of analytes. Use the solid phase extraction cartridges in Method 3630
(Silica Gel) for separating the PCBs away from most organochlorine pesticides.
Method 3611 (Alumina) is for the fractionation of aliphatic, aromatic and polar
analytes. Method 3620 (Florisil) provides fractionation of the organochlorine
pesticides.
1.5 Cleanup capacity is another factor that must be considered in
choosing a cleanup technique. The adsorption methods (3610, 3620, and 3630)
provide the option of using standard column chromatography techniques or solid
phase extraction cartridges. The decision process in selecting between the
different options available generally depends on the amount of interferences/high
boiling material in the sample extract and the degree of cleanup required by the
determinative method. The sol id phase extraction cartridges require less elution
solvent and less time, however, their cleanup capacity is drastically reduced
when comparing a 0.5 or 1.0 g Florisil cartridge to a 20 g standard Florisil
November 1992
column. The same factor enters into the choice of the 70 g gel permeation column
specified in Method 3640 versus a high efficiency column.
1.6 Table 1 indicates the recommended cleanup techniques for the
indicated groups of compounds. This information can also be used as guidance for
compounds that are not listed. Compounds that are chemically similar to these
groups of compounds should behave similarly when taken through the cleanup
procedure,however, this must be demonstrated by determining recovery of standards
taken through the method.

2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES
3.1 Analytical interferences may be caused by contaminants in solvents,
reagents, glassware, and other samp 1e processing hardware. All of these
materials must be routinely demonstrated to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be

4.1 Refer to the specific cleanup method for apparatus and materials
needed.
5.0 REAGENTS
5.1 Refer to the specific cleanup method for the reagents needed.

Section 4.1.
7.0 PROCEDURE
7 .1 Prior to using the cleanup procedures, samp 1es norma 11 y undergo
solvent extraction. Chapter Two, Section 2.0, may be used as a guide for
choosing the appropriate extraction procedure based on the physical composition
of the waste and on the analytes of interest in the matrix (see also Method 3500
for a general description of the extraction technique). For some organic
liquids, extraction prior to cleanup may not be necessary.
November 1992
7. 2 Most soil/sediment and waste sample extracts wi 11 require some degree
of cleanup. The extract is then analyzed by one of the determinative methods.
If interferences still preclude analysis for the analytes of interest, additional
cleanup may be required.
7 .3 Many of the determinative methods specify cleanup methods that should
be used when determining particular analytes (e.g. Method 8060, gas
chromatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup) or Method 3620 (Floris il column cleanup) if interferences prevent
analysis. However, the experience of the analyst may prove invaluable in
determining which cleanup methods are needed. As indicated in Section 1.0 of
this method, many matrices may require a combination of cleanup procedures in
order to ensure proper analytical determinations.
7.4 Guidance for cleanup is specified in each of the methods that follow.
The amount of extract cleanup required prior to the final determination depends
on the concentration of interferences in the sample, the selectivity of both the
extraction procedure and the determinative method and the required detection
limit.
7.5 Following cleanup, the sample is concentrated to whatever volume is
required in the determinative method. Analysis follows as specified in the
determinative procedure.
8.0 QUALITY CONTROL

8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered by the cleanup technique before the cleanup is
applied to actual samples. For sample extracts that are cleaned up, the
associated quality control samples (e.g. spikes, blanks, replicates, and
duplicates) must also be processed through the same cleanup procedure.
8.3 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup al so be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
interest and to verify the absence of interferences from reagents.

9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES
10.1 Refer to the specific cleanup method.
November 1992
TABLE 1.
RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Determinative 8 Cleanup
Analyte Group Method Method Options
Phenols 8040 3630b, 3640, 3650, 8040c

Phthalate esters 8060/8061 3610, 3620, 3640
Nitrosamines 8070 3610, 3620, 3640
Organochlorine pesticides & PCBs 8080/8081 3620, 3640, 3660
PCBs 8080/8081 3665
Nitroaromatics and cyclic ketones 8090 3620, 3640
Polynuclear aromatic hydrocarbons 8100/8310 3611, 3630, 3640
Chlorinated hydrocarbons 8120/8121 3620, 3640
Organophosphorus pesticides 8140/8141 3620
Chlorinated herbicides 8150/8151 8150d, 3620
Semivolatile organics 8250/8270 3640, 3650, 3660
Petroleum waste 8250/8270 3611, 3650
PCDDs and PCDFs by LR/MS 8280 8280
PCDDs and PCDFs by HR/MS 8290 8290
N-methyl carbamate pesticides 8318 8318
a
The GC/MS Methods, 8250 and 8270, are also appropriate determinative methods
for all analyte groups, unless lower detection limits are required.
b
Cleanup applicable to derivatized phenols.
c
Method 8040 includes a derivatization technique followed by GC/ECD analysis,
if interferences are encountered using GC/FID.
d
Method 8150 incorporates an acid-base cleanup step as an integral part of the
method.
November 1992
METHOD 36008
CLEANUP
7.1
Do solvent
extraction
7.2
Analyze analyte
by a determinative
method from Sec. 4.3
7.3
Use clean~ method
y specified for the
determinative method
No
Stop 7.5
Concentrate sample
to required volume
November 1992
METHOD 36308
SILICA GEL CLEANUP

1.1 Silica gel is a regenerative adsorbent of amorphous silica with
weakly acidic properties. It is produced from sodium silicate and sulfuric acid.
Silica gel can be used in column chromatography for the separation of analytes
from interfering compounds of a different chemical polarity. It may be used
activated after heating to 150 - 160°C or deactivated with up to 10% water.
1.2 This method includes guidance for standard column cleanup of sample
extracts containing polynuclear aromatic hydrocarbons, derivatized phenolic
compounds, organochlorine pesticides and, PC8s as Aroclors.
1.3 This method also provides cleanup procedures using solid-phase
extraction cartridges for pentafluorobenzyl bromide derivatized phenols and
organochlorine pesticides/PC8s as Aroclors. This technique also provides the
best separation of PC8s from most single component organochlorine pesticides.
When only PC8s are to be measured, this method can be used in conjunction with
sulfuric acid/permanganate cleanup (Method 3665).
1.4 Other analytes may be cleaned up using this method if the analyte
recovery meets the criteria specified in Section 8.0.

2.1 This method provides the option of using either standard column
chromatography techniques or solid-phase extraction cartridges. Generally, the
standard column chromatography techniques use larger amounts of adsorbent and,
therefore, have a greater cleanup capacity.
2.2 In the standard column cleanup protocol, the column is packed with
the required amount of adsorbent, topped with a water adsorbent, and then loaded
with the sample to be analyzed. Elution of the anal ytes is effected with a
suitable solvent(s) leaving the interfering compounds on the column. The eluate
is then concentrated (if necessary).
2.3 The cartridge cleanup protocol uses silica solid-phase extraction
cartridges packed with 1 g or 2 g of adsorbent. Each cartridge is solvent washed
immediately prior to use. Aliquots of sample extracts are loaded onto the
cartridges which are then eluted with suitable solvent(s). A vacuum manifold is
required to obtain reproducible results. The collected fractions may be further
concentrated prior to gas chromatographic analysis.
2.4 The appropriate gas chromatographic method is listed at the end of
each technique. Analysis may also be performed by gas chromatography/mass
spectrometry (Method 8270).
November 1992
3.0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
See Section 8 for guidance on a reagent blank check.
3.2 Phthalate ester contamination may be a problem with certain
cartridges The more inert the column and/or cartridge material (i.e., glass or
Teflon), the less problem with phthalates. Phthalates create interference
problems for all method analytes, not just the phthalate esters themselves.

4.1 Chromatographic column - 250 mm long x 10 mm ID; with Pyrex glass
wool at bottom and a Teflon stopcock.
fr its may be purchased. Use a sma 11 pad of Pyrex glass wool to
4.2 Beakers - 500 ml.
4.3 Vials - 2, 10, 25 ml, glass with Teflon lined screw-caps or crimp
tops.
4.4 Muffle furnace.
4.5 Reagent bottle - 500 ml.
4.6 Erlenmeyer flasks - 50 and 250 ml.
4.7 Vacuum manifold: VacElute Manifold SPS-24 (Analytichem
International), Visiprep (Supelco, Inc.) or equivalent, consisting of glass
vacuum basin, collection rack and funnel, collection vials, replaceable stainless
steel delivery tips, built-in vacuum bleed valve and gauge. The system is
connected to a vacuum pump or water aspirator through a vacuum trap made from a
500 ml sidearm flask fitted with a one-hole stopper and glass tubing.
5.0 REAGENTS
November 1992
5.3 Silica gel for chromatography columns.
5.3.l Silica Gel for Phenols and Polynuclear Aromatic Hydrocarbons:
100/200 mesh desiccant (Davison Chemical grade 923 or equivalent). Before
use, activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil.
5.3.2 Silica Gel for Organochlorine pesticides/PCBs: 100/200 mesh
desiccant (Davison Chemical grade 923 or equivalent). Before use,
activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil. Deactivate it to 3.3% with reagent water in a 500 ml
glass jar. Mix the contents thoroughly and allow to equilibrate for 6
hours. Store the deactivated silica gel in a sealed glass jar inside a
desiccator.
5.4 Silica cartridges: 40 µm particles, 60 A pores. The cartridges from
which this method were developed consist of 6 ml serological-grade polypropylene
tubes, with the 1 g of silica held between two polyethylene or stainless steel
frits with 20 µm pores. 2 g silica cartridges are also used in this method, and
0.5 g cartridges are available. The compound elution patterns must be verified
when cartridges other than the specified size are used.
5.5 Sodium sulfate (granular, anhydrous), Na 2SO. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning lhe sodium sulfate with
methylene chloride. A method blank must be analyzed in order to demonstrate that
there is no interference from the sodium sulfate.
5.6 Eluting solvents
5.6.1 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6 H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3 ) 2CHOH - Pesticide quality or equivalent.
5.6.4 Toluene, C6 H5CH 3 - Pesticide quality or equivalent.
5.6.6 Pentane, C5H12 - Pesticide quality or equivalent.
5.6.7 Acetone, CH 3 COCH3 - Pesticide quality or equivalent.
5.6.8 Diethyl Ether, C 2 H 5 0C 2 H~. Pesticide quality or equivalent.
Must be free of peroxides as ind1cated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
test strips. After cleanup, 20 ml of ethanol preservative must be added
to each liter of ether.
November 1992
6.1 See the introductory material to this chapter, Organic Ana1ytes,
Section 4.1.
7.0 PROCEDURE
7.1 General Guidance
7.1.1 The procedure contains two cleanup options for the derivatized
phenols and organochlorine pesticides/Aroclors, but only one technique for
the polynuclear aromatic hydrocarbons (PAHs) (standard column
chromatography). Cleanup techniques by standard column chromatography for
all analytes are found in Section 7.2. Cleanup techniques by solid-phase
cartridges for derivatized phenols and PAHs are found in Section 7.3. The
standard column chromatography techniques are packed with a greater amount
of silica gel adsorbent and, therefore, have a greater cleanup capacity.
A rule of thumb relating to cleanup capacity is that 1 g of sorbent
material will remove 10 to 30 mg of total interferences. (However,
capacity is also dependent on the sorbent retentiveness of the
interferences.) Therefore, samp 1es that exhibit a greater degree of
sample interference should be cleaned up by this technique. However, both
techniques have limits on the amount of interference that can be removed.
If the interference is caused by high boiling material, then Method 3640
should be used prior to this method. If the interference is caused by
relatively polar compounds of the same boiling range as the analytes, then
multiple column or cartridge cleanups may be required. If crystals of
sulfur are noted in the extract, then Method 3660 should be utilized prior
to this method. The cartridge cleanup techniques are often faster and use
less solvent, however they have less cleanup capacity.
7.1.2 Allow the extract to reach room temperature if it was in cold
storage. Inspect the extracts visually to ensure that there are no
particulates or phase separations and that the volume is as stated in the
accompanying documents. Verify that the solvent is compatible with the
cleanup procedures. If crystals of sulfur are visible or if the presence
of sulfur is suspected, proceed with Method 3660.
7 .1. 3 The extract so 1vent for most cleanup techniques must be
exchanged to hexane if it is in methylene chloride. (For the PAHs,
exchange to cyclohexane as per Section 7.2.1). Follow the standard
Kuderna-Danish concentration technique provided in each extraction method.
The volume of methylene chloride should have been reduced to 1 - 2 ml.
Add 40 ml of hexane, a fresh boiling chip and repeat the concentration as
written. The final volume required for the cleanup techniques is normally
2 ml.
7.2 Standard Column Cleanup Techniques

7.2.1 Polynuclear aromatic hydrocarbons
7. 2.1.1 Before the s il; ca gel cleanup technique can be
utilized, the extract solvent must be exchanged to cyclohexane. The
November 1992
exchange is performed by adding 4 ml of cyclohexane following
reduction of the sample extract to 1-2 ml using the macro Snyder
column. Attach the two ball micro Snyder column and reduce the
volume to 2 ml.
semivolatile analytes may be lost. If the
extract goes to dryness, the extraction must be
repeated.
7.2.1.2 Prepare a slurry of 10 g of activated silica gel
(Section 5.3.1) in methylene chloride and place this into a 10 mm IO
chromatographic column. Tap the column to settle the silica gel and
elute the methylene chloride. Add 1 to 2 cm of anhydrous sodium
sulfate to the top of the silica gel.
7.2.1.3 Preelute the column with 40 ml of pentane. The
rate for all elutions should be about 2 ml/min. Discard the eluate
and just prior to exposure of the sodium sulfate layer to the air,
transfer the 2 ml cyclohexane sample extract onto the column using
an additional 2 ml cyclohexane to complete the transfer. Just prior
to exposure of the sodium sulfate layer to the air, add 25 ml of
pentane and continue the elution of the column. Discard this
pentane eluate.
7.2.1.4 Next, elute the column with 25 ml of methylene
chloride/pentane (2:3)(v/v) into a 500 ml K-D flask equipped with a
10 ml concentrator tube. Concentrate the collected fraction to
whatever volume is required (1-10 ml). Proceed with HPlC (Method
8310) or GC analysis (Method 8100). Validated components that elute
in this fraction are:
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
7.2.2 Derivatized Phenols
7.2.2.1 This silica gel cleanup procedure is performed on
sample extracts that have undergone pentafluorobenzyl bromide
derivatization as described in Method 8040. The sample extract must
November 1992
be in 2 ml of hexane at this point.
7.2.2.2 Place 4.0 g of activated silica gel (Section
5.3.1) into a 10 mm ID chromatographic column. Tap the column to
settle the silica gel and add about 2 g of anhydrous sodium sulfate
to the top of the silica gel.
7.2.2.3 Preelute the column with 6 ml of hexane. The rate
for all elutions should be about 2 ml/min. Discard the eluate and
just prior to exposure of the sodium sulfate layer to the air, pipet
onto the column 2 ml of the hexane solution that contains the
derivatized sample or standard. Elute the column with 10.0 ml of
hexane and discard the eluate.
7.2.2.4 Elute the column, in order, with 10.0 ml of 15%
toluene in hexane (Fraction l); 10.0 ml of 40% toluene in hexane
(Fraction 2); 10.0 ml of 75% toluene in hexane (Fraction 3); and
10.0 ml of 15% 2-propanol in toluene (Fraction 4). All elution
mixtures are prepared on a volume:volume basis. Elution patterns
for the phenolic derivatives are shown in Table 1. Fractions may be
combined, as desired, depending upon the specific phenols of
interest or level of interferences. Proceed with GC analysis
(Method 8040).
7.2.3 Organochlorine Pesticides and Aroclors
7.2.3.l Transfer a 3 g portion of deactivated silica gel
(Section 5.3.2) into a 10 mm ID glass chromatographic column and top
it with 2 to 3 cm of anhydrous sodium sulfate.
7.2.3.2 Add 10 ml of hexane to the top of the column to
wet and rinse the sodium sulfate and silica gel. Just prior to
exposure of the sodium sulfate layer to air, stop the hexane eluate
flow by closing the stopcock on the chromatographic column. Discard
the eluate.
7.2.3.3 Transfer the sample extract (2 ml in hexane) onto
the column. Rinse the extract vial twice with 1 to 2 ml of hexane
and add each rinse to the column. Elute the column with 80 ml of
hexane (Fraction I) at a rate of about 5 ml/min. Remove the
collection flask and set it aside for later concentration. Elute
the column with 50 ml of hexane (Fraction I I) and co 11 ect the
eluate. Perform a third elution with 15 ml of methylene chloride
(Fraction III). The elution patterns for the organochlorine
pesticides, Aroclor-1016, and Aroclor-1260 are shown in Table 2.
7.2.3.4 Prior to gas chromatographic analysis, the
extraction solvent must be exchanged to hexane. Fractions may be
combined, as desired, depending upon the specific
pest i cides/Arocl ors of interest or level of interferences. If
mixtures of Aroclors and pesticides are expected, it is best to
analyze Fraction I separately since it contains the Aroclors
separated from most pesticides. Proceed with GC analysis as per
Method 8080 or 8081.
November 1992
7.3 Cartridge Cleanup Techniques
7.3.1 Cartridge Set-up and Conditioning
7.3.1.1 Arrange the 1 g Florisil cartridges (2 g for
phenol cleanup) on the manifold in the closed-valve position. Other
size cartridges may be used, however the data presented in the
Tables is all based on 1 g cartridges for pesticides/Aroclors and 2
g cartridges for phenols. Therefore, supporting recovery data must
be developed for other sizes. Larger cartridges wi 11 probably
require larger volumes of elution solvents.
7 .3 .1. 2 Turn vacuum pump on and set pump vacuum to 10
inches or 254 mm of Hg. Do not exceed the manufacturer's
recommendation for manifold vacuum. Flow rates can be controlled by
opening and closing cartridge valves.
7.3.1.3 Condition the cartridges by adding 4 ml of hexane
to each cartridge. Slowly open the cartridge valves to allow hexane
to pass through the sorbent beds to the lower frits. Allow a few
drops per cartridge to pass through the manifold to remove all air
bubbles. Close the valves and allow the solvent to soak the entire
sorbent bed for 5 minutes. Do not turn off the vacuum.
7.3.1.4 Slowly open cartridge valves to allow the hexane
to pass through the cartridges. Close the cartridge valves when
there is still at least 1 mm of solvent above the sorbent bed. Do
not allow cartridges to become dry. If cartridges go dry, repeat
the conditioning step.
7.3.2 Derivatized Phenols
7.3.2.1 Reduce the sample extract volume to 2 ml prior to
cleanup. The extract solvent must be hexane and the phenols must
have undergone derivatization by pentafluorobenzyl bromide as per
Methods 8040 or 8041.
7.3.2.2 Transfer the extract to the 2 g cartridge
conditioned as described in Section 7.3.1. Open the cartridge valve
to allow the extract to pass through the cartridge bed at
approximately 2 ml/minute.
7. 3. 2. 3 When the entire extract has passed through the
cartridges, but before the cartridge becomes dry, rinse the sample
vials with an additional 0.5 ml of hexane, and add the rinse to the
cartridges to complete the quantitative transfer.
7.3.2.4 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never gets dry.
7.3.2.5 Place a 5 ml vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
November 1992
and align with the collection vial.
7.3.2.6 Add 5 ml of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches or 254 mm of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve, and collect the eluate (this is
Fraction 1, and should be discarded).
NOTE: If cartridges smaller than 2 g are used, then Fraction
1 cannot be discarded, since it contains some of the
phenols.
7.3.2.7 Close the cartridge valve, replace the collection
vial, and add 5 ml of toluene/hexane (25/75, v/v) to the cartridge.
Slowly open the cartridge valve and collect the eluate into the
collection vial. This is Fraction 2, and should be retained for
analysis.
7.3.2.8 Adjust the final volume of the eluant to a known
volume which will result in analyte concentrations appropriate for
the project requirements (normally 1 - 10 ml). Table 3 shows
compound recoveries for 2 g silica cartridges. The cleaned up
extracts are ready for analysis by Methods 8040 or 8041.
7.3.3 Organochlorine Pesticides/Aroclors
NOTE: The silica cartridge procedure is appropriate when
polychlorinated biphenyls are known to be present.
7.3.3.1 Reduce the sample extract volume to 2 ml prior to
cleanup. The extract solvent must be hexane.
7.3.3.2 Use the 1 g cartridges conditioned as described in
Section 7.3.1.
7.3.3.3 Transfer the extract to the cartridge. Open the
cartridge valve to allow the extract to pass through the cartridge
bed at approximately 2 ml/minute.
· 7.3.3.4 When the entire extract has passed through the
cartridges, but before the cartridge becomes dry, rinse the sample
vials with an additional 0.5 ml of solvent, and add the rinse to the
cartridges to complete the quantitative transfer.
7.3.3.5 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never goes dry.
7.3.3.6 Place a 5 ml vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.
November 1992
7.3.3.7 Add 5 ml of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches or 254 mm of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve and collect the eluate into the
collection vial (Fraction 1).
7.3.3.8 Close the cartridge valve, replace the collection
vial, and add 5 ml of diethyl ether/hexane (50/50, v/v) to the
cartridge. Slowly open the cartridge valve and collect the eluate
into the collection vial (Fraction 2).
7.3.3.9 Adjust the final volume of the two fractions to a
known volume which will result in analyte concentrations appropriate
for the project requirements (normally 1 - 10 ml). The fractions
may be combined prior to final adjustment of volume, if analyte
fractionation is not required. Table 4 shows compound recoveries
for 1 g silica cartridges. The cleaned up extracts are ready for
analysis by Methods 8080 or 8081.
~.O QUALITY CONTROL

8 .1 Refer to Chapter One· for specific quality control procedures and
~ethod 3600 for cleanup procedures.
8.2 A reagent blank (consisting of the elution solvents) must be passed
through the column or cartridge and checked for the compounds of interest, prior
to the use of this method. This same performance check is required with each new
lot of adsorbent or cartridges. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
8.3 The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before applying this method to actual samples. See the
attached Tables for acceptable recovery data. For compounds that have not been
tested, recovery must be ~ 853.
8.3.1 Before any samples are processed using the solid-phase
extraction cartridges, the efficiency of the cartridge must be verified.
A recovery check must be performed using standards of the target analytes
at known concentration. Only lots of cartridges that meet the recovery
criteria for the spiked compounds can be used to process the samples.
8.3.2 A check should also be performed on each individual lot of
cartridges and for every 300 cartridges of a particular lot.
8.4 For sample extracts that are cleaned up using this method, the
associated quality control samples should also be processed through this cleanup
method.

9.1 Table 1 provides performance information on the fractionation of
phenolic derivatives using standard column chromatography.
November 1992
9.2 Table 2 provides performance information on the fractionation of
organochlorine pesticides/Aroclors using standard column chromatography.
9.3 Table 3 shows recoveries of derivatized phenols obtained using 2 g
silica cartridges.
9.4 Table 4 shows recoveries and fractionation of organochlorine
pesticides obtained using 1 g silica cartridges.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures
for the Analysis of Pollutants Under the Clean Water Act; Final Rule
and Interim Final Rule and Proposed Rule," October 26, 1984.
2. U.S EPA· "Evaluation of Sample Extract Cleanup Using Solid-Phase
Extraction Cartridges," Project Report, December 1989.
36308 - 10 Revision 2
November 1992
TABLE l
SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
Percent Recovery by Fraction 8

Parameter l 2 3 4
2-Chlorophenol 90 l
2-Nitrophenol 9 90
Phenol 90 10
2,4-Dimethylphenol 95 7
2,4-Dichlorophenol 95 l
2,4,6-Trichlorophenol 50 50
4-Chloro-3-methylphenol 84 14
Pentachlorophenol 75 20
4-Nitrophenol 1 90
a Eluant composition:
Fraction 1 15% toluene in hexane.
Fraction 2 40%·toluene in hexane.
Fraction 3 75% toluene in hexane.
Fraction 4 15% 2-propanol in toluene.
Data from Reference 1 (Method 604)
36308 - 11 Revision 2
November 1992
TABLE 2
DISTRIBUTION AND PERCENT RECOVERIES OF ORGANOCHLORINE 8
PESTICIDES AND PCBs AS AROCLORS IN SILICA GEL COLUMN FRACTIONS 'b,c,d,e
Fraction I Fraction II Fraction II I Total Recovery

Compound Cone. Cone. Cone. Cone. Cone. Cone. Cone. Cone.
1 2 1 2 1 2 1 2
alpha-BHCf 82(1. 7) 74(8.0) 82 ( 1. 7) 74(8.0)

beta-BHC 107(2.1) 98(12.5) 107(2.1) 98(12.5)
gamma-BHC 91(3.6) 85( 10. 7) 91(3.6) 85(10. 7)
delta-BHC 92(3.5) 83(10.6) 92(3.5) 83(10.6)
Heptachlor 109 (4. 1) 118 (8. 7) 109(4.1) 118(8.7)
Aldrin 97(5.6) 104(1.6) 97(5.6) 104( 1.6)
Heptachlor epoxide 95(4.7) 88(10.2) 95(4. 7} 88(10.2)
Technical chlordane 14(5.5) 22(5.3) 19(6.8) 39(3.6) 29(5.0) 37(5.1) 62(3.3) 98(1. 9)
Endosulfan I 95(5.1) 87(10.2) 95(5.1) 87(10.2)
4,4'-DDE 86(5.4) 94(2.8) 86(5.4) 94(2.8)
Dieldrin 96(6.0) 87(10.6) 96(6.0) 87(10.6)
Endrin 85(10.5) 71(12.3) 85(10.5) 71(12.3)
Endosulf,n II 97(4.4) 86(10 .4) 97(4.4) 86(10.4)
4,4'-DDD 102(4.6) 92(10.2) 102(4.6) 92(10.2)
Endrin aldehyde 81(1.9) 76(9.5) 81(1.9) 76(9.5)
Endosulf,n sulfate 93(4.9) 82(9.2) 93(4.9) 82(9.2)
4,4'-DDT 86(13.4) 73 ( 9. 1) 15 ( 17. 7) 8. 7( 15. 0) 101(5.3) 82(23. 7)
4,4'-Meth?xychlor 99(9.9) 82(10. 7) 99(9.9) 82( 10. 7)
Toxaphene 15(2.4) 17(1.4) 73(9.4) 84(10. 7) 88(12.0) 101(10.1)
Aroclor-1016 86(4.0) 87(6.1) 86(4.0) 87(6.1)
Aroclor-1260 91(4.1) 95(5.0) 91(4.1) 95(5.0)
November 1992
TABLE 2
(Continued)
a
Effluent composition: Fraction I, 80 ml hexane; Fraction II, 50 ml hexane; Fraction III, 15 ml methylene
chloride.
b
Concentration 1 is 0.5 µg per column for BHCs, heptachlor, aldrin, heptachlor epoxide, and endosulfan I; 1.0
µg per column for dieldrin, endosulfan II, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, endrin, endrin aldehyde, and
endosulfan sulfate; 5 µg per column for 4,4'-methoxychlor and technical chlordane; 10 µg per column for
toxaphene, Aroclor-1016, and Aroclor-1260.
c
For Concentration 2, the amounts spiked are 10 times as high as those for Concentration 1.
d
Values given represent the average recovery of three determinations; numbers in parentheses are the standard
deviation; recovery cutoff point is 5 percent.
e
Data obtained with standards, as indicated in footnotes b and c, dissolved in 2 ml hexane.
f
It has been found that because of batch-to-batch variation in the silica gel material, these compounds cross
over in two fractions and the amounts recovered in each fraction are difficult to reproduce.
36308 - 13 Revision 2
November 1992
TABLE 3
PERCENT RECOVERIES AND ELUTION PATTERNS 8FOR 18
PHENOLS FROM 2 g SILICA CARTRIDGES
Fraction 2
Average Percent
Compound Recovery RSD
Phenol 74.1 5.2

2-Methylphenol 84.8 5.2
2,4-Dimethylphenol 91.8 5.6
2-Chlorophenol 88.5 5.0
2,6-Dichlorophenol 90.4 4.4
4-Chloro-3-methylphenol 94.4 7.1
2,4,6-Trichlorophenol 97.8 6.6
2,3,5,6-Tetrachlorophenol 97.5 5.3
Pentachlorophenol 96.2 8.8
a
Silica cartridges (Supelco, Inc.) were used; each cartridge was conditioned
with 4 ml of hexane prior to use. Each experiment was performed in duplicate
at three spiking concentrations (0.05 µg, 0.2 µg, and 0.4 µg per compound per
cartridge). Fraction 1 was eluted with 5 ml hexane and was discarded.
Fraction 2 was eluted with 5 ml toluene/hexane (25/75, v/v).
Data from Reference 2
36308 - 14 Revision 2
November 1992
TABLE 4
PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17 8
ORGANOCHLORINE PESTICIDES FROM 1 g SILICA CARTRIDGES
Fraction 1 Fraction 2
Average Percent Average Percent
Compound Recovery RSD Recovery RSD
alpha-BHC 0 98.7 2.3

gamma-BHC 0 94.8 1. 9
beta-BHC 0 94.3 3.0
Heptachlor 97.3 1.3 0
delta-BHC 0 90.8 2.5
Aldrin 95.9 1.0 0
Heptachlor epoxide 0 97.9 2.1
Endosulfan I 0 102 2.3
4,4'-DDE 99.9 1. 7 0
Dieldrin 0 92.3 2.0
Endri n 0 117 2.6
4, 4' -ODD 10.7 41 92.4 3.3
Endosulfan II 0 96.0 2.2
4,4'-DDT 94.1 2.0 0
Endrin aldehyde 0 59.7 2.6
Endosulfan sulfate 0 97.8 2.1
4,4'-Methoxychlor 0 98.0 2.4
Aroclor 1016 124
Aroclor 1221 93.5
Aroclor 1232 118
Aroclor 1242 116
Aroclor 1248 114
Aroclor 1254 108
Aroclor 1264 112
a
Silica cartridges (Supelco, Inc. lot SP0161) were used; each cartridge was
conditioned with 4 ml hexane prior to use. The organochlorine pesticides were
tested separately from PCBs. Each organochlorine pesticides experiment was
performed in duplicate, at three spiking concentrations (0.2 µg, 1.0 µg, and
2.0 µg per compound per cartridge). Fraction 1 was eluted with 5 ml of hexane,
Fraction 2 with 5 ml of diethyl ether/hexane (50/50, v/v). PCBs were spiked
at 10 µg per cartridge and were eluted with 3 ml of hexane. The value given
for PCBs is the percent recovery for a single determination.
Data from Reference 2
36308 - 15 Revision 2
November 1992
METHOD 36308
SILICA GEL CLEANUP
Start
oc Pesticide
PCBs & Phenols------<
~--------<10- 30 mg
7 .3 9artJ1dge
Cleanup
7.2.2. 1 Do PFBB 7.2.3.1 Deactivate

derivatization on silica gel, prepare
sample extract
column
(8040)
7.3.2.1 Do PFBB 7.3.3.1 Exchange
derivatization on
solvent ID
sample extract
7.2.2.2 Place (8040) hexane
activated silica gel 7.2.3.2 Bute the
in dlromatographic GC column
column; add with hexane
anhydrous Na,.SO, 7.3.2.3 & 7.3.2.4 7.3.3.3 & 7.3.3.4
Transfer extract Transfer extract
to cartridge to cartridge
7.2.2.3 Preelute 7.2.3.3 Transfer
column with hexane; extract onto column
pipet hexane and elute with
solution onto column; specified solvents 7.3.2.6 & 7.3.2.7 7.3.3.6 & 7.3.3.7
elute Rinse cartridge Bute cartridge
with hexane & with hexane as
discard Fraction I
7.2.2.4 Elute column 7.3.4 Exdlange the

with specified elution solvent
to hexane (Section 7.3.2.8 Bute 7.3.3.8 Bute
solvents car1ridge with
7.1.3) cartridge With
toluene/hexane ether/hexane as
Fraction II
Analyze by
GC Method Analyze
by GC Method
8040 or GCIMS
36308 - 16 Revision 2
November 1992
METHOD 36308
(continued)
cp(PAHs)
7.2 Standard
Column Cleanup
7.2.1.1 Exchange
extract solvent to
cydohexane during
K-0 procedure
7.2.1.2 Prepare
slurry activated
silica gel, prepare
column
7.2.1.3 Preelute
column with
pentane, transfer
extract onto coll.nm
and elute with
pentane
7.2.1.4 Elute column

with CH 2 Cl 2 I
pentane: concentrate
collected fraction:
adjust volume
Analyze
by GC Method
8100 or GC/MS
Method 8270
36308 - 17 Revision 2
November 1992
METHOD 3640A
GEL-PERMEATION CLEANUP

1.1 Gel-permeation chromatography (GPC) is a size exclusion cleanup
procedure using organic sol vents and hydrophobic gels in the separation of
synthetic macromolecules (1). The packing gel is porous and is characterized by
the range or uniformity (exclusion range) of that pore size. In the choice of
gels, the exclusion range must be larger than the molecular size of the molecules
to be separated (2). A cross linked divinylbenzene-styrene copolymer (SX-3 Bio
Beads or equivalent) is specified for this method.
1.2 General cleanup application - GPC is recommended for the elimination
from the sample of lipids, polymers, copolymers, proteins, natural resins and
polymers, cellular components, viruses, steroids, and dispersed high-molecular-
weight compounds (2). GPC is appropriate for both polar and non-polar analytes,
therefore, it can be effectively used to cleanup extracts containing a broad
range of analytes.
1.3 Specific application - This method includes guidance for cleanup of
sample extracts containing the following analytes from the RCRA Appendix VIII and
Appendix IX lists:
Acenaphthene 83-32-9
Acenaphthylene 208-96-8
Acetophenone 98-86-2
2-Acetylaminofluorene 53-96-3
Aldrin 309-00-2
4-Aminobiphenyl 92-67-1
Aniline 62-53-3
Anthracene 120-12-7
Benomyl 17804-35-2
Benzenethiol 108-98-5
Benzi dine 92-87-5
Benz(a)anthracene 56-55-3
Benzo(b)fluoranthene 205-99-2
Benzo(a)pyrene 50-32-8
Benzo(ghi}perylene 191-24-2
Benzo(k}fluoranthene 207-08-9
Benzoic acid 65-85-0
Benzotrichloride 98-07-7
Benzyl ale oho l 100-51-6
Benzyl chloride 100-44-7
alpha-BHC 319-84-6
beta-BHC 319-85-7
gamma-BHC 58-89-9
November 1992
Compound Name CAS No. a
delta-BHC 319-86-8
4-Bromophenyl phenyl ether 101-55-3
Butyl benzyl phthalate 85-68-7
2-sec-butyl-4,6-dinitrophenol (Dinoseb) 88-85-7
Carbazole 86-74-8
Carbendazim 10605-21-7
alpha-Chlordane 5103-71-9
gamma-Chlordane 5566-34-7
4-Chloro-3-methylphenol 59-50-7
4-Chloroanil ine 106-47-8
Chlorobenzilate 510-15-6
Bis(2-chloroethoxy)methane 111-91-1
Bis(2-chloroethyl) ether 111-44-4
Bis(2-chloroisopropyl) ether 108-60-1
2-Chloronaphthalene 91-58-7
2-Chlorophenol 95-57-8
4-Chlorophenyl phenyl ether 7005-72-3
3-Chloropropionitrile 542-76-7
Chrysene 218-01-9
2-Cresol 95-48-7
3-Cresol 108-39-4
4-Cresol 106-44-5
Cyclophosphamide 50-18-0
DOD 72-54-8
DOE 72-55-9
DDT 50-29-3
Di-n-butyl phthalate 84-74-2
Diallate 2303-16-4
Dibenzo{a,e)pyrene 192-65-4
Dibenzo{a,i)pyrene 189-55-9
Dibenz(a,j)acridine 224-42-0
Dibenz(a,h)anthracene 53-70-3
Dibenzofuran 132-64-9
Dibenzothiophene 132-65-0
1,2-Dibromo-3-chloropropane 96-12-8
1,2-Dibromoethane 106-93-4
trans-1,4-Dichloro-2-butene 110-57-6
cis-1,4-Dichloro-2-butene 1476-11-5
1,2-Dichlorobenzene 95-50-1
1,3-Dichlorobenzene 106-46-7
1,4-0ichlorobenzene 541-73-1
3,3'-Dichlorobenzidine 91-94-1
2,6-Dichlorophenol 87-65-0
2,4-Dichlorophenoxyacetic acid (2,4-0) 94-75-7
2,4-Dichlorophenol 120-83-2
2,4-Dichlorotoluene 95-73-8
1,3-Dichloro-2-propanol 96-23-1
November 1992
Dieldrin 60-57-1
Diethyl phthalate 84-66-2
Dimethoate 60-51-5
Dimethyl phthalate 131-11-3
p-Dimethylaminoazobenzene 60-11-7
7,12-Dimethyl-benz(a)anthracene 57-97-6
2,4-Dimethylphenol 105-67-9
3,3-Dimethylbenzidine 119-93-7
4,6-Dinitro-o-cresol 534-52-1
1,3-Dinitrobenzene 99-65-0
2,4-Dinitrophenol 51-28-5
2,4-Dinitrotoluene 121-14-2
2,6-Dinitrotoluene 606-20-2
Di phenyl amine 122-39-4
Diphenyl ether 101-84-8
1,2-Diphenylhydrazine 122-66-7
Disulfoton 298-04-4
Endosulfan sulfate 1031-07-8
Endosulfan I 959-98-8
Endosul fan II 33213-65-9
Endrin 72-20-8
Endrin aldehyde 7421-93-4
Endrin ketone 53494-70-5
Ethyl methane sulfonate 62-50-0
Ethyl methacrylate 97-63-2
Bis(2-ethylhexyl) phthalate 117-81-7
Famphur 52-85-7
Fluorene 86-73-7
Fluoranthene 206-44-0
Heptachlor 76-44-8
Heptachlor epoxide 1024-57-3
Hexachlorobenzene 118-74-1
Hexachlorobutadiene 87-68-3
Hexachlorocyclopentadiene 77-47-4
Hexachloroethane 67-72-1
Hexachloropropene 1888-71-7
Indeno{l,2,3-cd)pyrene 193-39-5
lsodrin 465-73-6
Isophorone 78-59-1
cis-lsosafrole 17627-76-8
trans-Isosafrole 4043-71-4
Kepone 143-50-0
Malononitrile 109-77-3
Merphos 150-50-5
Methoxychlor 72-43-5
3-Methylcholanthrene 56-49-5
2-Methylnaphthalene 91-57-6
Methyl parathion 298-00-0
4,4'-Methylene-bis(2-chloroaniline) 101-14-4
November 1992
Naphthalene 91-20-3
1,4-Naphthoquinone 130-15-4
2-Naphthylamine 91-59-8
1-Naphthylamine 134-32-7
5-Nitro-o-toluidine 99-55-8
2-Ni troanil i ne 88-74-4
3-Nitroanil i ne 99-09-2
4-Nitroaniline 100-01-6
Nitrobenzene 98-95-3
2-Nitropheno 1 79-46-9
4-Nitrophenol 100-02-7
N-Nitrosodi-n-butylamine 924-16-3
N-Nitrosodiethanolamine 1116-54-7
N-Nitrosodiethylamine 55-18-5
N-Nitrosodimethylamine 62-75-9
N-Nitrosodiphenylamine 86-30-6
N-Nitrosodi-n-propylamine 621-64-7
N-Nitrosomethylethylamine 10595-95-6
N-Nitrosomorpholine 59-89-2
N-Nitrosopiperidine 100-75-4
N-Nitrosopyrolidine 930-55-2
Di-n-octyl phthalate 117-84-0
Parathion 56-38-2
Pentachlorobenzene 608-93-5
Pentachloroethane 76-01-7
Pentachloronitrobenzene (PCNB) 82-68-8
Pentachlorophenol 87-86-5
Phenacetin 62-44-2
Phenanthrene 85-01-8
Phenol 108-95-2
1,2-Phenylenediamine 95-54-5
Phorate 298-02-2
2-Picoline 109-06-8
Pronamide 23950-58-5
Pyrene 129-00-0
Resorcinol 108-46-3
Safrole 94-59-7
1,2,4,5-Tetrachlorobenzene 95-94-3
2,3,5,6-Tetrachloronitrobenzene 117-18-0
2,3,5,6-Tetrachlorophenol 935-95-5
2,3,4,6-Tetrachlorophenol 58-90-2
Tetraethyl dithiopyrophosphate (Sulfotep) 3689-24-5
Thiosemicarbazide 79-19-6
2-Toluidine 106-49-0
4-Toluidine 95-53-4
Thiourea, 1-(o-chlorophenyl) 5344-82-1
Toluene-2,4-diamine 95-80-7
1,2,3-Trichlorobenzene 87-61-6
1,2,4-Trichlorobenzene 120-82-1
November 1992
2,4,6-Trichlorophenol 88-06-2
2,4,5-Trichlorophenol 95-95-4
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) 93-76-5
2,4,5-Trichlorophenoxypropionic acid {2,4,5-TP) 93-72-1
Warfarin 81-81-2

Table 1 presents average percent recovery and percent RSD data for these
analytes, as well as the retention volumes of each analyte on a single GPC
system. Retention volumes vary from column to column. Figure 1 provides
additional information on retention volumes for certain classes of compounds.
The data for the semivolatiles was determined by GC/MS, whereas, the pesticide
data was determined by GC/ECD or GC/FPD. Compounds not amenable to GC were
determined by HPLC. Other analytes may also be appropriate for this cleanup
technique, however, recovery through the GPC should be >70%.
1.4 Normally, this method is most efficient for removing high boiling
materials that condense in the injection port area of a gas chromatograph (GC)
or the front of the GC column. This residue will ultimately reduce the
chromatographic separation efficiency or column capacity because of adsorption
of the target analytes on the active sites. Pentachlorophenol is especially
susceptible to this problem. GPC, operating on the principal of size exclusion,
will not usually remove interference peaks that appear in the chromatogram since
the molecular size of these compounds is relative similar to the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must be used to eliminate this type of interference.

2.1 The column is packed with the required amount of preswelled
absorbent, and is flushed with solvent for an extended period. The column is
calibrated and then loaded with the sample extract to be cleaned up. Elution is
effected with a suitable solvent(s) and the product is then concentrated.
3.0 INTERFERENCES
3 .1 A reagent blank should be analyzed for the compound of interest prior
to the use of this method. The level of interferences must be below the
estimated quantitation limits (EQLs) of the analytes of interest before this
method is performed on actual samples.
November 1992
4.0 APPARATUS
4.1 Gel-permeation chromatography system - GPC Autoprep Model 1002 A
or B, or equivalent, Analytical Biochemical Laboratories, Inc. Systems that
perform very satisfactorily have also been assembled from the following
components - an HPLC pump, an auto sampler or a valving system with sample loops,
and a fraction collector. All systems, whether automated or manual, must meet
the calibration requirements of Section 7.2.2.
4.1.1 Chromatographic column - 700 mm x 25 mm ID glass column. Flow
is upward. {Optional) To simplify switching from the UV detector during
calibration to the GPC collection device during extract cleanup, attach a
double 3-way valve {Rheodyne Type 50 Teflon Rotary Valve #10-262 or
equivalent) so that the column exit flow can be shunted either to the UV
flow-through cell or to the GPC collection device.
4.1.2 Guard column - {Optional) 5 cm, with appropriate fittings to
connect to the inlet side of the analytical column (Supelco 5-8319 or
equivalent).
4.1.3 Bio Beads {S-X3) - 200-400 mesh, 70 gm {Bio-Rad Laboratories,
Richmond, CA, Catalog 152-2750 pr equivalent). An additional 5 gm of Bio
Beads is required if the optional guard column is employed. The quality
of Bio Beads may vary from lot to lot because of excessive fines in some
lots. The UV chromatogram of the Calibration solution should be very
similar to that in Figure 2, and the backpressure should be within 6-10
psi. Also, the gel swell ratio in methylene chloride should be in the
range of 4.4 - 4.8 ml/gm. In addition to fines having a detrimental
effect on chromatography, they can also pass through the column screens
and damage the valve.
4.1.4 Ultraviolet detector - Fixed wavelength (254 nm) with a semi-
prep flow-through cell.
4.1.5 Strip chart recorder, recording integrator or laboratory data
system.
4.1.6 Syringe - 10 ml with Luerlok fitting.
4.1.7 Syringe filter assembly, disposable - Bio-Rad "Prep Disc"
sample filter assembly #343-0005, 25 mm, and 5 micron filter discs or
equivalent. Check each batch for contaminants. Rinse each filter
assembly (prior to use) with methylene chloride if necessary.
4.3 Volumetric flasks, Class A - 10 ml to 1000 ml
4.4 Graduated cylinders
November 1992
5. 0 REAGENTS
5.1 Methylene chloride, CH 2Cl 2 . Pesticide quality or equivalent.
5.1.1 Some brands of methylene chloride may contain unacceptably
high levels of acid (HCl). Check the pH by shaking equal portions of
methylene chloride and water, then check the pH of the water layer.
5.1.1.1 If the pH of the water layer is~ 5, filter the
entire supply of solvent through a 2 in. x 15 in. glass column
containing activated basic alumina. This column should be
sufficient for processing approximately 20-30 liters of solvent.
Alternatively, a different supply of methylene chloride should be
found.
5.2 Cyclohexane, C6 H12 • Pesticide quality or equivalent.
5.3 n-Butyl chloride, CH 3CH 2CH 2CH 2Cl. Pesticide quality or equivalent.
5.4 GPC Calibration Solution. Prepare a calibration 5olution in
methylene chloride containing the following analytes (in elution order):
Compound mgL1_
corn oil 25,000
bis(2-ethylhexyl) phthalate 1000
methoxychlor 200
perylene 20
sulfur 80
NOTE: Sulfur is not very soluble in methylene chloride, however, it is
soluble in warm corn oil. Therefore, one approach is to weigh out
the corn oil, warm it and transfer the weighed amount of sulfur into
the warm corn oil. Mix it and then transfer into a volumetric flask
with methylene chloride, along with the other calibration compounds.
Store the calibration solution in an amber glass bottle with a Teflon lined
screw-cap at 4°C, and protect from light. (Refrigeration may cause the corn oil
to precipitate. Before use, allow the calibration solution to stand at room
temperature until the corn oil dissolves.) Replace the calibration standard
solution every 6 months, or more frequently if necessary.
5.5 Corn Oil Spike for Gravimetric Screen. Prepare a solution of corn
oil in methylene chloride (5 mg/100 µL).

Section 4.1.
November 1992
7. 0 PROCEDURE
7.1 It is very important to have consistent laboratory temperatures
during an entire GPC run, which could be 24 hours or more. If temperatures are
not consistent, retention times will shift, and the dump and collect times
determined by the calibration standard will no longer be appropriate. The ideal
laboratory temperature to prevent outgassing of the methylene chloride is 72°F.
7.2 GPC Setup and Calibration
7.2.1 Column Preparation
7.2.1.1 Weigh out 70 gm of Bio Beads (SX-3). Transfer
them to a quart bottle with a Teflon lined cap or a 500 ml
separatory funnel with a large bore stopcock, and add approximately
300 ml of methylene chloride. Swirl the container to ensure the
wetting of all beads. Allow the beads to swell for a minimum of 2
hours. Maintain enough solvent to sufficiently cover the beads at
all times. If a guard column is to be used, repeat the above with
5 gm of Bio Beads in a 125 ml bottle or a beaker, using 25 ml of
methylene chloride.
7.2.1.2 Turn ihe column upside down from its normal
position, and remove the inlet bed support plunger (the inlet
plunger is longer than the outlet plunger). Position and tighten
the outlet bed support plunger as near the end as possible, but no
closer than 5 cm (measured from the gel packing to the collar).
7. 2.1. 3 Raise the end of the outlet tube to keep the
solvent in the GPC column, or close the column outlet stopcock if
one is attached. Place a small amount of solvent in the column to
minimize the formation of air bubbles at the base of poured column
packing.
7.2.1.4 Swirl the bead/solvent slurry to get a homogeneous
mixture and, if the wetting was done in a quart bottle, quickly
transfer it to a 500 ml separatory funnel with a large bore
stopcock. Drain the excess methylene chloride directly into the
waste beaker, and then start draining the slurry into the column by
placing the separatory funnel tip against the column wall. This
will help to minimize bubble formation. Swirl occasionally to keep
the slurry homogeneous. Drain enough to fill the column. Place the
tubing from the column outlet into a waste beaker below the column,
open the stopcock (if attached) and allow the excess solvent to
drain. Raise the tube to stop the flow and close the stopcock when
the top of the gel begins to look dry. Add additional methylene
chloride to just rewet the gel.
7. 2. 1. 5 Wipe any remaining beads and sol vent from the
inner wa 11 s of the top of the column with a laboratory tis sue.
Loosen the seal slightly on the other plunger assembly (long
plunger) and insert it into the column. Make the seal just tight
enough so that any beads on the glass surface wi 11 be pushed
forward, but loose enough so that the plunger can be pushed forward.
November 1992
CAUTION: Do not tighten the seal if beads are between the
seal and the glass surface because this can
damage the seal and cause leakage.
7.2.1.6 Compress the column as much as possible without
applying excessive force. Loosen the seal and gradually pull out
the plunger. Rinse and wipe off the plunger. Slurry any remaining
beads and transfer them into the column. Repeat Section 7.2.1.5 and
reinsert the plunger. If the plunger cannot be inserted and pushed
in with out a11 owing beads to escape around the seal , continue
compression of the beads without tightening the seal, and loosen and
remove the plunger as described. Repeat this procedure until the
plunger is successfully inserted.
7. 2.1. 7 Push the plunger until it meets the gel, then
compress the column bed about four centimeters.
7.2.1.8 Pack the optional 5 cm column with approximately
5 gm of preswelled beads (different guard columns may require
different amounts). Connect the guard column to the inlet of the
analytical column.
7.2.1.9 Connect the column inlet to the solvent reservoir
(reservoir should be placed higher than the top of the column) and
pl ace the column outlet tube in a waste container. Placing a
restrictor in the outlet tube will force air out of the column more
quickly. A restrictor can be made from a piece of capillary
stainless steel tubing of 1/16" OD x 10/1000" ID x 2". Pump
methylene chloride through the column at a rate of 5 ml/min for one
hour.
7.2.1.10 After washing the column for at least one hour,
connect the column outlet tube, without the restrictor, to the inlet
side of the UV detector. Connect the system outlet to the outlet
side of the UV detector. A restrictor (same size as in Section
7.2.1.9) in the outlet tube from the UV detector will prevent bubble
formation which causes a noisy UV baseline. The restrictor will not
ef feet fl ow rate. After pumping methylene ch 1ori de through the
column for an additional 1-2 hours, adjust the inlet bed support
plunger until approximately 6-10 psi backpressure is achieved. Push
the plunger in to increase pressure or slowly pull outward to reduce
pressure.
7.2.1.11 When the GPC column is not to be used for several
days, connect the column outlet line to the column inlet to prevent
column drying and/or channeling. If channeling occurs, the gel must
be removed from the column, reswelled, and repoured as described
above. If drying occurs, methylene chloride should be pumped
through the column until the observed column pressure is constant
and the column appears wet. Always recalibrate after column drying
has occurred to verify retention volumes have not changed.
November 1992
7.2.2 Calibration of the GPC Column
7.2.2.1 Using a 10 ml syringe, load sample loop #1 with
calibration solution (Section 5.6). With the ABC automated system,
the 5 ml sample loop requires a minimum of 8 ml of the calibration
solution. Use a firm, continuous pressure to push the sample onto
the loop. Switch the valve so that GPC flow is through the UV flow-
through cell.
7.2.2.2 Inject the calibration solution and obtain a UV
trace showing a discrete peak for each component. Adjust the
detector and/or recorder sensitivity to produce a UV trace similar
to Figure 2 that meets the following requirements. Differences
between manufacturers' cell volumes and detector sensitivities may
require a dilution of the calibration solution to achieve similar
results. An analytical flow-through detector cell will require a
much less concentrated solution than the semi-prep cell, and
therefore the analytical cell is not acceptable for use.
7.2.2.3 Following are criteria for evaluating the UV
chromatogram for column condition.
7.2.2.3.1 Peaks must be observed, and should be
symmetrical, for all compounds in the calibration solution.
7.2.2.3.2 Corn oil and phthalate peaks must exhibit
>85% resolution.
7.2.2.3.3 Phthalate and methoxychlor peaks must
exhibit >85% resolution.
7.2.2.3.4 Methoxychlor and perylene peaks must exhibit
>85% resolution.
7.2.2.3.5 Perylene and sulfur peaks must not be
saturated and must exhibit >90% baseline resolution.
7.2.2.4 Calibration for Semivolatiles Using the
information from the UV trace, establish appropriate collect and
dump time periods to ensure collection of all target analytes.
Initiate column eluate collection just before elution of bis(2-
ethylhexyl) phthalate and after the elution of the corn oil. Stop
eluate collection shortly after the elution of perylene. Collection
should be stopped before sulfur elutes. Use a "wash" time of 10
minutes after the elution of sulfur. Each laboratory is required to
establish its specific time sequences. See Figure 2 for general
guidance on retention time. Figure 1 illustrates retention volumes
for different classes of compounds.
7.2.2.5 Calibration for Organochlorine Pesticides/PCBs -
Determine the elution times for the phthalate, methoxychlor,
perylene, and sulfur. Choose a dump time which removes >85% of the
phthalate, but collects >95% of the methoxychlor. Stop collection
after the elution of perylene, but before sulfur elutes.
November 1992
7.2.2.6 Verify the flow rate by collecting column eluate
for 10 minutes in a graduated cylinder and measure the volume, which
should be 45-55 ml (4.5-5.5 ml/min). If the flow rate is outside of
this range, corrective action must be taken, as described above.
Once the flow rate is within the range of 4.5-5.5 ml/min, record the
column pressure (should be 6-10 psi) and room temperature. Changes
in pressure, solvent flow rate, and temperature conditions can
affect analyte retention times, and must be monitored. If the flow
rate and/or column pressure do not fall within the above ranges, a
new column should be prepared. A UV trace that does not meet the
criteria in Section 7.2.2.3 would also indicate that a new column
should be prepared. It may be necessary to obtain a new lot of Bio
Beads if the column fails all the criteria.
7.2.2.7 Reinject the calibration solution after
appropriate collect and dump cycles have been set, and the solvent
flow and column pressure have been established.
7.2.2.7.l Measure and record the volume of collected
GPC eluate in a graduated cylinder. The volume of GPC eluate
collected for each sample extract processed may be used to
indicate problems with the system during sample processing.
7.2.2.7.2 The retention times for bis(2-ethylhexyl)
phthalate and perylene must not vary more than ±5% between
calibrations. If the retention time shift is >5%, take
corrective action. Excessive retention time shifts are caused
by:
7. 2. 2. 7. 2. 1 Poor laboratory tempera tu re control or
system leaks.
7.2.2.7.2.2 An unstabilized column that requires
pumping methylene chloride through it for several more
hours or overnight.
7.2.2.7.2.3 Excessive laboratory temperatures,
causing outgassing of the methylene chloride.
7.2.2.8 Analyze a GPC blank by loading 5 ml of methylene
chloride into the GPC. Concentrate the methylene chloride that
passes through the system during the collect cycle using a Kuderna-
Danish (KO) evaporator. Analyze the concentrate by whatever
detectors will be used for the analysis of future samples. Exchange
the solvent if necessary. If the blank exceeds the estimated
quantitation limit of the analytes, pump additional methylene
chloride through the system for 1-2 hours. Analyze another GPC
blank to ensure the system is sufficiently clean. Repeat the
methylene chloride pumping if necessary.
7.3 Extract Preparation
7.3.l Adjust the extract volume to 10.0 ml. The solvent extract
must be primarily methylene chloride. All other solvents, e.g. 1:1
November 1992
methylene chloride/acetone, must be concentrated to 1 ml (or as low as
possible if a precipitate forms) and diluted to IO.O ml with methylene
chloride. Thoroughly mix the sample before proceeding.
7.3.2 Filter the extract through a 5 micron filter disc by attaching
a syringe filter assembly containing the filter disc to a 10 ml syringe.
Draw the sample extract through the filter assembly and into the IO ml
syringe. Disconnect the filter assembly before transferring the sample
extract into a small glass container, e.g. a 15 ml culture tube with a
Teflon lined screw cap. Alternatively, draw the extract into the syringe
without the filter assembly. Attach the filter assembly and force the
extract through the filter and into the glass container. The latter is
the preferred technique for viscous extracts or extracts with a lot of
solids. Particulate larger than 5 microns may scratch the valve, which
may result in a system leak and cross-contamination of sample extracts in
the sample loops. Repair of the damaged valve is quite expensive.
NOTE: Viscosity of a sample extract should not exceed the viscosity
of I: I water/glycerol. Oil ute samples that exceed this
viscosity.
7.4 Screening the Extract
7.4.1 Screen the extract to determine the concentration of dissolved
residue by evaporating a 100 µl aliquot to dryness and weighing the
residue. The concentration of dissolved residue loaded on the GPC column
cannot exceed 0.500 g. Concentrations exceeding 0.500 g will very likely
result in incomplete extract cleanup and contamination of the GPC
switching valve (which results in cross-contamination of sample extracts).
7. 4. I. I Transfer IOO µl of the filtered extract from
Section 7.3.2 to a tared aluminum weighing dish.
7.4.1.2 A suggested evaporation technique is to use a heat
lamp. Set up a 250 watt heat lamp in a hood so that it is 8 ±
0.5 cm from a surface covered with a clean sheet of aluminum foil.
Surface temperature should be 80-I00°C (check temperature by placing
a thermometer on the foil and under the lamp). Place the weighing
dish under the lamp using tongs. Allow it to stay under the lamp
for 1 min. Transfer the weighing dish to an analytical balance or
a micro balance and weigh to the nearest 0.1 mg. If the residue
weight is less than 10 mg/100 µl, then further weighings are not
necessary. If the residue weight is greater than 10 mg/100 µl, then
determine if constant weight has been achieved by placing the
weighing dish and residue back under the heat lamp for 2 or more
additional 0.5 min. intervals. Reweigh after each interval.
Constant weight is achieved when three weights agree within ±10%.
7.4.1.3 Repeat the above residue analysis on a blank and
a spike. Add 100 µl of the same methylene chloride used for the
sample extraction, to a weighing dish and determine residue as
above. Add 100 µl of a corn oil spike (5 mg/100 µl) to another
weighing dish and repeat the residue determination.
November 1992
7.4.2 A residue weight of 10 mg/100 µl of extract represents 500 mg
in 5 ml of extract. Any sample extracts that exceed the 10 mg/100 µL
residue weight must be diluted so that the 5 ml loaded on the GPC column
does not exceed 0.500 g. When making the dilution, keep in mind that a
minimum volume of 8 ml is required when loading the ABC GPC unit.
Following is a calculation that may be used to determine what dilution is
necessary if the residue exceeds 10 mg.
Y ml taken = 10 ml final x 10 mg maximum
for dilution volume X mg of residue
Example:
Y ml taken = 10 ml final x 10 mg maximum
for dilution volume 15 mg of residue
Y ml taken for dilution = 6.7 ml
Therefore, taking 6.7 ml of sample extract from Section 7.3.2, and
diluting to 10 ml with methylene chloride, will result in 5 ml of diluted
extract loaded on the GPC column that contains 0.500 g of residue.
NOTE: This dilution factor must be included in the final calculation
of analyte concentrations. In the above example, the dilution
factor is 1. 5.
7.5 GPC Cleanup
7.5.1 Calibrate the GPC at least once per week following the
procedure outlined in Sect i ans 7. 2. 2 through 7. 2. 2. 6. Ensure that UV
trace requirements, flow rate and column pressure criteria are acceptable.
Also, the retention time shift must be <5% when compared to retention
times in the last calibration UV trace.
7.5.1.1 If these criteria are not met, try cleaning the
column by loading one or more 5 ml portions of butyl chloride and
running it through the column. Butyl chloride removes the
discoloration and particulate that may have precipitated out of the
methylene chloride extracts. If a guard column is being used,
replace it with a new one. This may correct the problem. If column
maintenance does not restore acceptable performance, the column must
be repacked with new Bio Beads and calibrated.
7.5.2 Draw a minimum of 8 ml of extract (diluted, if necessary, and
filtered) into a 10 ml syringe.
7.5.3 Attach the syringe to the turn lock on the injection port.
Use firm, continuous pressure to push the sample onto the 5-ml sample
loop. If the sample is difficult to load, some part of the system may be
blocked. Take appropriate corrective action. If the back pressure is
normal (6-10 psi), the blockage is probably in the valve. Blockage may be
flushed out of the valve by reversing the in 1et and outlet tubes and
pumping solvent through the tubes. (This should be done before sample
loading.)
November 1992
NOTE: Approximately 2 ml of the extract remains in the lines between
the injection port and the sample loop; excess sample also
passes through the sample loop to waste.
7.5.4 After loading a loop, and before removing the syringe from the
injection port, index the GPC to the next loop. This will prevent loss of
sample caused by unequal pressure in the loops.
7.5.5 After loading each sample loop, wash the loading port with
methylene chloride in a PTFE wash bottle to minimize cross-contamination.
Inject approximately 10 ml of methylene chloride to rinse the common
tubes.
7.5.6 After loading all the sample loops, index the GPC to the 00
position, switch to the "RUN" mode and start the automated sequence.
Process each sample using the collect and dump cycle times established in
Section 7.2.2.
7.5.7 Collect each sample in a 250 ml Erlenmeyer flask, covered with
aluminum foil to reduce solvent evaporation, or directly into a Kuderna-
Danish evaporator. Monitor sample volumes collected. Changes in sample
volumes collected may indi~ate one or more of the following problems:
7.5.7.1 Change in solvent flow rate, caused by channeling
in the column or changes in column pressure.
7.5.7.2 Increase in column operating pressure due to the
absorption of particles or gel fines onto either the guard column or
the analytical column gel, if a guard column is not used.
7.5.7.3 Leaks in the system or significant variances in
room temperature.
7.6 Concentrate the extract by the standard K-D technique (see any of the
extraction methods, Section 4.2 of this chapter). See the determinative methods
(Chapter Four, Section 4.3) for the final volume.
7.7 It should be remembered that only half of the sample extract is
processed by the GPC (5 ml of the 10 ml extract is loaded onto the GPC column),
and thus, a dilution factor of 2 (or 2 multiplied by any dilution factor in
Section 7.4.2) must be used for quantitation of the sample in the determinative
method.
8.0 QUALITY CONTROL

8.1 Refer to Chapter One and Method 3600 for specific quality control
procedures.
8.2 The analyst should demonstrate that the compound(s) of interest are
being quantitatively recovered before applying this method to actual samples.
November 1992
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.

9.1 Refer to Table 1 for single laboratory performance data.
10.0 REFERENCES
1. Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges"; U.S. EPA
Municipal Environmental Research Laboratory: Cincinnati, Ohio 45268.
2. Czuczwa, J.; Alford-Stevens, A. "Optimized Gel Permeation Chromatographic
Cleanup for Soil, Sediment, Waste and Waste Oil Sample Extracts for GC/MS
Determination of Semivolatile Organic Pollutants, JAOAC, submitted April
1989.
3. Marsden, P.J.; Taylor, V.; Kennedy, M.R. "Evaluation of Method 3640 Gel
Permeation Cleanup"; Contract No. 68-03-3375, U.S. Environmental
Protection Agency, Cincinnati, Ohio, pp. 100, 1987.
November 1992
TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
APPENDIX VIII ANALYTES
Compound % Rec 1 % RSD 2 Ret. Vol. 3 (ml)
Acenaphthene 97 2 196-235
Acenaphthylene 72 10 196-235
Acetophenone 94 7 176-215
2-Acetylaminofluorene 97 2 156-195
Aldrin 99 9 196-215
4-Aminobiphenyl 96 7 176-215
Aniline 93 4 196-235
Anthracene 89 2 196-235
Benomyl 131 8 146-195
Benzenethiol 92 11 196-235
Benzi dine 95 5 176-215
Benz(a)anthracene 100 3 196-235
Benzo(b)fluoranthene 93 5 196-235
Benzo(a)pyrene 93 3 196-235
Benzo(ghi)perylene 90 6 196-235
Benzo(k)fluoranthene 91 4 196-235
Benzoic acid 66 7 176-195
Benzotrichloride 93 7 176-215
Benzyl alcohol 95 17 176-215
Benzyl chloride 99 4 176-215
alpha-BHC 84 13 196-215
beta-BHC 94 9 196-215
gamma-BHC 93 4 196-215
delta-BHC 102 7 216-255
4-Bromophenyl phenyl ether 93 1 176-215
Butyl benzyl phthalate 104 3 136-175
2-sec-butyl-4,6-dinitrophenol (Dinoseb) 103 18 176-195
Carbazole 99 5 196-255
Carbendazim 131 8 146-195
alpha-Chlordane 97 2 196-235
gamma-Chlordane 93 2 196-215
4-Chloro-3-methylphenol 87 1 196-255
4-Chloroanil ine 88 3 196-235
Chlorobenzilate 92 5 176-235
Bis(2-chloroethoxy)methane 89 1 156-195
Bis(2-chloroethyl) ether 76 2 156-215
Bis(2-chloroisopropyl) ether 83 2 156-195
2-Chloronaphthalene 89 1 196-235
2-Chlorophenol 90 1 196-215
4-Chlorophenyl phenyl ether 98 2 176-215
3-Chloropropionitrile 80 5 176-215
Chrysene 102 1 196-235
2-Cresol 91 1 196-215
3-Cresol 70 3 196-215
November 1992
TABLE 1 (continued)
Compound % Rec 1 %RSD 2 Ret. Vol. 3 (ml)
4-Cresol 88 2 196-215
Cyclophosphamide 114 10 146-185
DOD 94 4 196-235
ODE 94 2 196-235
DDT 96 6 176-215
Di-n-butyl phthalate 104 3 136-175
Diallate 97 6 156-175
Dibenzo(a,e)pyrene 94 10 216-235
Dibenzo(a,i)pyrene 99 8 216-235
Dibenz(a,j)acridine 117 9 176-195
Dibenz(a,h)anthracene 92 5 196-235
Dibenzofuran 94 1 176-235
Dibenzothiophene 94 3 196-235
1,2-Dibromo-3-chloropropane 83 2 176-215
1,2-Dibromoethane 121 8 196-215
trans-1,4-Dichloro-2-butene 107 6 176-195
cis-1,4-Dichloro-2-butene 106 6 176-215
1,2-Dichlorobenzene 81 1 196-235
3,3'-Dichlorobenzidine 98 3 176-215
2,6-Dichlorophenol 86 3 196-215
2,4-Dichlorophenoxyacetic acid (2,4-D) 80 NA 76-215
2,4-Dichlorophenol 87 2 96-215
2,4-Dichlorotoluene 70 9 196-235
l,3-Dichloro-2-propanol 73 13 176-215
· Dieldrin 100 5 196-215
Diethyl phthalate 103 3 136-195
Dimethoate 79 15 146-185
3,3'-Dimethoxybenzidine 8 15 11 156-195
Dimethyl phthalate 100 1 156-195
p-Dimethylaminoazobenzene 96 1 176-215
7,12-Dimethyl-benz(a)anthracene 77 1 176-215
2,4-Dimethylphenol 93 2 176-215
3,3'-Dimethylbenzidine 93 2 156-215
4,6-Dinitro-o-cresol 100 1 156-195
1,3-Dinitrobenzene 99 2 156-195
2,4-Dinitrophenol 118 7 176-195
2,4-Dinitrotoluene 93 4 156-195
2,6-Dinitrotoluene 101 2 156-175
Di phenyl amine 95 6 176-235
Diphenyl ether 67 12 196-215
1,2-Diphenylhydrazine 92 1 176-215
Di sul foton 81 15 146-165
Endosulfan sulfate 94 2 176-195
Endosulfan I 99 8 176-215
Endosulfan II 92 6 196-215
Endrin 95 6 196-215
November 1992
TABLE 1 (continued)
Compound % Rec 1 %RS02 Ret. Vol. 3 (ml)
Endrin aldehyde 97 1 176-215

Endrin ketone 94 4 176-215
Ethyl methane sulfonate 62 7 176-235
Ethyl methacrylate 126 7 176-195
Bis(2-ethylhexyl) phthalate 101 1 120-145
Famphur 99 NA 126-165
Fluorene 95 1 176-235
Fluoranthene 94 1 196-235
Heptachlor 85 2 195-215
Heptachlor epoxide 91 11 156-195
Hexachlorobenzene 108 2 196-235
Hexachlorobutadiene 86 2 176-215
Hexachlorocyclopentadiene 89 3 176-215
Hexachloroethane 85 1 196-235
Hexachloropropene 91 2 196-235
Indeno(l,2,3-cd)pyrene 79 13 216-255
Isodrin 98 5 196-235
Isophorone 68 7 156-195
cis-Isosafrole 90 4 176-215
trans-Isosafrole 88 16 156-195
Ke pone 102 NA 196-235
Malononitrile 111 9 156-195
Merphos 93 12 126-165
Methoxychlor 94 6 156-195
3-Methylcholanthrene 74 12 176-195
2-Methylnaphthalene 67 6 196-215
Methyl parathion 84 13 146-185
4,4'-Methylene-bis(2-chloroaniline) 96 1 176-215
Naphthalene 95 7 196-215
1,4-Naphthoquinone 73 7 176-215
2-Naphthylamine 94 8 196-235
1-Naphthylamine 96 6 196-235
5-Nitro-o-toluidine 77 2 176-195
2-Nitroanil i ne 96 8 176-215
3-Nitroanil i ne 96 2 176-215
4-Nitroani line 103 8 176-215
Nitrobenzene 86 2 176-195
2-Nitrophenol 95 3 176-195
4-Nitrophenol 77 3 196-215
N-Nitroso-di-n-butylamine 89 4 156-175
N-Nitrosodiethanolamine 104 3 146-185
N-Nitrosodiethylamine 94 2 156-175
N-Nitrosodimethylamine 86 13 156-195
N-Nitrosodiphenylamine 99 2 156-195
N-Nitrosodi-n-propylamine 85 4 156-175
N-Nitrosomethylethylamine 83 7 156-175
N-Nitrosomorpholine 86 4 156-195
N-Nitrosopiperidine 84 4 156-195
November 1992
TABLE 1 (continued)
Compound % Rec 1 %RSD 2 Ret. Vol. 3 (ml)
N-Nitrosopyrolidine 92 1 156-175
Di-n-octyl phthalate 83 4 120-156
Parathion 109 14 146-170
Pentachlorobenzene 95 2 196-235
Pentachloroethane 74 1 196-235
Pentachloronitrobenzene (PCNB) 91 8 156-195
Pentachlorophenol 102 1 196-215
Phenacetin 100 3 156-195
Phenanthrene 94 2 196-235
Phenol 83 2 156-195
1,2-Phenylenediamine 91 1 196-215
Phorate 74 NA 116-135
2-Picoline 99 14 156-215
Pron amide 105 15 156-195
Pyrene 98 2 215-235
Resorcinol 70 6 196-215
Sa fro le 93 1 176-215
Streptozotocin 8 6 48 225-245
1,2,4,5-Tetrachlorobenzene 96 2 196-235
2,3,5,6-Tetrachloro-nitrobenzene 85 9 176-215
2,3,4,6-Tetrachlorophenol 95 1 196-215
2,3,5,6-Tetrachlorophenol 96 7 196-215
Tetraethyl dithiopyrophosphate (Sulfotep) 89 14 116-135
Thiosemicarbazide 74 3 146-185
2-Toluidine 92 3 176-235
4-Toluidine 87 8 176-235
Thiourea, 1-(o-chlorophenyl) 75 11 166-185
Toluene-2,4-diamine 69 7 176-215
1,2,3-Trichlorobenzene 87 1 196-235
1,2,4-Trichlorobenzene 89 1 196-235
2,4,5-Trichlorophenol 77 1 216-235
2,4,6-Trichlorophenol 95 1 216-235
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) 71 23 156-235
2,4,5-Trichlorophenoxypropionic acid 67 NA 216-215
Warfarin 94 2 166-185
NA= Not applicable, recovery presented as the average of two determinations.

a
Not an appropriate analyte for this method.
The percent recovery is based on an average of three recovery values.
2
The% relative standard deviation is determined from three recovery values.
3
These Retention Volumes are for guidance only as they will differ from column to
column and from system to system.
November 1992
Figure I
GPC RETENTION VOLUME OF CLASSES OF ANALYTES
PAH't
CHLOR08ENZENES
~ NJTROSAMINES, NITAOAROMA TICS
AROMA TIC AMINES
PHTHALATS- NtTAOPHl!NOLS
~ CHLOROPHENOLS
OROANOCHLORINE
PESTICIOES/PCB'I
~~HERBICIDES (8150)
ORGANOPMOSPHATI! wzi~~Wfij
PESTICIDES
... -PCP
COAN OIL·•
C - Collect
0 10 20 30 40 50 70
c TIME (minutes)
November 1992
Figure 2
UV CHROMATOGRAM OF THE CALIBRATION SOLUTION
Injection 0 minu~es
) t':tL s
on column
15 111inuc:es
Corn oil -·- -- .

25 mg/uL ~-----
Bis(2-ethylhexy~l~)~-~-~~h:·~~h:·a~~:a;~:-e:.:.:·-:____~:_:._~=.:
1.0 mg/mL
30 minutes
Methoxychlor
0.2 rng/mL
Perylene
0.02 mg/mL 45 minutes
Sulfur -. --- . - -- - -
0.08 rng/t:JL
. - . --l - - -
700 mm X25 Cllll col Sm-'J.·-_·,1::-=:__;s _.-:;7 ___ · -.;- _:.1. _:·~- :;1 _--'...'J
70 ~ Bio-Beads SX -·)".:-=...: - ~-=--- -~~ _:_-·--=-~ ~- - - --- - ·
Bed leno-th = 490 - --------·---~=~-~~-~:-:----=-.:-- - ------------ -- -~---_::: -~ --- ---~ 60 minutes
() -
CH2Clz at 5 .o nL nir:.:_:_- -- ~ ---- - - . .
25z+ nu - - - - - ------------ - - - - - - · ------~--
November 1992
METHOD 3640A
GEL-PERMEATION CLEANUP
7.1 Ensure ambient temp. consistent

throughout GPC run.
.
+
7.2 GPC Setup and Calibration
~
7.2.1 Column Preparation 7.2.1.6 Compress column. Slurry
remaining beads and repeat Section
7.2.1.5 and column compression .
•
7.2.1.1 Place Bio Beads and MeCI
in a container. Swirl and
allow beads to swell. 7 .2.1. 7 Compress column bed
approximately four cm .
•
7.2.1 2 Remove column inlet bed
support plunger. Position and tighten
outlet bed support plunger to column end. 7.2.1.8 Pack option 5 cm. guard
column w/ roughly 5 gm.
preswelled beads .
•
7.2.1.3 Ensure GPC column outlet
contains solvent. Place small amount
7.2.1.9 Connect column inlet ID
solvent in column to minimize
bubble formation. solvent reservoir. Pump MeCI at
5 ml/mm. for 1 hr
7 2.1.4 Transfer bead mixture into

sep. tunnel. Drain excess solvent;
drain beads into column. Keep
•
7.2.1.1 O Connect column outlet to
UV-Vis detector. Place restrictor
at detector outlet. Run MeCI for
beads wet throughout.
additional 1-2 tvs. Compress
column bed to provide 6-1 o psi
backpressure.
7.2.1.5 Loosen seal on opposite
•
plunger assembly, insert into column.
7.2.1.11 Connect outlet line to column

inlet when column not in use. Repack
column when chameling is observed.
Assure consistent backpressure when
beads are rewetted alter drying.
cb
November 1992
METHOD 3640A
continued
7.2.2 Calibration of the GPC column
7.2.2.1 Load sample loop with

calibration solutJon.
7.2.2.2 Inject calibration soln.; adjust

recorder or detector sensilivtty
to produce similar UV trace as Fig. 2. 7.2.2. 7 Reinject calibration soln. when
collect and dump cycles are set,
and column criteria are met
7.2.2.3 Evaluation criteria for

UV chromatogram.
7.2.2.7.1 Measure and record
volume ot GPC eluate.
7.2.2.4 Calibration for Semivolaliles
Use information from UV trace to
obtain collect and dump limes.
Initiate collection before bis(2-elhylhexyl) 7.2.2. 7.2 Correct tor retention time
phthalate, stop after perylene. Stop run shifts of> +/- 5% for
before sulfur elutes. bis(2-ethylhexyt) phthalate
and perylene.
7.2.2.5 Calibration for Organoctilorine

Pesticides/PCBs
7.2.2.8 Inject and analyze GPC blank
Choose dump lime which removes
for column deanliness. Plmp
> 85% phthalate, but collects at
through MeCI as column wash.
times > 95% methoxychlor. Stop
collection between perylene and
sulfur elution.
7.2.2.6 Verity column flow rate and

backpressure. Correct
inconsistencies when criteria
are not met
November 1992
METHOD 3640A
contin:Jed
7.3 Extract Preparation 7.5 GPC Cleanup
7.3.1 Adjwt extract volime to 10 ml. 7.5.1 catibral8 GPC waefdy. Assure
Primary solvent should be MeCI. column critaria, UV trace, retention
lime shift critaria are met
7.3.2 Fill8r extract ltrough 5 micron flltar

dlsasyringe assembly into small 7.5.1.1 Clean colurm wlbutyl chloride
glass conlalner. loadings, Of replacement of
column.
7.4 Screening lhe Extract

7.5.2 Draw 8 ml. extract Into syringe.
7.4.1 Screen extract by determining

residue wt. of 100 ut aliquot 7.5.3 Load samS*t Into ir1ection loop.
7.4.1.1 Transfer 100 ul of filtered

7.5.4 Index GPC to next loop to
extract from Section 7.3.2 to tared
pnMKlt sample lass.
alum1r um weighing dish.
7.5.5 Wash samS*t port w/MeCI

7.4.1.2 Evaporate extract solvent under
between samS*t loadings.
healing lamp. Weigh residue to nearest
0.1 mg.
7.5.6 At end of loadings, index GPC to

00, switch t> "RUN" mode, start
7.4.1.3 Repeat residue analysis of Seclion
automated sequence.
7.4.1.2 wtblankand spike sample.
7.5.7 Collect samS*t int> aluminum foil

7.4.2 Use dilution example to determine covered Erlenmey• flask or Into
necessary dilution when residue Kudema-Danish evaporator.
WIS.> 10mg.
7.6 Concentra'9 extract by std.

Kudema-Danish tecmique.
7. 7 Note dilution fact>r of GPC method

into final determinations.
November 1992
METHOD 3665
SULFURIC ACID/PERMANGANATE CLEANUP

1.1 This method is suitable for the rigorous cleanup of sample extracts
prior to analysis for polychlorinated biphenyls. This method should be used
whenever elevated baselines or overly complex chromatograms prevent accurate
quantitation of PCBs. This method cannot be used to cleanup extracts for other
target analytes, as it will destroy most organic chemicals including the
pesticides Aldrin, Dieldrin, Endrin, Endosulfan (I and II), and Endosulfan
sulfate.

2.1 An extract is so 1vent exchanged to hexane, then the hexane is
sequentially treated with (1) concentrated sulfuric acid and (2) 5% aqueous
potassium permanganate. Appropriate caution must be taken with these corrosive
reagents.
2.2 Blanks and replicate analysis samples must be subjected to the same
cleanup as the samples associated with them.
2.3 It is important that all the extracts be exchanged to hexane before
initiating the following treatments.
3.0 INTERFERENCES
3.1 This technique will not destroy chlorinated benzenes, chlorinated
naphthalenes (Halowaxes), and a number of chlorinated pesticides.
4.0 APPARATUS
4.1 Syringe or Class A volumetric pipet, glass; 1.0, 2.0 and 5.0 ml.
4.2 Vials - 1, 2 and 10 ml, glass with Teflon lined screw caps or crimp
tops.
4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
extracts.
equivalent.
3665 - 1 Revision 0
November 1992
equivalent).
equivalent).
4.4 Vortex mixer.
5.0 REAGENTS
5.3 Sulfuric acid/Water, H2SOjH 20, (1:1, v/v).
5.4 Hexane, C6H14 - Pesticide grade or equivalent.
5.5 Potassium permanganate, KMn04 , 5 percent aqueous solution (w/v).

Section 4.1.
7. 0 PROCEDURE
7.1 Sulfuric acid cleanup
7.1.1 Using a syringe or a volumetric pipet, transfer 1.0 or 2.0 ml
of the hexane extract to a 10 ml vial and, in a fume hood, carefully add
5 ml of the 1:1 sulfuric acid/water solution.
7.1.2 The volume of hexane extract used depends on the requirements
of the GC autos ampler used by the laboratory. If the autos ampler
functions reliably with 1 ml of sample volume, 1.0 ml of extract should be
used. If the autosampler requires more than 1 ml of sample volume, 2.0 ml
of extract should be used.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
3665 - 2 Revision 0
November 1992
7.1.3 Cap the vial tightly and vortex for one minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks, AVOID
SKIN CONTACT, SULFURIC ACID BURNS.
7.1.4 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer; it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.1.5 If a clean phase separation is achieved, proceed to
Section 7 .1.8.
7.1.6 If the hexane layer is colored or the emulsion persists for
several minutes, remove the sulfuric acid layer from the vial and dispose
of it properly. Add another 5 ml of the clean 1:1 sulfuric acid/water.
NOTE: Do not remove any hexane at this stage of the procedure.
7.1. 7 Vortex the sample for one minute and a11 ow the phases to
separate.
7.1.8 Transfer the hexane layer to a clean 10 ml vial.
7.1.9 Add an additional 1 ml of hexane to the sulfuric acid layer,
cap and shake. This second extraction is done to ensure quantitative
transfer of the PCBs and Toxaphene.
7 .1.10 Remove the second hexane layer and combine with the
hexane from Section 7.1.8.
7.2 Permanganate cleanup
7. 2 .1 Add 5 ml of the 5 percent aqueous potassium permanganate
solution to the combined hexane fractions from 7.1.10.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
7.2.2 Cap the vial tightly and vortex for 1 minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks. AVOID
SKIN CONTACT, POTASSIUM PERMANGANATE BURNS.
7.2.3 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer, it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.2.4 If a clean phase separation is achieved, proceed to
Section 7.2.7.
7.2.5 If the hexane layer is colored or the emulsion persists for
several minutes, remove the permanganate solution from the vi al vi a a
3665 - 3 Revision O
November 1992
glass pipette and dispose of it properly. Add another 5 ml of the clean
aqueous permanganate solution.
NOTE: Do not remove any hexane at this stage of the procedure.
7.2.6 Vortex the sample and allow the phases to separate.
7.2.7 Transfer the hexane layer to a clean 10 ml vial.
7.2.8 Add an additional 1 ml of hexane to the permanganate layer,
cap the vial securely and shake. This second extraction is done to ensure
quantitative transfer of the PCBs and Toxaphene.
7.2.9 Remove the second hexane layer and combine with the hexane
from Section 7.2.7.
7.3 Final preparation
7. 3 .1 Reduce the vo 1ume of the combined hexane 1ayers to the
original volume (1 or 2 ml) using the Kuderna-Danish Technique
(Section 7.3.1.1).
7.3.1.1 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 ml of hexane to the top of the column. Place the K-D
apparatus on a hot water bath (15-20°C above the boiling point of
the solvent) so that the concentrator tube is partially immersed in
the hot water and the entire lower rounded surface of the flask is
bathed with hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to complete the
concentration in 10-20 minutes. At the proper rate of distillation
the balls of the column will actively chatter, but the chambers will
not flood. When the apparent vo 1ume of l i quid reaches 1-2 ml,
remove the K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes.
7.3.1.2 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 ml of hexane.
The extract may be further concentrated by using either the micro
Snyder column technique (Section 7.3.2) or nitrogen blowdown
technique (Section 7.3.3).
7.3.2 Micro Snyder Column Technique
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0. 5 ml of hexane to the top of the
column. Place the K-D apparatus in a hot water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
the vertical position of the apparatus and the water temperature, as
required, to complete the concentration in 5-10 minutes. At the
proper rate of distillation the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water
3665 - 4 Revision 0
November 1992
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse the fl ask and its lower joints with
about 0.2 ml of hexane and add to the concentrator tube. Adjust the
final volume to 1.0-2.0 ml, as required, with hexane.
7.3.3.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
7.3.4 Remove any remaining organochlorine pesticides from the
extracts using Florisil Column Cleanup (Method 3620) or Silica Gel Cleanup
(Method 3630).
7.3.5 The extracts obtained may now be analyzed for the target
analytes using the appropriate organic technique(s) (see Section 4.3 of
this Chapter). If analysis of the extract will not be performed
immediately, stopper the concentrator tube and store in a refrigerator.
If the extract will be stored longer than 2 days, it should be transferred
to a vial with a Teflon lined screw cap or crimp top, and labeled
appropriately.
8.0 QUALITY CONTROL


9.1 No performance data are currently available.
10.0 REFERENCES
None required.
3665 - 5 Revision 0
November 1992
METHOD 3665
SULFURIC ACID/PERMANGANATE CLEANUP
Stare
7 2 l Add
i..i .. ~ n ... .. KMnO,
H,SO.;H,J sol u. t. ... on
so ..... t. 1 on
7 l 2 722-723
Transier the Cap vortex,
appropriate and allow
volume to pnase
vial separ-al1on
J J -7 • 4
: 7 2 4 I• 7 2 5 Remove
Cap vorte>< phase No a~d ~:soose
allow
and s e p a r a / 1 o n ~MnO. so .. ~t.~n
.__a_d_d~-c-·-e~a-n~K-M~n-0_,_,
phase
sepa:-allon clean? solut1on
Yes
7 l 5 Is 7 1 6 Remove 7 2 7 7 2 6 Cap.
pha•e No and dlspose Transfer vortex, and
separal1on H,SO, •oluti.on. hexane layer allow ohase
clean? add clean H,SO, lo clean v1a.L separa t.!..on
.tolutlon
Ye•
7 1 8 7 l 7 Cap, 7 2 8 Add 731-733

Transfer vortex, a.nd hexane to Reduce volume
he>eane layer allow phase KMnO, layer. ,......... u•i.ng K-D
to clean v1al separal1on cap ilnd shake and/or nitrogen
blowdown tech
7 l 9 Add 7 3 4 u.e
hexane to 7 2 9 Combi.n• Method 3620 or
H,SO, layer two hexane ---- Method 3630 to
cap and shake layers further remove
contaminants
7 3 5 Stopper
7 l l0 and
Combine two refr19erate
hexane layers for further
analysis
Stop
3665 6 Revision 0
November 1992
METHOD 8000
GAS CHROMATOGRAPHY

1.1 Gas chromatography is a quantitative analytical technique useful for
organic compounds capable of being volatilized without being decomposed or
chemi ca 11 y rearranged. Gas chromatography ( GC), al so known as vapor phase
chromatography (VPC), has two subcategories di st i ngui shed by: gas-sol id
chromatography (GSC), and gas-1 iquid chromatography (GLC) or gas-1 iquid
partition chromatography (GLPC) . This last group is the most commonly used,
distinguished by type of column adsorbent or packing.
1.2 The gas chromatographic methods are recommended for use only by, or
under the close,supervision of, experienced residue analysts.
2.1 Each organic analytical method that follows provides a recommended
technique for extraction, cleanup, and occasionally, derivatization of the
samples to be analyzed. Before the prepared sample is introduced into the GC,
a procedure for standardization must be followed to determine the recovery and
the limits of detection for the analytes of interest. Following sample
introduction into the GC, analysis proceeds with a comparison of sample values
with standard values. Quantitative analysis is achieved through integration
of peak area or measurement of peak height.
3.0 INTERFERENCES
3 .1 Contamination by carryover can occur whenever high-level and low-
1eve l samples are sequentially analyzed. To reduce carryover, the sample
syringe or purging device must be rinsed out between samples with water or
solvent. Whenever an unusually concentrated sample is encountered, it should
be followed by an analysis of a solvent blank or of water to check for cross
contamination. For volatile samples containing large amounts of water-soluble
materials, suspended solids, high boiling compounds or high organohalide
levels, it may be necessary to wash out the syringe or purging device with a
detergent solution, rinse it with distilled water, and then dry it in a 105°C
oven between analyses.
4.1 Gas chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections and all required accessories,
including detectors, column supplies, recorder, gases, and syringes. A data
system for measuring peak height and/or peak areas is recommended.
4.2 Gas chromatographic columns - See the specific determinative method.
Other packed or capillary (open-tubular) columns may be used if the
requirements of Step 8.6 are met.
8000 - 1 Revision 1
December 1987
5.0 REAGENTS
5.1 See the specific determinative method for the reagents needed.
6 .1 See the introductory material to this chapter, Organic Anal ytes,
Step 4.1.
7.0 PROCEDURE
7.1 Extraction - Adhere to those procedures specified in the referring
determinative method.
7.2 Cleanup and separation - Adhere to those procedures specified in the
referring determinative method.
7.3 The recommended gas chromatographic columns and operating conditions
for the instrument are specified in the referring determinative method.
7.4 Calibration
7.4.1 Establish gas chromatographic operating parameters equivalent
to those indicated in Section 7.0 of the determinative method of
interest. Prepare calibration standards using the procedures indicated
in Section 5. 0 of the determinative method of interest. Ca 1i brate the
chromatographic system using either the external standard technique (Step
7.4.2) or the internal standard technique (Step 7.4.3).
7.4.2 External standard calibration procedure
7.4.2.1 For each analyte of interest, prepare calibration
standards at a minimum of five concentration levels by adding
volumes of one or more stock standards to a volumetric fl ask and
diluting to volume with an appropriate solvent. One of the external
standards should be at a concentration near, but above, the method
detection limit. The other concentrations should correspond to the
expected range of concentrations found in real samples or should
define the working range of the detector.
7.4.2.2 Inject each calibration standard using the technique
that wi 11 be used to introduce the actual samples into the gas
chromatograph (e.g. 2-5-uL injections, purge-and-trap, etc.).
Tabulate peak height or area responses against the mass injected.
The results can be used to prepare a calibration curve for each
analyte. Alternatively, for samples that are introduced into the
gas chromatograph using a syringe, the ratio of the response to the
amount injected, defined as the calibration factor (CF), can be
calculated for each analyte at each standard concentration. If the
percent relative standard deviation (%RSD) of the calibration factor
is less than 20% over the working range, linearity through the
origin can be assumed, and the average calibration factor can be
used in place of a calibration curve.
8000 - 2 Revision 1
December 1987
Calibration factor= _____ JQ~~l-~r~~~Qf_~~~~----
*
Mass 1nJected (1n nanograms)
*For multiresponse pesticides/PCBs use the total area of all peaks
used for quantitation.
7.4.2.3 The working calibration curve or calibration factor
must be verified on each working day by the injection of one or more
ca 1 i brat ion standards. The frequency of veri fi cation is dependent
on the detector. Detectors, such as the electron capture detector,
that operate in the sub-nanogram range are more susceptible to
changes in detector response caused by GC column and sample effects.
Therefore, more frequent verification of calibration is necessary.
The flame ionization detector is much 1ess sensitive and requires
less frequent verification. If the response for any analyte varies
from the predicted response by more than ± 15%, a new calibration
curve must be prepared for that analyte.
RI - R2
Percent Difference = ------- x 100
Rl
where:
R1 Calibration Factor from first analysis.
R2 Calibration Factor from succeeding analyses.
7.4.3 Internal standard calibration procedure
7.4.3.l To use this approach, the analyst must select one or
more internal standards that are similar in analytical behavior to
the compounds of interest. The analyst must further demonstrate
that the measurement of the internal standard is not affected by
method or matrix interferences. Due to these 1 imitations, no
internal standard applicable to all samples can be suggested.
7.4.3.2 Prepare calibration standards at a minimum of five
concentration levels for each analyte of interest by adding volumes
of one or more stock standards to a volumetric flask. To each
ca 1 i brat ion standard, add a known constant amount of one or more
internal standards and dilute to volume with an appropriate solvent.
One of the standards should be at a concentration near, but above,
the method detection 1 imit. The other concentrations should
correspond to the expected range of concentrations found in real
samples or should define the working range of the detector.
7.4.3.3 Inject each calibration standard using the same
introduction technique that will be applied to the actual samples
(e.g. 2- to 5-ul injection, purge-and-trap, etc.). Tabulate the
peak height or area responses against the concentration of each
compound and internal standard. Calculate response factors (RF) for
each compound as follows:
8000 - 3 Revision 1
December 1987
where:
As = Response for the analyte to be measured.

Ais = Response for the internal standard.
Cis = Concentration of the internal standard, ug/l.
Cs = Concentration of the analyte to be measured, ug/l.
If the RF value over the working range is constant (< 20% RSD), the
RF can be assumed to be invariant, and the average RF can be used
for calculations. Alternatively, the results can be used to plot a
calibration curve of response ratios, As/Ais versus RF.
7.4.3.4 The working calibration curve or RF must be verified
on each working day by the measurement of one or more ca 1 i brat ion
standards. The frequency of veri fi cation is dependent on the
detector. Detectors, such as the electron capture detector, that
operate in the sub-nanogram range are more susceptible to changes in
detector response caused by GC column and sample effects.
Therefore, more frequent verification of calibration is necessary.
The flame ionization detector is much less sensitive and requires
less frequent verification. If the response for any analyte varies
from the predicted response by more than ± 15%, a new calibration
curve must be prepared for that compound.
7.5 Retention time windows
7.5.1 Before establishing windows, make sure the GC system is
within optimum operating conditions. Make three injections of all single
component standard mixtures and multi response products (i.e. PCBs)
throughout the course of a 72-hour period. Serial injections over less
than a 72-hour period result in retention time windows that are too
tight.
7.5.2 Calculate the standard deviation of the three absolute
retention times for each single component standard. For multiresponse
products, choose one major peak from the envelope and cal cul ate the
standard deviation of the three retention times for that peak. The peak
chosen should be fairly immune to losses due to degradation and
weathering in samples.
7. 5. 2 .1 Pl us or mi nus three times the standard deviation of
the ab so 1ute retention ti mes for each standard wi 11 be used to
define the retention time window; however, the experience of the
analyst should weigh heavily in the interpretation of chromatograms.
For multi response products (i.e. PCBs), the analyst should use the
retention time window but should primarily rely on pattern
recognition.
8000 - 4 Revision 1
December 1987
7.5.2.2 In those cases where the standard deviation for a
particular standard is zero, the laboratory must substitute the
standard deviation of a close eluting, similar compound to develop a
valid retention time window.
7.5.3 The laboratory must calculate retention time windows for each
standard on each GC column and whenever a new GC column is installed.
The data must be retained by the laboratory.
7.6 Gas chromatographic analysis
7.6.1 Introduction of organic compounds into the gas chromatograph
varies depending on the volatility of the compound. Volatile organics
are primarily introduced by purge-and-trap (Method 5030). However, there
are limited applications where direct injection is acceptable. Use of
Method 3810 or 3820 as a screening technique for volatile organic
analysis may be valuable with some sample matrices to prevent overloading
and contamination of the GC systems. Semivolatile organics are
introduced by direct injection.
7.6.2 The appropriate detector(s) is given in the specific method.
7.6.3 Samples are analyzed in a set referred to as an analysis
sequence. The sequence begins with instrument calibration followed by
sample extracts interspersed with multilevel calibration standards. The
sequence ends when the set of samples has been injected or when
qualitative and/or quantitative QC criteria are exceeded.
7.6.4 Direct Injection - Inject 2-5 ul of the sample extract using
the solvent flush technique. Smaller (1.0-ul) volumes can be injected if
automatic devices are employed. Record the volume injected to the
nearest 0.05 ul and the resulting peak size in area units or peak height.
7. 6. 5 If the responses exceed the linear range of the system,
dilute the extract and reanalyze. It is recommended that extracts be
diluted so that all peaks are on scale. Overlapping peaks are not always
evident when peaks are off scale. Computer reproduction of
chromatograms, manipulated to ensure all peaks are on scale over a
100-fold range, are acceptable if linearity is demonstrated. Peak height
measurements are recommended over peak area integration when overlapping
peaks cause errors in area integration.
7.6.6 If peak detection is prevented by the presence of
interferences, further cleanup is required.
7.6.7 Examples of chromatograms for the compounds of interest are
frequently available in the referring analytical method.
7.6.8 Calibrate the system immediately prior to conducting any
analyses (see Step 7 .4). A midlevel standard must al so be injected at
intervals specified in the method and at the end of the analysis
sequence. The calibration factor for each anal yte to be quant i tated,
must not exceed a 15% difference when compared to the initial standard of
8000 - 5 Revision 1
December 1987
the analysis sequence. When this criteria is exceeded, inspect the GC
system to determine the cause and perform whatever maintenance is
necessary (see Step 7.7) before recalibrating and proceeding with sample
analysis. All samples that were injected after the sample exceeding the
criteria must be reinjected.
7.6.9 Establish daily retention time windows for each analyte. Use
the absolute retention time for each analyte from Step 7.6.8 as the
midpoint of the window for that day. The da i1 y retention ti me window
equals the midpoint ± three times the standard deviation determined in
Step 7.5.
7.6.9.1 Tentative identification of an ana1yte occurs when a
peak from a sample extract falls within the daily retention time
window. Normally, confirmation is required: on a second GC column,
by GC/MS if concentration permits, or by other recognized
confirmation techniques. Confirmation may not be necessary if the
composition of the sample matrix is well established by prior
analyses.
7.6.9.2 Validation of GC system qualitative performance: Use
the midlevel standards interspersed throughout the analysis sequence
(Step 7.6.8) to evaluate this criterion. If any of the standards
fall outside their daily retention time window, the system is out of
control. Determine the cause of the problem and correct it (see
Step 7.7).
7. 7 Suggested chromatography system maintenance - Corrective measures
may require any one or more of the following remedial actions.
7.7.1 Packed columns - For instruments with injection port traps,
replace the demister trap, clean, and deactivate the glass injection port
insert or replace with a cleaned and deactivated insert. Inspect the
injection end of the column and remove any foreign material (broken glass
from the rim of the column or pieces of septa). Replace the glass wool
with fresh deactivated glass wool. Also, it may be necessary to remove
the first few millimeters of the packing material if any discoloration is
noted, a1so swab out the inside walls of the co 1umn if any residue is
noted. If these procedures fail to eliminate the degradation problem, it
may be necessary to deactivate the metal injector body (described in Step
7.7.3) and/or repack/replace the column.
7.7.2 Capillary columns - Clean and deactivate the glass injection
port insert or replace with a cleaned and deactivated insert. Break off
the first few inches, up to one foot, of the injection port side of the
column. Remove the column and solvent backflush according to the
manufacturer's instructions. If these procedures fail to eliminate the
degradation problem, it may be necessary to deactivate the metal injector
body and/or replace the column.
7. 7. 3 Meta 1 injector body - Turn off the oven and remove the
analytical column when the oven has cooled. Remove the glass injection
port insert (instruments with off-column injection or Grob). Lower the
8000 - 6 Revision 1
December 1987
injection port temperature to room temperature. Inspect the injection
port and remove any noticeable foreign material.
7.7.3.1 Place a beaker beneath the injector port inside the GC
oven. Using a wash bottle, serially rinse the entire inside of the
injector port with acetone and then toluene; catching the rinsate in
the beaker. ·
7.7.3.2 Prepare a solution of deactivating agent (Sylon-CT or
equivalent) following manufacturer's directions. After all metal
surfaces inside the injector body have been thoroughly coated with
the deactivation solution, serially rinse the injector body with
toluene, methanol,acetone, and hexane. Reassemble the injector and
replace the GC column.
7.8 Calculations
7.8.1 External standard calibration - The concentration of each
analyte in the sample may be determined by calculating the amount of
standard purged or injected, f'rom the peak response, using the
calibration curve or the calibration factor determined in Step 7. 4. 2.
The concentration of a specific analyte is calculated as follows:
Aqueous samples
Concentration (ug/L) = [(Ax)(A)(Vt)(D)]/[(As)(Vi)(Vs)]
where:
Ax = Response for the analyte in the sample, units may be in area
counts or peak height.
A = Amount of standard injected or purged, ng.
As = Response for the external standard, units same as for Ax.
Vi = Volume of extract injected, uL. For purge-and-trap analysis,
Vi is not applicable and therefore = 1.
D =Dilution factor, if dilution was made on the sample prior to
analysis. If no dilution was made, D = 1, dimensionless.
Vt = Volume of total extract, ul. For purge-and-trap analysis, Vt is
not applicable and therefore= 1.
Vs = Volume of sample extracted or purged, ml.
Nonaqueous samples
Concentration (ng/g) = [(Ax)(A)(Vt)(D)]/[(As)(Vi)(W)]
8000 - 7 Revision 1
December 1987
where:
W = Weight of sample extracted or purged, g. The wet weight or dry
weight may be used, depending upon the specific applications of
the data.
Ax, As, A, Vt, D, and Vi have the same definition as for aqueous
samples.
7.8.2 Internal standard calibration - For each analyte of interest,
the concentration of that analyte in the sample is calculated as follows:
Aqueous samples
Concentration (ug/L) [(Ax)(Cis)(D)]/[(Ais)(RF)(Vs)]
where:
Ax = Response of the analyte being measured, units may be in area
counts or peak height.
C;s =Amount of internal standard added to extract or volume purged,
ng.
D = Dilution factor, if a dilution was made on the sample prior to
analysis. If no dilution was made, D = 1, dimensionless.
Ais = Response of the internal standard, units same as Ax.
RF =Response factor for analyte, as determined in Step 7.4.3.3.
Vs = Volume of water extracted or purged, ml.
Nonaqueous samples
Concentration (ug/kg} [(As}(Cis)(D}]/[(Ais}(RF}(Ws}]
where:
Ws = Weight of sample extracted, g. Either a dry weight or wet
weight may be used, depending upon the specific application of
the data.
As, Cis' D, Ais' and RF have the same definition as for aqueous
samples.
8.0 QUALITY CONTROL
8 .1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum requirements of this program
consist of an initial demonstration of laboratory capability and an ongoing
analysis of spiked samples to evaluate and document quality data. The
laboratory must maintain records to document the qua 1 ity of the data
8000 - 8 Revision 1
December 1987
generated. Ongoing data quality checks are compared with established
performance criteria to determine if the results of analyses meet the
performance characteristics of the method. When results of sample spikes
indicate atypical method performance, a quality control check standard must be
analyzed to confirm that the measurements were performed in an in-control mode
of operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a reagent blank, that interferences from the
analytical system, glassware, and reagents are under control. Each time a set
of samples is extracted or there is a change in reagents, a reagent water
blank should be processed as a safeguard against chronic laboratory
contamination. The blank samples should be carried through all stages of the
sample preparation and measurement steps.
8.3 For each analytical batch (up to 20 samples), a reagent blank, matrix
spike, and replicate or matrix spike replicate must be analyzed (the frequency
of the spikes may be different for different monitoring programs). The blank
and spiked samples must be carried through all stages of the sample
preparation and measurement steps.
8.4 The experience of the analyst performing gas chromatography is
invaluable to the success of the methods. Each day that analysis is
performed, the daily calibration sample should be evaluated to determine if
the chromatographic system is operating properly. Questions that should be
asked are: Do the peaks look normal?; Is the response obtained comparable to
the response from previous calibrations? Careful examination of the standard
chromatogram can indicate whether the column is still good, the injector is
leaking, the injector septum needs replacing, etc. If any changes are made to
the system (e.g. column changed), recalibration of the system must take place.
8.5 Required instrument QC
8.5.1 Step 7.4 requires that the %RSD vary by< 203 when comparing
calibration factors to determine if a five point calibration curve is
linear.
8.5.2 Step 7 .4 sets a limit of ± 15% difference when comparing
daily response of a given analyte versus the initial response. If the
limit is exceeded, a new standard curve must be prepared.
8.5.3 Step 7.5 requires the establishment of retention time
windows.
8.5.4 Step 7.6.8 sets a limit of± 153 difference when comparing
the initial response of a given analyte versus any succeeding standards
analyzed during an analysis sequence.
8.5.5 Step 7 .6.9.2 requires that all succeeding standards in an
analysis sequence must fall within the daily retention time window
established by the first standard of the sequence.
8000 - 9 Revision 1
December 1987
precision, the analyst must perform the following operations.
8.6.1 A quality (QC) check sample concentrate is required

containing each analyte of interest. The QC check sample concentrate may
be prepared from pure standard materi a 1 s or purchased as certified
solutions. If prepared by the laboratory, the QC check sample
concentrate must be made using stock standards prepared independently
from those used for calibration.
8.6.1.1 The concentration of the QC check sample concentrate

is highly dependent upon the analytes being investigated.
Therefore, refer to Method 3500, Section 8.0 for the required
concentration of the QC check sample concentrate.
8.6.2 Preparation of QC check samples
8.6.2.1 Volatile organic analytes (Methods 8010, 8020, and

8030) - The QC check sample is prepared by adding 200 ul of the QC
check sample concentrate (Step 8.6.1) to 100 ml of water.
8.6.2.2 Semivolatile organic analytes (Methods 8040, 8060,

8080, 8090, 8100, and 8120) - The QC check sample is prepared by
adding 1.0 ml of the QC check sample concentrate (Step 8.6.1) to
each of four 1-L aliquots of water.
8.6.3 Four aliquots of the well-mixed QC check sample are analyzed

by the same procedures used to analyze actual samples (Section 7.0 of
each of the methods). For volatile organics, the preparation/analysis
process is purge-and-trap/gas chromatography. For semivolatile organics,
the QC check samples must undergo solvent extraction (see Method 3500)
prior to chromatographic analysis.
8.6.4 Calculate the average recovery (x) in ug/L, and the standard
deviation of the recovery (s) in ug/L, for each analyte of interest using
the four results.
8.6.5 For each analyte compare s and :x with the corresponding

acceptance criteria for precision and accuracy, respectively, given the
QC Acceptance Criteria Table at the end of each of the determinative
methods. If s and :x for all analytes of interest meet the acceptance
criteria, the system performance is accept ab 1 e and analysis of actual
samples can begin. If any individual s exceeds the precision limit or
any individual x falls outside the range for accuracy, then the system
performance is unacceptable for that analyte.
NOTE: The large number of analytes in each of the QC Acceptance Criteria

Tables present a substantial probability that one or more will
fail at least one of the acceptance criteria when all analytes of
a given method are determined.
December 1987
8.6.6 When one or more of the analytes tested fail at least one of
the acceptance criteria, the analyst must proceed according to Step
8.6.6.1 or 8.6.6.2.
8.6.6.l Locate and correct the source of the problem and repeat
the test for all analytes of interest beginning with Step 8.6.2.
8.6.6.2 Beginning with Step 8.6.2, repeat the test only for
those analytes that failed to meet criteria. Repeated failure,
however, will confirm a general problem with the measurement system.
If this occurs, locate and correct the source of the problem and
repeat the test for all compounds of interest beginning with Step
8.6.2.
8.7 The laboratory must, on an ongoing basis, analyze a reagent blank and
a matrix spiked replicate for each analytical batch (up to a maximum of 20
samples/batch) to assess accuracy. For soi 1 and waste samples where
detectable amounts of organics are present, replicate samples may be
appropriate in place of spiked replicates. For laboratories analyzing one to
ten samples per month, at least one spiked sample per month is required.
8. 7 .1 The concentration of the spike in the sample should be
determined as follows:
8.7.1.1 If, as in compliance monitoring, the concentration of a
specific analyte in the sample is being checked against a regulatory
concentration limit, the spike should be at that 1 imit or 1 to 5
times higher than the background concentration determined in Step
8.7.2, whichever concentration would be larger.
8.7.1.2 If the concentration of a specific analyte in a water
sample is not being checked against a limit specific to that analyte,
the spike should be at the same concentration as the QC reference
sample (Step 8.6.2) or 1 to 5 times higher than the background
concentration determined in Step 8.7.2, whichever concentration would
be larger. For other matrices, the recommended spiking concentration
is 20 times the PQL.
8.7.1.3 For semivolatile organics, it may not be possible to
determine the background concentration levels prior to spiking (e.g.
maximum holding times will be exceeded). If this is the case, the
spike concentration should be (1) the regulatory concentration limit,
if any; or, if none (2) the larger of either 5 times higher than the
expected background con cent ration or the QC reference sample
concentration (Step 8.6.2). For other matrices, the recommended
spiking concentration is 20 times the PQL.
8.7.2 Analyze one unspiked and one spiked sample aliquot to
determine percent recovery of each of the spiked compounds.
8.7.2.1 Volatile organics - Analyze one 5-ml sample aliquot to
determine the background concentration (B) of each analyte. If
necessary, prepare a new QC reference sample concentrate (Step 8.6.1)
December 1987
appropriate for the background concentration in the sample. Spike a
second 5-ml sample aliquot with 10 ul of the QC reference sample
concentrate and analyze it to determine the concentration after
spiking (A) of each analyte. Calculate each percent recovery (p) as
lOO(A - 8)%/T, where T is the known true value of the spike.
8.7.2.2 Semivolatile organics - Analyze one sample aliquot

(extract of 1-L sample) to determine the background concentration (8)
of each anal yte. If necessary, prepare a new QC reference sample
concentrate (Step 8.6.1) appropriate for the background concentration
in the sample. Spike a second 1-L sample aliquot with 1.0 ml of the
QC reference sample concentrate and analyze it to determine the
concentration after spiking (A) of each analyte. Calculate each
percent recovery (p) as lOO(A - 8)%/T, where T is the known true
value of the spike.
8.7.3 Compare the percent recovery (p) for each analyte in a water
sample with the corresponding criteria presented in the QC Acceptance
Criteria Table found at the end of each of the determinative methods.
These acceptance criteria were calculated to include an allowance for
error in measurement of both the background and spike concentrations,
assuming a spike to background ratio of 5:1. This error will be accounted
for to the extent that the analyst's spike to background ratio approaches
5:1. If spiking was performed at a concentration lower than the QC
reference sample concentration (Step 8.6.2), the analyst must use either
the QC acceptance criteria presented in the Tables, or option al QC
acceptance criteria calculated for the specific spike concentration. To
calculate opt i ona 1 acceptance criteria for the recovery of an ana 1yte:
(l} Calculate accuracy (x'} using the equation found in the Method
Accuracy and Precision as a Function of Concentration Table (appears at
the end of each determinative method}, substituting the spike
concentration (T} for C; (2) calculate overall precision (S') using the
equation in the same Table, substituting x' for x; (3) calculate the range
for recovery at the spike concentration as (lOOx'/T) ± 2.44(100S'/T)%.
8.7.4 If any individual p falls outside the designated range for

recovery, that analyte has failed the acceptance criteria. A check
standard containing each analyte that failed the criteria must be analyzed
as described in Step 8.8.
8.8 If any analyte in a water sample fails the acceptance criteria for
recovery in Step 8. 7, a QC reference standard containing each analyte that
failed must be prepared and analyzed.
NOTE: The frequency for the required analysis of a QC reference standard will
depend upon the number of analytes being simultaneously tested, the
complexity of the sample matrix, and the performance of the laboratory.
If the entire list of analytes given in a method must be measured in the
sample in Step 8. 7, the probability that the analysis of a QC check
standard will be required is high. In this case the QC check standard
should be routinely analyzed with the spiked sample.
December 1987
8.8.l Preparation of the QC check sample - For volatile organics,
add 10 ul of the QC check sample concentrate (Step 8.6.l or 8.7.2) to 5 ml
of water. For semivolatile organics, add 1.0 ml of the QC check sample
concentrate {Step 8.6.1 or 8.7.2) to 1 l of water. The QC check sample
needs only to contain the analytes that failed criteria in the test in
Step 8.7. Prepare the QC check sample for analysis following the
guidelines given in Method 3500 {e.g. purge-and-trap, extraction, etc.).
8.8.2 Analyzed the QC check sample to determine the concentration
measured {A) of each analyte. Calculate each percent recovery {Ps) as 100
(A/T)%, where T is the true value of the standard concentration.
8.8.3 Compare the percent recovery (Ps) for each analyte with the
corresponding QC acceptance criteria found in the appropriate Table in
each of the methods. Only analytes that failed the test in Step 8.7 need
to be compared with these criteria. If the recovery of any such anal yte
fa 11 s outside the designated range, the laboratory performance for that
anal yte is judged to be out of control, and the problem must be
immediately identified and corrected. The result for that analyte in the
unspi ked sample is suspect and may not be reported for regulatory
compliance purposes.
8. 9 As part of the QC program for the laboratory, method accuracy for
each matrix studied must be assessed and records must be maintained. After
the analysis of five spiked samples (of the same matrix type) as in Step 8.7,
calculate the average percent recovery {p) and the standard deviation of the
percent recovery (sp). Express the accuracy assessment as a percent recovery
interval from p - 2sp to p + 2sp. If p = 90% and Sp = 10%, for example, the
accuracy interval is expressed as 70-110%. Update the accuracy assessment for
each analyte on a regular basis (e.g. after each five to ten new accuracy
measurements).
8.10 To determine acceptable accuracy and precision limits for surrogate
standards the following procedure should be performed.
8.10.1 For each sample analyzed, calculate the percent recovery of
each surrogate in the sample.
8.10.2 Once a minimum of thirty samples of the same matrix have
been analyzed, calculate the average percent recovery (p) and standard
deviation of the percent recovery (s) for each of the surrogates.
8.10.3 For a given matrix, calculate the upper and lower control
limit for method performance for each surrogate standard. This should be
done as fo 11 ows:
Upper Control limit (UCL) = p + 3s
Lower Control limit (LCL) = p - 3s
8.10.4 For aqueous and soil matrices, these laboratory established
surrogate control limits should, if applicable, be compared with the
control limits listed in Tables A and 8 of Methods 8240 and 8270,
December 1987
respectively. The limits given in these methods are multi-laboratory
performance based limits for soil and aqueous samples, and therefore, the
single-laboratory limits established in Step 8.10.3 must fall within
those given in Tables A and B for these matrices.
8.10.5 If recovery is not within limits, the following is required.
Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also, check
instrument performance.
Recalculate the data and/or reanalyze the extract if any of
the above checks reveal a problem.
Reextract and reanalyze the sample if none of the above are
a problem or flag the data as "estimated concentration."
8.10.6 At a minimum, each laboratory should update surrogate
recovery limits on a matrix-by-matrix basis, annually.
8.11 It is recommended that the laboratory adopt additional quality
assurance practices for use with this method. The specific practices that are
most productive depend upon the needs of the laboratory and the nature of the
samples. Field duplicates may be analyzed to assess the precision of the
environmental measurements. When doubt exists over the identification of a
peak on the chromatogram, confirmatory techniques such as gas chromatography
with a dissimilar column, specific element detector, or mass spectrometer must
be used. Whenever possible, the laboratory should analyze standard reference
materials and participate in relevant performance evaluation studies.
9.1 The method detection 1 imit (MDL) is defined as the min1mum
concentration of a substance that can be measured and reported with 99%
confidence that the value is above zero. The MDL concentrations listed in the
referring analytical methods were obtained using water. Similar results were
achieved using representative wastewaters. The MDL actually achieved in a
given analysis will vary depending on instrument sensitivity and matrix
effects.
9. 2 Ref er to the determinative method for specific method performance
information.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures
for the Analysis of Pollutants Under the Clean Water Act; Final Rule and
2. U.S. EPA 40 CFR Part 136, Appendix B. "Guidelines Establishing Test
Procedures for the Analysis of Pollutants Under the Clean Water Act; Final
Rule and Interim Final Rule and Proposed Rule," October 26, 1984.
December 1987
3. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, July 1985, Revision.
5. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard
Specification for Reagent Water"; ASTM: Philadelphia, PA, 1985; Dll93-77.
December 1987
METHOO 8000
GAS CHROMATOGRAPHY
Start
7 .... 3
7. l .... C?. 1_, Prepar-e
,...7____
Refe.- to Select 1nter-na1
aeter•1n•t1ve stanaar-ds navlng .>-~~~~-11 cal1br-atlon
•etnod for- s1m1lsr- 1>enav1or- to standards tor-
eatr-ac:t1on comoounos of inter-est eacn oar-a11eter-
pr-oc:edur-e of 1nter-est
7 .... C?
7.2 Refer- 7 .... 3. C?
,____,.to deter-- Iniect ca11br-atlon
•1nat1ve 111atnod stanaar-d; pr-ei:ra.-e
for cleanup and Pr-epar-e cal1br-at1on cur-ve
seperatton cal11>r-at1on or- ce11Dr-at1on factor-
procedures standar-ds
7 .... l
7 .... 3.3 7 .... 2 .3
Establtsn gas
cnr-0111eto;r-eon Inlect
operating par-ameter-s: cal1Dr-at1o,, ver-tfy wor-1<1ng
prepare c:al1bratlon standards: cal1Dr-at1on
stanoar-os calculate RF cu,.ve each a•y
7. 4.3 ... 7.5

Ver-try wor-1<1ng
cal1Dr-•t1on Calculate
curve Or"" RF r-etentton tl"'o
each day wtndows
December 1987
METHOO 8000
GAS CHROMATOGRAPH
(Cont 1nueal
7. 6. l Use 7.6.1 7.6.8

Met ho a .....---~-;;::;;"; Introduce i-----"C•llbrete
3810 or 3820 ~ co•s:iounas 1nto syste"'
es screen1ng ges c,,rometo- tmmedletely
tecl'\n 1 Que. greo,, by d1rect pr 1or to
1t necessery 1n)ectlon en•lyses
7.6.1 Introauce
1----
lnto
come>ounas
a,,ro-
ges
7.6.• In1ect
sample
extrect us1ng
i----
7.6.9
Esteb l lsh
ly Ciel
••togreph by solvent flush retention t1me
ourge-ena-trep tecl'ln1oue; w1naows for
(Met,,Od 5030) record volume each enelyte
7.6.5 7.7
Oo
chrometogrephy
01lute extract syste"'
end re ene l y z:e 111e 1ntenence
1f neeaed
7.8
7.6.6 Calculate
concentretlon of
eech enelyte. uslng
Oo further epproorlete formul•
cleenup for metrlx ena type
of stenderd
Stop
December 1987
METHOD 80108
HALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY

1.1 Method 8010 is used to determine the concentration of various
volatile halogenated organic compounds. The following compounds can be
determined by this method:
Aggrogriate Technigue
Direct
Compound Name CAS No. 8 Purge-and-Trap Injection
Allyl chloride 107-05-1 b b

Benzyl chloride 100-44-7 pp b
Bis(2-chloroethoxy)methane 111-91-1 pp pc
Bis(2-chloroisopropyl) ether 39638-32-9 b b
Bromoacetone 598-31-2 pp b
Bromobenzene 108-86-1 b b
Bromodichloromethane 75-27-4 b b
Bromoform 75-25-2 b b
Bromomethane 74-83-9 b b
Carbon tetrachloride 56-23-5 b b
Chloroacetaldehyde 107-20-0 b b
Chlorobenzene 108-90-7 b b
Chloroethane 75-00-3 b b
2-Chloroethanol 107-07-03 pp b
2-Chloroethyl vinyl ether 110-75-8 b b
Chloroform 67-66-3 b b
1-Chlorohexane 544-10-5 pc pc
Chloromethane 74-87-3 b b
Chloromethyl methyl ether 107-30-2 pp pc
Chloroprene 126-99-8 b b
4-Chlorotoluene 106-43-4 b b
Dibromochloromethane 124-48-1 b b
1,2-Dibromo-3-chloropropane 96-12-8 b b
Dibromomethane 74-95-3 b b
1,2-Dichlorobenzene 95-50-1 b b
1,4-Dichloro-2-butene 764-41-0 b b
Dichlorodifluoromethane 75- 71-8 b b
1,1-Dichloroethane 75-34-3 b b
1,1-Dichloroethene 75-35-4 b b
trans-1,2-Dichloroethene 156-60-5 b b
Dichloromethane 75-09-2 b b
1,2-Dichloropropane 78-87-5 b b
l,3-Dichloro-2-propanol 96-23-1 pp b
cis-1,3-Dichloropropene 10061-01-5 b b
trans-1,3-Dichloropropene 10061-02-6 b b
November 1992
Appropriate Technique
Direct
Compound Name CAS No. a Purge-and-Trap Injection
Epichlorhydrin 106-89-8 pp b
Ethylene dibromide 106-93-4 b b
Methyl iodide 74-88-4 pp b
1,1,2,2-Tetrachloroethane 79-34-5 b b
Tetrachloroethene 127-18-4 b b
1,1,1-Trichloroethane 71-55-6 b b
Trichloroethene 79-01-6 b b
Trichlorofluoromethane 75-69-4 b b
1,2,3-Trichloropropane 96-18-4 b b
Vinyl Chloride 75-01-4 b b
a Chemical Abstract Services Registry Number

b Adequate response using this technique
pp Poor purging efficiency, resulting in high EQLs
pc Poor chromatographic performance.
1.2 Table 1 indicates compounds that may be analyzed by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit for other matrices.

2.1 Method 8010 provides gas chromatographic conditions for the
detection of halogenated volatile organic compounds. Samples can be introduced
into the GC using direct injection or purge-and-trap (Method 5030). Ground water
samples must be analyzed using Method 5030. A temperature program is used in the
gas chromatograph to separate the organic compounds. Detection is achieved by
a electrolytic conductivity detector (HECD).
2.2 The method provides an optional gas chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.
3.0 INTERFERENCES
container septum during shipment and storage. A trip blank prepared from
November 1992
4.1 Gas chromatograph
4.1.1 Gas chromatograph - analytical system complete with gas
chromatograph suitable for on-column injections or purge-and-trap sample
introduction and all required accessories, including detector, analytical
columns, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4 .1. 2 Co 1umns
4.1.2.1 Column 1 - 8 ft x 0.1 in. ID stainless steel or
glass column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
4.1.2.2 Column 2 - 6 ft x 0.1 in. ID stainless steel or
glass column packed with chemically bonded n-octane on Porasil-C
100/120 mesh (Durapak) or equivalent.
4.1.3 Detector - Electrolytic conductivity (HECD).
4.2 Sample introduction apparatus, refer to Method 5030 for the
appropriate equipment for sample introduction purposes.
4.3 Syringes, 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.
4.4 Volumetric flask, Class A, Appropriate sizes with ground glass
stoppers.
4.5 Microsyringe, 10 and 25 µL with a 0.006 in. ID needle (Hamilton 702N
or equivalent) and a 100 µL.
5. 0 REAGENTS
otherwise indicated, it is intended that all reagents shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5.3 Methanol, CH3 0H. Pesticide quality or equivalent. Store away from
other solvents.
5.4 Stock standards - Stock solutions may be prepared from pure standard
materials or purchased as certified solutions. Prepare stock standards in
November 1992
methanol using assayed liquids or gases, as appropriate. Because of the toxicity
of some of the organohalides, primary dilutions of these materials should be
prepared in a hood.
5.4.l Place about 9.8 ml of methanol in a 10 ml tared ground glass
stoppered volumetric flask. Allow the flask to stand, unstoppered, for
about 10 minutes until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.0001 g.
5.4.2 Add the assayed reference material, as described below.
5.4.2.1 Liquids. Using a 100 µL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5. 4. 2. 2 Gases. To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane,
chloromethane, dichlorodifluoromethane, trichlorofluoromethane,
vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas rapidly
dissolves in the methanol. This may also be accomplished by using
a lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600). Attach Teflon tubing to the side-arm relief valve and
direct a gentle stream of gas into the methanol meniscus.
5.4.3 Reweigh, dilute to volume, stopper, and then mix by inverting
the flask several times. Calculate the concentration in milligrams per
liter (mg/L) from the net gain in weight. When compound purity is assayed
to be 96% or greater, the weight may be used without correction to
calculate the concentration of the stock standard. Commercially prepared
stock standards may be used at any concentration if they are certified by
the manufacturer or by an independent source.
5.4.4 Transfer the stock standard solution into a bottle with a
Teflon lined screw-cap. Store, with minimal headspace, at -10°C to -20°C
and protect from light.
5. 4. 5 Prepare fresh standards every 2 months, for gases or for
reactive compounds such as 2-chloroethyl vinyl ether. All other standards
must be replaced after 6 months, or sooner if comparison with check
standards indicates a problem.
5.5 Secondary dilution standards. Using stock standard solutions,
prepare secondary dilution standards in methanol, as needed, containing the
compounds of interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Section 5.6 will bracket the working range of the
analytical system. Secondary dilution standards should be stored with minimal
headspace for volatiles and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
November 1992
5.6 Calibration standards. Prepare calibration standards in
organic-free reagent water from the secondary dilution of the stock standards,
at a minimum of five concentrations. One of the concentrations should be at a
concentration near, but above, the method detection 1imit. The remaining
concentrations should correspond to the expected range of the concentrations
found in rea 1 samp 1es or should define the working range of the GC. Each
standard should contain each analyte for detection by this method (e.g. some or
all of the compounds listed in Table 1 may be included). In order to prepare
accurate aqueous standard solutions, the following precautions must be observed.
5.6.1 Do not inject more than 20 µl of alcoholic standards into
100 ml of water.
5.6.2 Use a 25 µl Hamilton 702N microsyringe or equivalent
(variations in needle geometry will adversely affect the ability to
deliver reproducible volumes of methanolic standards into water).
5.6.3 Rapidly inject the alcoholic standard into the filled
volumetric flask. Remove the needle as fast as possible after injection.
5.6.4 Mix aqueous standards by inverting the flask three times only.
5.6.5 Fill the sample syringe from the standard solution contained
in the expanded area of the flask (do not use any solution contained in
the neck of the flask}.
5.6.6 Never use pipets to dilute or transfer samples or aqueous
standards.
5.6.7 Aqueous standards are not stable and should be discarded after
one hour, unless properly sealed and stored. The aqueous standards can
be stored up to 24 hours, if held in sealed vials with zero headspace.
5.7 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds of interest. The analyst
must further demonstrate that the measurement of the internal standard is not
affected by method or matrix interferences. Because of these limitations, no
internal standard can be suggested that is app 1icab1 e to a11 samples. The
compounds recommended for use as surrogate spikes (Section 5.8) have been used
successfully as internal standards, because of their generally unique retention
times.
5.7.l Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Section 5.5.
5.7.2 Prepare a spiking solution containing each of the internal
standards using the procedures described in Sections 5.4 and 5.5. It is
recommended that the secondary dilution standard be prepared at a
concentration of 15 ng/ µl of each i nterna 1 standard compound. The
addition of 10 µl of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 µg/l.
November 1992
5.7.3 Analyze each calibration standard according to Section 7.0,
adding 10 µL of internal standard spiking solution directly to the
syringe.
5.8 Surrogate standards - The analyst should monitor both the
performance of the anal yt i cal system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and
organic-free reagent water blank with surrogate halocarbons. A combination of
bromochloromethane, bromochlorobenzene and bromofluorobenzene is recommended to
encompass the range of temperature program used in this method. From stock
standard solutions prepared as in Section 5.4, add a volume to give 750 µg of
each surrogate to 45 ml of organic-free reagent water contained in a 50 ml
volumetric flask, mix, and dilute to volume for a concentration of 15 ng/µL.
Add 10 µL of this surrogate spiking solution directly into the 5 ml syringe with
every sample and reference standard analyzed. If the internal standard
calibration procedure is used, the surrogate compounds may be added directly to
the internal standard spiking solution (Section 5.7.2).

Section 4.1.
7. 0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph using
either direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-concentration contaminated soils and
sediments. For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatographic conditions (Recommended)
7.2.1 Column 1:
Helium flow rate= 40 ml/min
Temperature program:
Initial temperature = 45°C, hold for 3 minutes
Program = 45°C to 220°C at 8°C/mi n
Final temperature 220°C, hold for 15 minutes.
7.2.2 Column 2:
Helium flow rate= 40 ml/min
Temperature program:
Initial temperature = 50°C, hold for 3 minutes
Program = 50°C to 170°C at 6°C/min
Final temperature = 170°C, hold for 4 minutes.
7. 3 Calibration. The procedure for internal or external calibration may
be used. Refer to Method 8000 for a description of each of these procedures. Use
November 1992
Table 1 and Table 2 for guidance on selecting the lowest point on the calibration
curve.
7.3.1 Calibration must take place using the same sample introduction
method that will be used to analyze actual samples (see Section 7.4.1).
7.4.1 Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap} or the direct injection method (see
Section 7.4.1.1). If the internal standard calibration technique is used,
add 10 µL of internal standard to the sample prior to purging.
7.4.1.1 In very limited applications (e.g. aqueous process
wastes) direct injection of the sample onto the GC column with a
10 µL syringe may be appropriate. The detection limit is very high
(approximately 10,000 µg/L) therefore, it is only permitted where
concentrations in excess of 10,000 µg/L are expected or for water-
soluble compounds that do not purge. The system must be calibrated
by direct injection (bypassing the purge-and-trap device).
7.4.2 Method 8000 provides instructions on the analysis sequence,
appropriate dilutions, establishing daily retention time windows, and
identification criteria. Include a mid-concentration standard after each
group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
columns for a number of organic compounds analyzable using this method.
An example of the separation achieved by Column 1 is shown in Figure 1.
7.4.4 Record the sample volume purged or injected and the resulting
peak sizes (in area units or peak heights).
7.4.5 Refer to Method 8000 for guidance on calculation of
concentration.
7.4.6 If analytical interferences are suspected, or for the purpose
of confirmation, analysis using the second GC column is recommended.
7.4.7 If the response for a peak is off-scale, prepare a dilution
of the sample with organic-free reagent water. The dilution must be
performed on a second aliquot of the sample which has been properly sealed
and stored prior to use.
8.0 QUALITY CONTROL

Method 8000 for gas chromatographic procedures. Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.
8.2 Quality control required to validate the GC system operation is
found in Method 8000.
November 1992
8.2.1 The quality control check sample concentrate (Method 8000)
should contain each analyte of interest at a concentration of 10 mg/L in
methanol.
8.2.2 Table 3 indicates the calibration and QC acceptance criteria
for this method. Table 4 gives method accuracy and precision as functions
of concentration for the analytes of interest. The contents of both
Tables should be used to evaluate a laboratory's ability to perform and
generate acceptable data by this method.
8.3 Calculate surrogate standard recovery on all samples, blanks, and
spikes. Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).
8.3.1 If recovery is not within limits, the following is required:
• Check to be sure that there are no errors in
calculations, surrogate solutions and internal standards. Also,
check instrument performance.
• Recalculate the data and/or re-analyze the sample if
any of the above checks reveal a problem.
• Re-extract and re-analyze the sample if none of the
above are a problem or flag the data as "estimated concentration".

9.1 This method was tested by 20 laboratories using organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 8.0-500 µg/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the analyte, and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.
9.2 The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.
10. 0 REFERENCES
1. Bellar, T.A.; Lichtenberg, J.J. ~Amer. Water Works Assoc. 1974, 66(12),
pp. 739-744.
2. Bellar, T.A.; Lichtenberg, J.J., Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds, Measurement of Organic Pollutants in Water and Wastewater; Van
Hall, Ed.; ASTM STP 686, pp 108-129, 1979.
3. "Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeabl es and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane"; report for EPA
Contract 68-03-2635 (in preparation).
November 1992
,. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act: Final Rule and Interim
Final Rule and Proposed Rule", October 26, 1984.
>. "EPA Method Validation Study 23, Method 601 (Purgeable Halocarbons)";
Report for EPA Contract 68-03-2856 (in preparation).
>. Gebhart, J.E., S.V. Lucas, S.J. Naber, A.M. Berry, T.H. Danison and H.M.
Burkholder, "Validation of SW-846 Methods 8010, 8015, and 8020"; Report
for EPA Contract 68-03-1760, Work Assignment 2-15; US EPA, EMSL-
Cincinnati, 1987.
November 1992
TABLE 1.
CHROMATOGRAPHIC CONDITIONS ANO METHOD DETECTION LIMITS
FOR HALOGENATED VOLATILE ORGANICS
Method
CAS Retention Ti me Detection
Registry (minutes) Limita
Compound Number Column 1 Column 2 (µg/L)
Ally chloride 107-05-1 10 .17 (b) (b)

Benzyl chloride*,c 100-44-7 30.29 ( b) (b)
Bis(2-chloroethoxy)methane* 111-91-1 38.60 ( b) (b)
Bis(2-chloroisopropyl) ether* 39638-32-9 34.79 ( b) (b)
Bromobenzene 108-86-1 29.05 ( b) (b)
BromodichJoromethane 75-27-4 15.44 14.62 0.002
Bromoform 75-25-2 21.12 19.17 0.020
Bromomethane* * 74-83-9 2.90 7.05 0.030
Carbon tetrachloride 56-23-5 14.58 11.07 0.003
Chloroacetaldehyde* 107-20-0 ( b) ( b) ( b)
Chlorobenzene* 108-90-7 25.49 18.83 0.001
Chloroetha!Je 75-00-3 5.18 8.68 0.008
Chloroform 67-66-3 12.62 12.08 0.002
1-Chlorohexane 544-10-5 26.26 (b) (b)
2-Chloroethyl.vinyl ether* 110-75-8 19.23 (b) 0.130
Chloromethane 74-87-3 1.40 5.28 0.010
Chloromethyl methyl ether* 107-30-2 8.88 ( b) (b)
4-Chlorotoluene 106-43-4 34.46 ( b) (b)
Dibromochloromethane 124-48-1 18.22 16.62 (b)
.
l,2-D1bromo-3-fhloropropane * 96-12-8 28.09 ( b) 0.030
Dibromomethane 74-95-3 13.83 14.92 (b)
.
1,2-01chlorobenzene * 95-50-1 37.96 23.52 (b)
.
l,3-01chlorobenzene * 541-73-1 36.88 22.43 (b)
1,4-Dichlorobenzene* 106-46-7 38.64 22.33 (b)
1,4-0ichloro-2-butene 764-41-0 23.45 ( b) (b)
Di ch 1orod i fl uoromethane*,d 75-71-8 3.68 ( b) (b)
.
l,l-D1chloroethane * 75-34-3 11. 21 12.57 0.002
l,2-D1chloroethane *
. 107-06-2 13 .14 15.35 0.002
.
l,l-D1chloroethene * 75-35-4 10.04 7.72 0.003
trans-1,2-Dichl~roethene* 156-60-5 11.97 9.38 0.002
Dichloromethane 75-09-2 7.56 10.12 (b)
.
1,2-01chloropropane * 78-87-5 16.69 16.62 (b)
trans-1,3-Dichloropropene* 10061-02-5 16.97e 16.60 0.340
Ethylene dibromide * 106-93-4 19.59 ( b) (b)
1,1,2,2-Tetrachloroethane. 79-34-5 23.12 (b) 0.010
1,1,1,2-Tetrachloroethane 630-20-6 21.10 21. 70 (b)
Tetrachloroethene * 127-18-4 23.05 14.97 0.001
1,1,1-Trichloroethane 71-55-6 14.48 13 .10 0.003
1,1,2-Trichloro~thane* 79-00-5 18.27 18.07 0.007
Trichloroethene 79-01-6 17.40 13.12 0.001
Trichlorofluoromethane* 75-69-4 9.26 ( b) (b)
1,2,3-Trichlor~propane* 96-18-4 22.95 ( b) (b)
Vinyl Chloride 75-01-4 3.25 5.28 0.006
80108 - 10 Revision 2
November 1992
TABLE 1.
Continued
a = Using purge-and-trap method (Method 5030)

b = Not determined
* = Appendix VIII compounds
c = Demonstrated very erratic results when tested by purge-and-trap
d = See Section 4.10.2 of Method 5030 for guidance on selection of trapping
material
e = Estimated retention time
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICESa
Matrix Factorb
Ground water 10
Low-concentration soil 10
Water miscible liquid waste 500
High-concentration soil and sludge 1250
Non-water miscible waste 1250
a Sample EQLs are highly matrix-dependent. The EQLs listed herein

are provided for guidance and may not always be achievable.
b EQL = [Method detection limit (Table 1)] X [Factor (Table 2)].
For non-aqueous samples, the factor is on a wet-weight basis.
November 1992
TABLE 3.
CALIBRATION AND QC ACCEPTANCE CRITERIA8
Range Limit Rangg Range

for Q for S for x p, ps
Analyte (µg/L) (µg/L) (µg/L) (%)
Bromodichloromethane 15.2-24.8 4.3 10.7-32.0 42-172

Bromoform 14.7-25.3 4.7 5.0-29.3 13-159
Bromomethane 11. 7-28. 3 7.6 3.4-24.5 D-144
Carbon tetrachloride 13.7-26.3 5.6 11.8-25.3 43-143
Chlorobenzene 14.4-25.6 5.0 10.2-27.4 38-150
Chloroethane 15.4-24.6 4.4 11.3-25.2 46-137
2-Chloroethylvinyl ether 12.0-28.0 8.3 4.5-35.5 14-186
Chloroform 15.0-25.0 4.5 12.4-24.0 49-133
Chloromethane 11. 9-28.1 7.4 D-34.9 D-193
Dibromochloromethane 13.1-26.9 6.3 7.9-35.1 24-191
1,2-Dichlorobenzene 14.0-26.0 5.5 1. 7-38. 9 D-208
1,3-Dichlorobenzene 9.9-30.1 9.1 6.2-32.6 7-187
1,1-Dichloroethane 16.8-23.2 3.2 11.2-24.6 47-132
1,2-Dichloroethane 14.3-25.7 5.2 13.0-26.5 51-147
1,1-Dichloroethene 12.6-27.4 6.6 10.2-27.3 28-167
trans-1,2-Dichloroethene 12.8-27.2 6.4 11.4-27.1 38-155
Dichloromethane 15.5-24.5 4.0 7.0-27.6 25-162
1,2-Dichloropropane 14.8-25.2 5.2 10.1-29.9 44-156
cis-1,3-Dichloropropene 12.8-27.2 7.3 6.2-33.8 22-178
trans-1,3-Dichloropropene 12.8-27.2 7.3 6.2-33.8 22-178
1,1,2,2-Tetrachloroethane 9.8-30.2 9.2 6.6-31.8 8-184
Tetrachloroethene 14.0-26.0 5.4 8.1-29.6 26-162
1,1,1-Trichloroethane 14.2-25.8 4.9 10.8-24.8 41-138
1,1,2-Trichloroethane 15.7-24.3 3.9 9.6-25.4 39-136
Trichloroethene 15.4-24.6 4.2 9.2-26.6 35-146
Trichlorofluoromethane 13.3-26.7 6.0 7.4-28.1 21-156
Vinyl chloride 13.7-26.3 5.7 8.2-29.9 28-163
Q Concentration measured in QC check sample, in µg/L.

s Standard deviation of four recovery measurements, in µg/L.
x Average recovery for four recovery measurements, in µg/L.
Percent recovery measured.
D = Detected; result must be greater than zero.
a
Criteria from 40 CFR Part 136 for Method 601 and were calculated assuming
a QC check sample concentration of 20 µg/L.
80108 - 12 Revision 2
November 1992
TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION 8
Accuracy, as Single analyst Overall

recovery, x' precision, s/ precision,
Analyte (µ.g/L) (µ.g/L) S' (µ.g/L)
Bromodichloromethane l.12C-l.02 O.llX+0.04 0. 20X+l. 00

Bromoform 0.96C-2.05 0.12X+0.58 0.21X+2.41
Bromomethane 0. 76C-l. 27 0.28X+0.27 0.36X+0.94
Carbon tetrachloride 0. 98C-l. 04 0.15X+0.38 0.20X+0.39
Chlorobenzene 1. OOC-1. 23 0.15X-0.02 0.18X+l.21
Chloroethane 0. 99C-l. 53 0.14X-0.13 0.17X+0.63
2-Chloroethyl vinyl etherb l.OOC 0.20X 0.35X
Chloroform 0.93C-0.39 0.13X+0.15 0.19X-0.02
Chloromethane 0. 77C+0.18 0.28X-0.31 0. 52X+l. 31
Dibromochloromethane 0.94C+2.72 0.llX+l.10 0.24X+l.68
1,2-Dichlorobenzene 0. 93C+l. 70 0.20X+0.97 0.13X+6.13
1,3-Dichlorobenzene 0.95C+0.43 0.14X+2.33 0.26X+2.34
1,4-Dichlorobenzene 0.93C-0.09 0.15X+0.29 0.20X+0.41
1,1-Dichloroethane 0.95C-l.08 0.08X+0.17 0.14X+0.94
1,2-Dichloroethane 1. 04C-l. 06 O. llX+O. 70 0.15X+0.94
1,1-Dichloroethene 0.98C-0.87 0.21X-0.23 0.29X-0.04
trans-1,2-Dichloroethene 0.97C-0.16 0. llX+l. 46 0.17X+l.46
Dichloromethane 0.91C-0.93 O. llX+0.33 0. 21X+l. 43
1,2-Dichloropropaneb l.OOC 0.13X 0.23X
cis-1,3-Dichloropropeneb l.OOC 0.18X 0.32X
trans-1,3-Dichloropropeneb l.OOC 0.18X 0.32X
1,1,2,2-Tetrachloroethane 0.95C+0.19 0.14X+2.41 0.23X+2.79
Tetrachloroethene 0.94C+0.06 0.14X+0.38 0.18X+2.21
1,1,1-Trichloroethane 0.90C-0.16 0.15X+0.04 0.20X+0.37
1,1,2-Trichloroethane 0.86C+0.30 0.13X-0.14 0.19X+0.67
Trichloroethene 0.87C+0.48 0.13X-0.03 0.23X+0.30
Trichlorofluoromethane 0.89C-0.07 0.15X+0.67 0.26X+0.91
Vinyl chloride 0.97C-0.36 0 .13X+O. 65 0.27X+0.40
x' Expected recovery for one or more measurements of a sample containing

a concentration of C, in µ.g/L.
S I=
r
Expected single analyst standard deviation of measurements at an
average concentration of x, in µ.g/L.
S' Expected i nterl aboratory standard deviation of measurements at an
average concentration found of x, in µ.g/L.
C True value for the concentration, in µ.g/L.
X Average recovery found for measurements of samples containing a
concentration of C, in µ.g/L.
a From 40 CFR Part 136 for Method 601.
b Estimates based upon the performance in a single laboratory.
80108 - 13 Revision 2
November 1992
FIGURE 1.
GAS CHROMATOGRAM OF HALOGENATED VOLATILE ORGANICS
C.-.-: "sP ""'°-~ ..

..... _, 4..C-J ......_......_. . . nooc
Oetec-· Hell 100 A floldrefyttc C....Ctlwlty
•i
.
5
E
0
C;
6
!c
!0
0
5
6
...
•
0 J
• • 10 11 14 1• 11 20 n 14 :re :re JO ,, ,.. ,.
80108 - 14 Revision 2
November 1992
METHOD 80108
HALOGENATED VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
Start
?.4..4 Reco:z::d
7.2 Set volume purged
chxomatograph1.c
conditi()n• 1.njected.and
peak sizes.
7.4.5 Calcul.ate
7. 3 Calibrate concentration•
(rarer to (rerer to
NeChod •ooo) NeChod 8000).
7.4..1 Introduce 7.4. 6 Analyse

•a.rnpl.e into GC 7 4.. G Axe •ample uaing
by direct int4111rferences second ac
inJllCtion or suspected? column.
pu:rQ"e·and~ t:r::ap.
7.4.2 Pellow 7.4.7 Dilute

lleCbod 8000 eecoad
t'or analysis reapona@ a11Quot or
sequence, scale? aample.
etc.
•o
Stop
80108 15 Revision 2
November 1992
Method 8011
1.2-DIBROMOETHANE AND 1.2-DIBROM0-3-CHLOROPROPANE IN WATER
BY MICROEXTRACTION AND GAS CHROMATOGRAPHY

I.I This method is applicable to the determination of the followi.ng
compounds in drinking water and ground water:
Chemical Abstracts Service
Analyte Registry Number
1,2-Dibromoethane (EDB) 106-93-4
1,2-Dibromo-3-chloropropane (DBCP) 96-12-8
1.2 For compounds other than the above mentioned analytes, or for other
matrices, the 1aboratory must demonstrate the usefulness of the method by
collecting precision and accuracy data on actual samples and provide
qualitative confirmation of results by gas chromatography/mass spectrometry
(GC/MS).
1.3 The experimentally determined method detection limits (MDL) for EDB
and DBCP were calculated to be 0. 01 ug/L. The method has been shown to be
useful for these analytes over a concentration range from approximately 0.03
to 200 ug/L. Actual detection limits are highly dependent upon the
characteristics of the gas chromatographic system, sample matrix, and
calibration.
1.4 This method is restricted to use by or under the Supervision of
analysts experienced in the use of gas chromatography and in the
interpretation of gas chromatograms. Each analyst must demonstrate the ability
to generate acceptable results with this method using the procedure described
in Step 8.2.
1.5 1,2-Dibromoethane and 1,2-Dibromo-3-chloropropane have been
tentatively classified as known or suspected human or mammalian carcinogens.
Pure standard materials and stock standard solutions of these compounds should
be handled in a hood. A NIOSH/MESA approved toxic gas respirator should be
worn when the analyst handles high concentrations of these toxic compounds.
2.1 Thirty five ml of sample are extracted with 2 ml of hexane. Two ul
of the extract are then injected into a gas chromatograph equipped with a
linearized electron capture detector for separation and analysis. Aqueous
matrix spikes are extracted and analyzed in an identical manner as the samples
in order to compensate for possible extraction losses.
2.2 The extraction and analysis time is 30 to 50 minutes per sample
depending upon the analytical conditions chosen. See Table 1 and Figure 1.
8011 - 1 Revision 0
December 1987
2.3 Confirmatory evidence is obtained using a different column (Table 1).
3.0 INTERFERENCES
3.1 Impurities contained in the extracting solvent (hexane) usually
account for the majority of the analytical problems. Reagent blanks should be
analyzed on each new bottle of hexane before use. Indirect daily checks on
the hexane are obtained by monitoring the calibration and reagent blanks.
Whenever an interference is noted in the method or instrument blank, the
laboratory should reanalyze the hexane. Low level interferences generally can
be removed by distillation or column chromatography however, it is generally
more economical to obtain a new source of hexane solvent. Interference-free
hexane is defined as containing less than 0.01 ug/L of the analytes. Protect
interference-free hexane by storing it in an area known to be free of
organochlorine solvents.
3.2 Several instances of accidental sample contamination have been
attributed to diffusion of volatile organics through the septum seal into the
sample bottle during shipment and storage. Field blanks must be used to
monitor for this problem.
3.3 This liquid/liquid extraction technique extracts a wide boiling range
of non-polar organic compounds and, in addition, extracts some polar organic
compounds.
3.4 EDB at low concentrations may be masked by very high levels of
dibromochloromethane (DBCM), a common chlorinated drinking water contaminant,
when using the confirmation column.
4.1 Microsyringe - 10, 25, and 100 ul with a 2 in x 0.006 in needle
(Hamilton 702N or equivalent).
4.2 Gas Chromatograph
4.2.1 The GC must be capable of temperature programming and should
be equipped with a linearized electron capture detector and a capillary
column splitless injector.
4.2.2 Two gas chromatography columns are recommended. Column A is a
highly efficient column that provides separations for EDB and DBCP without
interferences from tri ha l omethanes. Column A should be used as the
primary analytical column unless routinely occurring analytes are not
adequately resolved. Column B is recommended for use as a confirmatory
column when GC/MS confirmation is not available. Retention times for EDB
and DBCP on these columns are presented in Table I.
4.2.3 Column A - 0.32 mm i.d. x 30 m fused silica capillary with
dimethyl silicone mixed phase (Durawax-DX 3, 0.25 um film, or equivalent).
The linear velocity of the helium carrier gas is established at 25 cm/sec.
The column temperature is programmed to hold at 40°C for 4 minutes, then
increase to 190°C at 8°C/min, and hold at 190°C for 25 minutes or until
8011 - 2 Revision 0
December 1987
all expected compounds have eluted. Injector temperature: 200°C.
Detector temperature: 290°C. See Figure 1 for a sample chromatogram and
Table 1 for retention data.
4.2.4 Column B (confirmation column) - 0.32 mm i.d. x 30 m fused
silica capillary with methyl polysiloxane phase (DB-1, 0.25 um film, or
equivalent). The linear velocity of the helium carrier gas is established
at 25 cm/sec. The column temperature is programmed to hold at 40°C for
4 minutes, then increase to 270°C at l0°C/min, and hold at 270°C for
10 minutes or until all expected compounds have eluted. Injector
temperature: 200°C. Detector temperature: 290°C. See Table 1 for
retention data.
5.0 REAGENTS
5.1 Hexane, C6H14. UV grade (Burdick and Jackson #216 or equivalent).
5.2 Methyl alcohol, CH30H. Demonstrated to be free of analytes.
5.3 Sodium chloride, NaCl. Pulverize a batch of NaCl and place it in a
muffle furnace at room temperature. Increase the temperature to 400°C for
30 minutes. Place it in a bottle and cap.
5.4 1,2-Dibromoethane (993), C2H4Br2, (Aldrich Chemical Company).
5.5 1,2-Dibromo-3-chloropropane (99.43), C3H5Br2Cl, (AMVAC Chemical
Corporation, Los Angeles, California).
the method refer to ASTM Type II unless otherwise specified. Must be free of
interferents at the method detection limit (MDL) of the analytes of interest.
ASTM Type II water is further purified by any of the following techniques:
5.6.1 Water may be generated by passing tap water through a carbon
filter bed containing about 453 g of activated carbon (Calgon Corp.,
Filtrasorb-300 or equivalent).
5.6.2 A water purification system (Millipore Milli-Q Plus with the
Organex-Q cartridge or equivalent) may be used to generate water.
5. 6. 3 Water may al so be prepared by boiling water for 15 minutes.
Subsequently, while maintaining the temperature at 90°C, bubble a
contaminant-free inert gas through the water for 1 hour. While it is still
hot, transfer the water to a narrow-mouth screw-cap bottle and seal with a
Teflon lined septum and cap.
5.7 Stock standards - These solutions may be purchased as certified
solutions or prepared from pure standards using the following procedures:
5.7.1 Place about 9.8 ml of methanol into a 10-ml ground glass
about 10 minutes and weigh to the nearest 0.1 mg.
8011 - 3 Revision 0
December 1987
5.7.2 Use a 25-uL syringe and immediately add two or more drops
( :.:: 10 uL) of standard to the fl ask. Be sure that the standard fa 11 s
directly into the alcohol without contacting the neck of the flask.
5.7.3 Reweigh, dilute to volume, stopper, then mix by inverting the
flask several times. Calculate the concentration in micrograms per
microliter from the net gain in weight (approximately 1000 ug/L).
5.7.4 Store stock standards in 15-mL bottles equipped with PTFE
lined screw-caps. Stock standards are stable for at least four weeks when
stored at 4°C and away from light.
5.8 Intermediate standard - Use stock standards to prepare an
intermediate standard that contains both analytes in methanol. The
intermediate standard should be prepared at a concentration that can be easily
diluted to prepare aqueous calibration standards that will bracket the working
concentration range. Store the intermediate standard with minimal heads pace
and check frequently for signs of deterioration or evaporation, especially
just before preparing calibration standards. The storage time described for
stock standards also applies to the intermediate standard.
5.9 Quality control (QC) reference sample - Prepare a QC reference sample
concentrate at 0. 25 ug/mL of both ana lytes from standards from a different
source than the standards used for the stock standard.
determination.
5.11 Check standard - Add an appropriate volume of the intermediate
standard to an aliquot of water in a volumetric flask. Do not add less than
20 uL of an alcoholic intermediate standard to the water or poor precision
will result. Use a 25-ul microsyringe and rapidly inject the alcoholic
intermediate standard into the expanded area of the almost filled volumetric
flask. Remove the needle as quickly as possible after injection. Mix by
inverting the flask several times. Discard the contents contained in the neck
of the flask. Aqueous calibration standards should be prepared every 8 hours.
6.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE
4.1.
7.0 PROCEDURE
7.1 Calibration
7.1.l At least five calibration standards are needed. One should
contain EDB and DBCP at a concentration near, but greater than, the method
8011 - 4 Revision 0
December 1987
detection limit (Table 1) for each compound. The others should be at
concentrations that bracket the range expected in samples. For example,
if the MDL is 0.01 ug/L, and a sample expected to contain approximately
0.10 ug/L is to be analyzed, aqueous calibration standards should be
prepared at concentrations of 0.03 ug/L, 0.05 ug/L, 0.10 ug/L, 0.15 ug/L,
and 0.20 ug/L.
7.1.2 Analyze each calibration standard and tabulate peak height or
area response versus the concentration in the standard. Prepare a
calibration curve for each compound. Alternatively, if the ratio of
response to concentration (calibration factor) is a constant over the
working range (< 10% relative standard deviation), linearity can be
assumed and the average ratio or calibration factor can be used in place
of a calibration curve.
7.2 Sample preparation
7. 2 .1 Remove samples and standards from storage and a11 ow them to
reach room temperature.
7.2.2 For samples and field blanks contained in 40-ml bottles,
remove the container cap. Discard a 5-ml volume using a 5-ml transfer
pipet. Replace the container cap and weigh the container with contents to
the nearest 0.1 g and record this weight for subsequent sample volume
determination.
7. 2. 3 For calibration standards, check standards, QC reference
samples, and blanks, measure a 35-ml volume using a 50-ml graduated
cylinder and transfer it to a 40-ml sample container.
7.3 Extraction
7.3.1 Remove the container cap and add 7 g of NaCl to all samples.
7.3.2 Recap the sample container and dissolve the NaCl by shaking by
hand for about 20 seconds.
7.3.3 Remove the cap and using a transfer pipet, add 2.0 ml of
hexane. Recap and shake vigorously by hand for 1 minute. Allow the water
and hexane phases to separate. If stored at this stage, keep the
container upside down.
7.3.4 Remove the cap and carefully transfer a sufficient amount
(0.5-1.0 ml) of the hexane layer into a vial using a disposable glass
pi pet.
7.3.5 Transfer the remaining hexane phase, being careful not to
include any of the water phase, into a second vial. Reserve this second
vial at 4°C for reanalysis if necessary.
8011 - 5 Revision 0
December 1987
7.4 Analysis
7.4.1 Transfer the first sample vial to an autosampler set up to
inject 2.0 ul portions into the gas chromatograph for analysis.
Alternately, 2 ul portions of samples, blanks and standards may be
manually injected, although an auto sampler is strongly recommended.
7.5 Determination of sample volume
7.5.1 For samples and field blanks, remove the cap from the sample
container. Discard the remaining sample/hexane mixture. Shake off the
remaining few drops using short, brisk wrist movements. Reweigh the empty
container with original cap and calculate the net weight of sample by
difference to the nearest 0.1 g. This net weight is equivalent to the
volume of water extracted.
7.6 Calculations
7.6.1 Identify EDB and DBCP in the sample chromatogram by comparing
the retention time of the suspect peak to retention times generated by the
calibration standards and the check standard.
7.6.2 Use the calibration curve or calibration factor to directly
calculate the uncorrected concentration (Ci) of each analyte in the sample
(e.g. calibration factor x response).
7.6.3 Calculate the sample volume (Vs) as equal to the net sample
weight:
Vs (ml) = gross weight (grams} - bottle tare (grams)
7.6.4 Calculate the corrected sample concentration as:
Concentration (ug/L) = Ci x 35
Vs
7.6.5 Report the results for the unknown samples in ug/L. Round the
results to the nearest 0.01 ug/L or two significant figures.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses this method is required to operate a formal
quality control program.
8.1.1 The laboratory must make an initial determination of the
method detection limits and demonstrate the ability to generate acceptable
accuracy and precision with this method. This is established as described
in Step 8.2.
8.1.2 In recognition of laboratory advances that are occurring in
chromatography, the laboratory is permitted certain options to improve the
separations or 1ower the cost of measurements. Each ti me such a
80ll - 6 Revision 0
December 1987
modification is made to the method, the analyst is required to repeat the
procedure in Steps 7.1 and 8.2.
8.1.3 The laboratory must analyze a reagent and calibration blank to

demonstrate that interferences from the ana lyt i ca 1 system are under
control every twenty samples or per analytical batch whichever is more
frequent.
8.1.4 The laboratory must, on an ongoing basis, demonstrate through

the ana 1yses of QC reference samp 1es and check standards that the
operation of the measurement system is in control. The frequency of the
check standard analyses is equivalent to 5% of all samples or every
analytical batch, whichever is more frequent. On a weekly basis, the QC
reference sample must be run.
8.2 To establish the ability to achieve low detection limits and generate
acceptable accuracy and precision, the analyst must perform the following
operations:
8.2.1 Prepare seven samples each at a concentration of 0.03 ug/L.
8.2.2 Analyze the samples according to the method beginning in

Section 7.0.
8. 2. 3 Ca 1cul ate the average concentration (X) in ug/L and the

standard deviation of the concentrations (s) in ug/L, for each analyte
using the seven results. Then calculate the MDL at 99% confidence level
for seven replicates as 3.143s.
8.2.4 For each analyte in an aqueous matrix sampler, X must be

between 60% and 140% of the true va 1ue. Additionally, the MDL may not
exceed the 0.03 ug/L spiked concentration. If both analytes meet the
acceptance criteria, the system performance is acceptable and analysis of
actual samples can begin. If either analyte fails to meet a criterion,
repeat the test. It is recommended that the 1aboratory repeat the MDL
determination on a regular basis.
8.3 The laboratory must demonstrate on a frequency equivalent to 5% of

the sample load or once per analytical batch, whichever is more frequent, that
the measurement system is in control by analyzing a check standard of both
analytes at 0.25 ug/L.
8.3.1 Prepare a check standard (0.25 ug/L) by diluting the

intermediate standard with water to 0.25 ug/L.
8.3.2 Analyze the sample according to Section 7.0 and calculate the
recovery for each analyte. The recovery must be between 60% and 140% of
the expected value for aqueous matrices. For non-aqueous matrices, the
U.S. EPA will set criteria after more interlaboratory data are gathered.
8.3.3 If the recovery for either analyte falls outside the

designated range, the analyte fails the acceptance criteria. A second
calibration verification standard containing each analyte that failed must
8011 - 7 Revision 0
December 1987
be analyzed. Repeated failure, however, will confirm a general problem
with the measurement system. If this occurs, locate and correct the
source of the problem and repeat the test.
8.4 On a weekly basis, the laboratory must demonstrate the ability to
analyze a QC reference sample.
8.4.1 Prepare a QC reference sample at 0.10 ug/l by diluting the QC
reference sample concentrate (Step 5.9).
8.4.2 For each analyte in an aqueous matrix, the recovery must be
between 60% and 140% of the expected value. When either analyte fails the
test, the analyst must repeat the test only for that analyte which failed
to meet the criteria. Repeated fa i 1ure, however, wi 11 confirm a genera 1
problem with the measurement system or faulty samples and/or standards.
If this occurs, locate and correct the source of the problem and repeat
the test. For non-aqueous matrices, the U.S. EPA will set criteria after
more interlaboratory data are gathered.
8.5 Instrument performance - Check the performance of the entire
analytical system daily using data gathered from analyses of blanks,
standards, and replicate samples.
8.5.1 Peak tailing significantly in excess of that shown in the
chromatogram (Figure 1) must be corrected. Tailing problems are generally
traceable to active sites on the GC column or to the detector operation.
8.5.2 Check the precision between replicate analyses. A properly
operating system should perform with an average re 1at i ve standard
deviation of less than 10%. Poor precision is generally traceable to
pneumatic leaks, especially at the injection port.
9.1 Single laboratory accuracy and prec1s1on at several concentrations in
tap water are presented in Table 2. The method detection limits are presented
in Table 1.
9.2 In a preservation study extending over a 4 week period, the average
percent recoveries and relative standard deviations presented in Table 3 were
observed for reagent water (acidified), tap water and ground water. The
results for acidified and non-acidified samples were not significantly
different.
10.0 REFERENCES
1. Optimization of liquid-liquid Extraction Methods for Analysis of Organics
in Water, EPA-600/$4-83-052, 1984.
2. Henderson, J.E.; Peyton, G.R.; Glaze, W.H. Identification and Analysis of
Organic Pollutants in Water; Keith, l.H., Ed; Ann Arbor Sci.: Ann Arbor,
MI; 1976.
801l - 8 Revision 0
December 1987
3. Richard J.J.; Junk, G.A. Journal AWWA 1977, 69, 62.
4. Handbook for Analytical Quality Control in Water and Wastewater
Laboratories, EPA-600/4-79-019, U.S. Environmental Protection Agency.
Environmental Monitorning and Support Laboratory, Cincinnati, OH, 1979.
5. Budde, W.L.; Eichelberger, J.W. Organic Analyses Using Gas Chromatography-
Mass Spectormetry; Ann Arbor Science: Ann Arbor, MI; 1978.
6. Glaser, J.A.; et al. Environmental Science and Technology 1981, ~' 1426.
7. Methods for the Determination of Organic Compounds in Finished Drinking
Water and Raw Source Water; U.S. Environmental Protection Agency.
Environmental Monitoring and Support Laboratory, Cincinnati, OH, 1986.
for Reagent Water"; ATSM: Philadelphia, PA, 1985; Dl193-77.
10. Methods for the Determination of Organic Compounds in Finished Drinking
Water and Raw Source Water; U.S. Environmental Protection Agency. Office
of Re search and Development. Environmental Monitoring and Support
Laboratory. ORD Publication Offices of Center for Environmental Research
Information: Cincinnati, OH 1986.
8011 - 9 Revision 0
December 1987
TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
LIMITS (MOL) FOR 1,2-DIBROMOETHANE (EDB) AND
1,2-DIBROM0-3-CHLOROPROPANE (DBCP)
Retention Time, Minutes

Analyte Column A Column B MDL (ug/L)
EDB 9.5 8.9 0.01

DBCP 17 .3 15.0 0.01
Column A: Durawax-DX 3
Co1umn B: DB-1
TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION
FOR EDB AND DBCP IN TAP WATER
Relative
Number Spike Average Standard
of Level Recovery Deviation
Analyte Samples (ug/L) (%) (%)
EDB 7 0.03 114 9.5

7 0.24 98 11.8
7 50.0 95 4.7
DBCP 7 0.03 90 11.4
7 0.24 102 8.3
7 50.0 94 4.8
December 1987
TABLE 3.
ACCURACY AND PRECISION AT 2.0 ug/L
OVER A 4-WEEK STUDY PERIOD
Average Relative
Number Accuracy Std. Dev.
Analyte Matrix! of Samples (% Recovery) (%)
EDB RW-A 16 104 4.7

GW 15 101 2.5
GW-A 16 96 4.7
TW 16 93 6.3
TW-A 16 93 6 .1
DBCP RW-A 16 105 8.2
GW 16 105 6.2
GW-A 16 101 8.4
TW 16 95 10.l
TW-A 16 94 6.9
lMatrix Identities
RW-A = Reagent water at pH 2
GW = Ground water, ambient pH
GW-A = Ground water at pH 2
TW = Tap water, ambient pH
TW-A = Tap water at pH 2
December 1987
FIGURE 1.
SAMPLE CHROMATOGRAM FOR EXTRACT OF WATER SPIKED
AT 0.114 ug/L WITH EDB AND DBCP
COl.lllf: Fused s111ca capillary

LIQUID PHASE: Durawax-DX3
FILM THICKNESS: 0.25 um
COLUMN DIMENSIONS: 30 Mx 0.317 nn ID
I I I I l l I I I I I I I I
:a • • a io ia 1• i• 11 20 22 2• • • •
TIME (MIN)
80ll - 12 Revision 0
December 1987
METHOD 8011
1,2-0IBROMOMETHANE AND 1,2-DIBROM0-3-CHLOROPROPANE IN WATER
BY MICROEXTRACTION AND GAS CHROMATOGRAPHY
T.a.1"''1ac1 to T.5 l>et.eniae

( ltart ) • all naplH • •upl• Yolua
1
7 .1 Calibrat.e 7 .S.S Ad4 lau.ae
iaatraaaat: prepare aa4 parfon 7.8 Calcalatioa1
calibration carYa Htractioa
1
1 1. 2 Clleclt 7.3.C Pat part of
inatruHat
parforaaaca
bu.aa ia Yial ( Stop
1
7.1.2 11 lo T.S.& Pat raaaiadar
relative of llau.ae i• ••coad
1tandard vial for raaaaly•i•
deviation < if •ecauar7
101?
Tn I
'
l
7 2 Prepare •••Pl•• 1.& Aaalyaa by QC
December 1987
METHOD 8015
NONHALOGENATED VOLATILE ORGANICS

nonhalogenated volatile organic compounds. Table 1 indicates the compounds
that may be investigated by this method.
detection of certain non halogenated volatile organic compounds. Samples may
be analyzed using direct injection or purge-and-trap (Method 5030). Ground
water samples must be analyzed by Method 5030. A temperature program is used
in the gas chromatograph to separate the organic compounds. Detection is
achieved by a flame ionization detector (FID).
2.2 If interferences are encountered, the method provides an optional
gas chromatographic column that may be helpful in resolving the analytes from
interferences that may occur and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.1.1 Gas Chromatograph - Analytical system complete with gas
introduction and all required accessories, including detectors, column
suppl i es, recorder, gases, and syringes. A data system for measuring
peak heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Column 1 - 8 ft x 0.1 in i.d. stainless steel or glass
column packed with 1% SP-1000 on Carbopack-B 60/80 mesh or
equivalent.
8015 - 1 Revision 1
December 1987
column packed with n-octane on Porasil-C 100/120 mesh {Durapak) or
equivalent.
4.1.3 Detector - Flame ionization (FID).
4.2 Sample introduction apparatus - Refer to Method 5030 for the
4.3 Syringes - A 5-ml Luerlok glass hypodermic and a 5-ml, gas-tight
with shutoff valve.
4.4 Volumetric flasks - 10-, 50-, 100-, 500-, and 1,000-ml with a
ground-glass stopper.
4.5 Microsyringes - 10- and 25-ul with a 0.006-in i.d. needle (Hamilton
702N or equivalent) and a 100-ul.
5.0 REAGENTS
determination.
materials or purchased as certified sol ut i ans. Prepare stock standards in
methanol using assayed liquids.
5.3.1 Place about 9.8 ml of methanol in a 10-ml tared ground-glass-
about 10 minutes or until all alcohol-wetted surfaces have dried. Weigh
the flask to the nearest 0.1 mg.
5.3.2 Using a 100-ul syringe, immediately add two or more drops of
assayed reference material to the flask; then reweigh. The liquid must
fall directly into the alcohol without contacting the neck of the flask.
the fl ask several times. Cal cul ate the concentration in micrograms per
microliter (ug/ul) from the net gain in weight. When compound purity is
assayed to be 96% or greater, the weight may be used without correction
to ca 1cul ate the concentration of the stock standard. Commercially
prepared stock standards may be used at any concentration if they are
certified by the manufacturer or by an independent source.
8015 - 2 Revision 1
December 1987
Teflon lined screw-cap. Store, with minimal headspace, at -l0°C to -20°C
and protect from light.
5.3.5 Standards must be replaced after 6 months, or sooner if
comparison with check standards indicates a problem.
5.4 Secondary dilution standards - Using stock standard solutions, pre-
pare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Step 5.5 will bracket the working range of
the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
5.5 Calibration standards - Calibration standards at a minimum of five
concentration levels are prepared in water from the secondary dilution of the
stock standards. One of the concentration levels should be at a concentration
near, but above, the method detection limit. The remaining concentration
levels should correspond to the expected range of concentrations found in real
samples or should define the working range of the GC. Each standard should
contain each analyte for detection by this method (e.g. some or all of the
compounds listed in Table 1 may be included). In order to prepare accurate
aqueous standard solutions, the following precautions must be observed:
5.5.1 Do not inject more than 20 ul of alcoholic standards into
100 ml of water.
5.5.2 Use a 25-ul Hamilton 702N microsyringe or equivalent
5.5.4 Mix aqueous standards by inverting the flask three times
only.
the neck of the flask).
standards.
5.5.7 Aqueous standards are not stable and should be discarded
after 1 hour, unless properly sealed and stored. The aqueous standards
can be stored up to 24 hours, if held in sealed vials with zero
headspace.
8015 - 3 Revision 1
December 1987
internal standard can be suggested that is applicable to all samples.
5.6.1 Prepare calibration standards at a minimum of five
concentration levels for each parameter of interest as described in Step
5.5.
standards using the procedures described in Steps 5.3 and 5.4. It is
concentration of 15 ug/ml of each internal standard compound. The
addition of 10 ul of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
adding 10 ul of internal standard spiking solution directly to the
syringe.
performance of the ana 1yt i cal system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and water
blank witb one or two surrogate compounds recommended to encompass the range
of temperature program used in this method. From stock standard solutions
prepared as in Step 5.3, add a volume to give 750 ug of each surrogate to
45 ml of water contained in a 50-ml volumetric flask, mix, and dilute to
volume for a concentration of 15 ng/ul. Add 10 ul of this surrogate spiking
solution directly into the 5-ml syringe with every sample and reference
standard analyzed. If the internal standard calibration procedure is used,
the surrogate compounds may be added directly to the internal standard spiking
solution (Step 5.6.2).
5.7 Methanol, CH30H. Pesticide quality or equivalent. Store away from
other solvents.
6.0 SAMPLE COLLECTION, PRESERVATION, ANO HANDLING
Step 4 .1.
7.0 PROCEDURE
7.1 Volatile compounds are introduced into the gas chromatograph either
by direct injection or purge-and-trap (Method 5030). Method 5030 may be used
directly on ground water samples or low-level contaminated soils and
sediments. For medium-level soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions (Recommended)
8015 - 4 Revision 1
December 1987
7.2.1 Column 1 - Set helium gas flow at 40 ml/min flow rate. Set
column temperature at 45°C for 3 minutes; then program an 8°C/min
temperature rise to 220°C and hold for 15 minutes.
column temperature at 50°C for 3 minutes; then program a 6°C/min
temperature rise to 170°C and hold for 4 minutes.
7.3 Calibration - Refer to Method 8000 for proper calibration
techniques.
7.3.1 Calibration must take place using the same sample
introduction method that will be used to analyze actual samples (see Step
7. 4 .1).
7.3.2 The procedure for internal or external calibration may be

used. Ref er to Method 8000 for a description of each of these
procedures.
either Method 5030 (purge-and-trap method) or the direct injection
method. If the internal standard calibration technique is used, add
10 ul of internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications (e.g.
aqueous process wastes), direct injection of the sample into the GC
system with a 10-ul syringe may be appropriate. One such
application is for verification of the alcohol content of an aqueous
sample prior to determining if the sample is ignitable (Methods 1010
or 1020). In this case, it is suggested that direct injection be
used. The detection limit is very high (approximately 10,000 ug/l);
therefore, it is only permitted when concentrations in excess of
10,000 ug/l are expected or for water-soluble compounds that do not
purge. The system must be calibrated by direct injection (bypassing
the purge-and-trap device).
7.4.2 Follow Step 7.6 in Method 8000 for instructions on the
analysis sequence, appropriate dilutions, establishing daily retention
time windows, and identification criteria. Include a mid-level standard
after each group of 10 samples in the analysis sequence.
7.4.4 Calculation of concentration is covered in Step 7.8 of Method
8000.
8015 - 5 Revision 1
December 1987
of the sample with water. The dilution must be performed on a second
aliquot of the sample which has been properly sealed and stored prior to
use.
8.0 QUALITY CONTROL
8.2 Mandatory quality control to validate the GC system operation is
found in Method 8000, Step 8.6.
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Step 8.10).
8.3.1 If recovery is not within limits, the following is required:
Check to be sure there are no errors in ca 1cul at ions,
surrogate solutions, and internal standards. Also, check
9.1 The accuracy and prec1s1on obtained will be determined by the sample
matrix, sample introduction technique, and calibration procedures used.
9.2 Specific method performance information will be provided as it
becomes available.
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, Determining Volatile Organics at
Microgram-per-Liter Levels by Gas Chromatography, J. Amer. Water Works
Assoc., 66(12), pp. 739-744 (1974).
2. Bellar, T.A., and J.J. Lichtenberg, Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeabl e Vol at i 1e Organic
Compounds, in Van Hall, ed., Measurement of-Organic Pollutants in Water
and Wastewater, ASTM STP 686, pp. 108-129, 1979.
3. Development and Application of Test Procedures for Specific Organic Toxic
Substances in Wastewaters: Category 11 - Purgeabl es and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA
8015 - 6 Revision 1
December 1987
4. Rohrbaugh, W. G. ; et a1 . Reagent Chemi ca 1s, American Chemi ca 1 Society
8015 - 7 Revision I
December 1987
TABLE 1.
NONHALOGENATED VOLATILE ORGANICS
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
8015 - 8 Revision 1
December 1987
ME""M:J: e:1~
~=~~~-=~f~£TE= v=_ATI-E o~~~,::s
, I ,
I~t-oouc• c:o~~=~...,os
, . 4 :!I
1ntc gas Flec:i-o
c,., ... omato; .... ac..., t:: 1 volu"'e ou·ge:l
01r-ec:t l"Jec:t::· c• or- l'"'l ec:teo a~:
P..J""ge-ar-o-t-a: pea._ a:zes
(Met"OC 5::::
i
•
41
Q
7 ..
Calculate
Set gas concer'\tl""'at 1on
C,.,l"'"Q"l'letcg-a;: .. (SectlO" 7 l!I.
c:c~d!t1:- Metnoo eooo;
, 3 I 7 • ~
Ca:: :::-8~ e A~altze ua1r-.,

r-e•e· t : seco""C G:
'"'•t•c:: a::: cc! ..J"I"'-.
, . :I
7 4 6
I~tr-oo~cevc:et1:e
comc:.-~s 1 ... : : ;as
C:""o-atc;•e:• t, Ol l1w:e sec::""::
"4.t .... := s:::: c- a:1a .... ct c•
d11"'"CCt l~;e:t~:- aalT'C le
I
I
7 ... 2 I
•
.. cl:::.
Sec::o· 7 e Stoa
1f"I Met,.,OC e:::
fc• ar-e:tsls
aeou•'"'C:e e::
0
8015 - 9 Revision 1
December 1987
METHOD 8020A
AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY

aromatic volatile organic compounds. The following compounds can be determined
by this method:
Direct
Compound Name CAS No. 8 Purge-and-Trap Injection
Benzene 71-43-2 b b
Ethyl benzene 100-41-4 b b
Toluene 108-88-3 b b
Xylenes b b

b adequate response by this technique.
1.2 Table 1 lists the method detection limit for each target analyte in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.

2.1 Method 8020 provides chromatographic conditions for the detection of
aromatic volatile compounds. Samples can be introduced into the GC using direct
injection or purge-and-trap (Method 5030). Ground water samples must be
determined using Method 5030. A temperature program is used in the gas
chromatograph to separate the organic compounds. Detection is achieved by a
photo-ionization detector (PIO).
2. 2 If interferences are encountered, the method provides an optional gas
chromatographic column that may be helpful in resolving the analytes from the
interferences and for analyte confirmation.
3.0 INTERFERENCES
3.1 Refer to Method 5030 and 8000.
November 1992
(particularly chlorofluorocarbons and methylene chloride} through the sample
container septum during shipment and storage. A field sample blank prepared from

4 .1.1 Gas Chromatograph - Ana 1yt i ca 1 system comp 1ete with gas
supplies, recorder, gases, and syringes. A data system for measuring peak
heights and/or peak areas is recommended.
4.1.2 Columns
4.1.2.1 Column 1: 6 ft x 0.082 in ID #304 stainless steel
or glass column packed with 5% SP-1200 and 1.75% Bentone-34 on
100/120 mesh Supelcoport~ or equivalent.
4.1.2.2 Column 2: 8 ft x 0.1 in ID stainless steel or
glass column packed with 5% l,2,3-Tris(2-cyanoethoxy}propane on
60/80 mesh Chromosorb W-AW, or equivalent.
4.1.3 Detector - Photoionization (PIO} (h-Nu Systems, Inc. Model
PI-51-02 or equivalent).
4. 2 Sample introduction apparatus - Refer to Method 5030 for the
4.3 Syringes - A 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.
4.4 Volumetric flask, Class A - Appropriate sizes with ground glass
stoppers.
4.5 Microsyringe - 10 and 25 µL with a 0.006 in ID needle (Hamilton 702N
or equivalent} and a 100 µL.
5.0 REAGENTS
5.2 Methanol (CH 30H) - pesticide quality or equivalent. Store away from
other solvents.
November 1992
methanol using assayed liquids. Because of the toxicity of benzene and
1,4-dichlorobenzene, primary dilutions of these materials should be prepared in
a hood.
5.3.1 Place about 9.8 ml of methanol in a 10 ml tared ground glass
about 10 min or until all alcohol wetted surfaces have dried. Weigh the
flask to the nearest 0.0001 g.
5.3.2 Using a 10 µl syringe, immediately add two or more drops of
fall directly into the alcohol without contacting the neck of the flask.
liter (mg/l) from the net gain in weight. When compound purity is assayed
5.3.4 Transfer the stock standard solution into a Teflon-sealed
screw-cap bottle. Store, with minimal headspace, at 4°C and protect from
l i ght.
5.3.5 All standards must be replaced after 6 months, or sooner if
5.4 Secondary dilution standards: Using stock standard solutions,
prepare in methanol secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary dilution
standards should be prepared at concentrations such that the aqueous calibration
standards prepared in Section 5.4 will bracket the working range of the
analytical system. Secondary dilution standards should be stored with minimal
headspace for volatiles and should be checked frequently for signs of degradation
or evaporation, especially just prior to preparing calibration standards from
them.
concentrations are prepared in organic-free reagent water from the secondary
dilution of the stock standards. One of the concentrations should be at a
concentration near, but above, the method detection 1imit. The remaining
in real samples or should define the working range of the GC. Each standard
should contain each analyte for detection by this method (e.g., some or all of
the compounds listed in the target analyte list may be included). In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
5.5.l Do not inject more than 20 µl of alcoholic standards into
100 ml of organic-free reagent water.
November 1992
5.5.2 Use a 25 µl Hamilton 702N microsyringe or equivalent
5.5.4 Mix aqueous standards by inverting the flask three times only.
standards.
5. 5. 7 Aqueous standards are not stable and should be discarded after
1 hr, unless properly sealed and stored. The aqueous standards can be
stored up to 24 hr, if held in sealed vials with zero headspace.
5.6 Internal standards (if internal standard calibration is used): To
affected by method or matrix interferences. Because of tQese limitations, no
Alpha,alpha,alpha-trifluorotoluene has been used successfully as an internal
standard.
concentrations for each parameter of interest as described in Section 5.5.
standards using the procedures described in Sections 5.3 and 5.4. It is
concentration of 15 mg/l of each internal standard compound. The addition
of 10 µl of this standard to 5.0 ml of sample or calibration standard
would be equivalent to 30 µg/l.
adding 10 µl of internal standard spiking solution directly to the
syringe.
5. 7 Surrogate standards: The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with each
sample matrix by spiking each sample, standard, and organic-free reagent water
blank with surrogate compounds (bromochlorobenzene, bromofluorobenzene, 1,1,1-
tri fl uoroto l uene, fl uorobenzene, and di fl uorobenzene are recommended) which
encompass the range of the temperature program used in this method. From stock
standard solutions prepared as in Section 5.3, add a volume to give 750 µg of
each surrogate to 45 ml of organic-free reagent water contained in a 50 ml
volumetric flask, mix, and dilute to volume for a concentration of 15 ng/µl.
Add 10 µl of this surrogate spiking solution directly into the 5 ml syringe with
November 1992
the internal standard spiking solution (Section 5.6.2).

Section 4. 1.
7. 0 PROCEDURE
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1.1 below).
7.2 Gas chromatography conditions (Recommended):
7.2.1 Column 1:
Carrier gas (He) flow rate: 36 ml/min
For lower boiling compounds:
Initial temperature: 50°C, hold for 2 min;
Temperature program: 50°C to 90°C at 6°C/min, hold until
all compounds have eluted.
For higher boiling range of compounds:
Column 1 provides outstanding separations for a wide variety of
aromatic hydrocarbons. Column I should be used as the primary analytical
column because of its unique ability to resolve para-, meta-, and ortho-
aromatic isomers.
7.2.2 Column 2:
Carrier gas (He) flow rate: 30 ml/min
Column 2, an extremely high polarity column, has been used for a
number of years to resolve aromatic hydrocarbons from alkanes in complex
samples. However, because resolution between some of the aromatics is not
as efficient as with Column 1, Column 2 should be used as a confirmatory
column.
November 1992
7 .3 Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
7. 3 .1 Ca 1i brat ion must take p1ace using the same samp 1e introduction
7. 3. 2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for a description of each of these procedures.
7.4 Gas chromatographic analysis:
7.4.l Introduce volatile compounds into the gas chromatograph using
either Method 5030 (purge-and-trap method) or the direct injection method.
If the internal standard calibration technique is used, add 10 µL of
internal standard to the sample prior to purging.
7.4.1.1 Direct injection: In very limited applications
(e.g., aqueous process wastes), direct injection of the sample into
the GC system with a 10 µL syringe may be appropriate. The
detection limit is very high (approximately 10,000 µg/L); therefore,
it is only permitted wher concentrations in excess of 10,000 µg/L
are expected or for water soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
Non-aqueous miscible wastes may also be analyzed by direct
injection if the concentration of target analytes in the sample
falls within the calibration range. If dilution of the sample is
necessary, follow the guidance for High Concentration samples in
Method 5030A, Section 7.3.3.2.
7.4.3 Table 1 summarizes the estimated retention times and detection
limits for a number of organic compounds analyzable using this method. An
example of the separation achieved by Column 1 is shown in Figure 1.
Figure 2 shows an example of the separation achieved using Column 2.
7.4.5 Calculation of concentration is covered in Method 8000.
7.4.7 If the response for a peak is off scale, prepare a dilution
November 1992
8.0 QUALITY CONTROL

8.2 Quality control required to validate the GC system operation is found
in Method 8000.
should contain each parameter of interest at a concentration of 10 mg/L
in methanol.
of concentration for the anal ytes of interest. The contents of both
• Check to be sure that there are no errors in
calculations, surrogate solutions and internal
standards. Also, check instrument performance.
• Recalculate the data and/or reanalyze the extract if any
of the above checks reveal a problem.
• Reextract and reanalyze the sample if none of the above
are a problem or flag the data as "estimated
concentration".

9.1 This method was tested by 20 laboratories using organic-free reagent
six concentrations over the range 2.1 - 500 µg/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the parameter and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.
November 1992
10.0 REFERENCES
1. Bellar, T.A., and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds", in Van Hall (ed.), Measurement of Organic Pollutants in Water
3. Dowty, B.J., S.R. Antoine, and J.L. Laseter, "Quantitative and Qualitative
Analysis of Purgeable Organics by High Resolution Gas Chromatography and
Flame Ionization Detection", in Van Hall, ed., Measurement of Organic
Pollutants in Water and Wastewater. ASTM STP 686, pp. 24-35, 1979.
Substances in Wastewaters. Category 11 - Purgeabl es and Category 12 -
Acrolein, Acrylonitrile, and Dichlorodifluoromethane. Report for EPA
5. "EPA Method Validation Study 24, Method 602 (Purgeable Aromatics)", Report
for EPA Contract 68-03-2856 (i~ preparation).
Final Rule and Proposed Rule", October 26, 1984.
November 1992
TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
FOR AROMATIC VOLATILE ORGANICS
Retention time Method

(min) detection
limita
Compound Col. 1 Col. 2 (µg/L)
Benzene 3.33 2.75 0.2

Chlorobenzeneb 9.17 8.02 0.2
1,4-Dichlorobenzene 16.8 16.2 0.3
Ethyl Benzene 8.25 6.25 0.2
Toluene 5.75 4.25 0.2
Xylenes
a Using purge-and-trap method (Method 5030).

b Chlorobenzene and m-xylene may co-elute on some columns.
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs)
FOR VARIOUS MATRICESa
Matrix Factorb
Ground water 10
a Sample EQLs are highly matrix dependent. The EQLs listed herein are
provided for guidance and may not always be achievable.
b EQL = [Method detection limit (Table l)] X [Factor (Table 2)]. For
non-aqueous samples, the factor is on a wet-weight basis.
November 1992
TABLE 3.
QC ACCEPTANCE CRITERIA 8
Range Limit Rangg_ Range

for Q for s for x p' PS
Parameter (µg/L) (µg/L) (µg/L) (%)
Benzene 15.4-24.6 4.1 10.0-27.9 39-150

Chlorobenzene 16.1-23.9 3.5 12.7-25.4 55-135
Ethyl benzene 12.6-27.4 6.7 10.0-28.2 32-160
Toluene 15.5-24.5 4.0 11.2-27.7 46-148
Q Concentration measured in QC check sample, in µg/L.

s = Standard deviation of fo~r recovery measurements, in µg/L.
-
x Average recovery for four recovery measurements, in µg/L.
P, Ps Percent recovery measured.
D Detected; result must be greater than zero.
a Criteria from 40 CFR Part 136 for Method 602, and were calculated assuming
as check sample concentration of 20 µg/L. These criteria are based
directly upon the method performance data in Table 4. Where necessary,
the limits for recovery have been broadened to assure applicability of the
limits to concentrations below those used to develop Table 1.
November 1992
TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION

Parameter (µg/L) (µg/L) S' (µg/L)
Benzene 0.92C+0.57 o.o9x+o.sg o.21x+o.s6

Chlorobenzene 0.95C+0.02 o.o9x+o.23 o.1?x+o.10
1,2-Dichlorobenzene 0.93C+0.52 O.llx-0.04 o.22x+o.s3
1,3-Dichlorobenzene 0.96C-0.04 0 .15x-O .10 o.19x+o.og
1,4-Dichlorobenzene 0.93C-0.09 o.1sx+o.2s o.2ox+o.41
Ethyl benzene 0.94C+0.31 o.17x+o.46 o.26x+o.23
Toluene 0.94C+0.65 o.o9x+o.4s 0.18x+O. 71
x' == Expected recovery for one or more measurements of a sample

containing concentration C, in µg/L.
Sr
I
== Expected single analyst ~tandard deviation of measurements at an
average concentration of x, in µg/L.
S' == Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in µg/L.
c True value for the concentration, in µg/L.
x == Average recovery found for measurements of samp 1es containing a
concentration of C, in µg/L.
November 1992
Figure 1
Chromatogram of Aromatic Volatile Organics
(column 1 conditions)
I n •-1200/1.11" ..,...,,. 34
~ Column:
Protr.,.: IODC-2 Mlnut11. 6°CIMin. to IO°C
Detector: Photoioni11tion
5.mple: 0.40 llf/t StMdard Mi•ture
J I
I• I 1
f -
I>
.
ca
1 "'- ~
~
I
I}
i
•c
:II
ii
•ci.
r-.
4
• I 10 12
RETENTION TIMI fMINUTEll
14 11 11 20
November 1992
Figure 2
Chromatogram of Aromatic Volatile Organics
(column 2 conditions)
Cotumn: I~ 1.2.3· Trit <2-CV"'°""oxv I

'1o1w on Olromoe~W
,,. . em: ~·2 Minut1120C/Min. io 100oC
Dl•w: "'°'°''"i11t10fl
llmlM•: 2.0""" Sc.Melara Mixture
t
)I(
I I
J .
• I
f
~ I
• j
j t• ~
ll\C
..I I
•
•
l
"' I
•
• 1f I
J
j~t
J - .
fl\ '
I
j
~
0 I
November 1992
METHOD 8020A
AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
7 .1
co1t1.po~1ul•
-~·-········
direct
lnt.J:oduc::•
inj•c:tion ~~
pur1•·and·trap
tl\t.o •••
0 '····
pur1ed
and
•••••4
o:i-
peak
••l•••
injeet.•d
•iz••
INet.hod ~OlOl
"·•·• calc"lat•
., . a aet. ••• concent.:ratton
cbz omato•rapb (refer to Method
condition I 1'00)
7. l CalUu;at.e 7,,.6 Analyze uainSJ

(refer to Wet:hod eacond QC eolu•n
• 000)
7.•.1 Introduce
volatile compound•
•.I
...............
into
chro111at.09r•ph
direet.
I••
&njeet1on
~V
.1o•pooee
a peak
fo.i
ott·•••lo't
7, Di lut.•
aliquot. of
••cond
•••Pl•
7 ••• 1 W•ll•• ••~lt.o4

•OOO for •n•lY•i• lit.op
••quence, etc.
'
8020A 14 Revision 1
November 1992
METHOD 8021A
HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING
PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS
IN SERIES: CAPILLARY COLUMN TECHNIQUE

1.1 Method 8021 is used to determine volatile organic compounds in a
variety of solid waste matrices. This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic liquors, acid liquors, waste solvents, oily wastes, mousses, tars,
fibrous wastes, polymeric emulsions, filter cakes, spent carbons, spent
catalysts, soils, and sediments. The following compounds can be determined by
this method:
Direct
Analyte CAS No.a Purge-and-Trap Injection
Benzene 71-43-2 b b
Bromobenzene 108-86-1 b b
Bromochloromethane 74-97-5 b b
Bromodichloromethane 75-27-4 b b
Bromoform 75-25-2 b b
Bromomethane 74-83-9 b b
n-Butylbenzene 104-51-8 b b
sec-Butyl benzene 135-98-8 b b
tert-Butylbenzene 98-06-6 b b
Carbon tetrachloride 56-23-5 b b
Chlorodibromomethane 124-48-1 b b
Chloroethane 75-00-3 b b
Chloroform 67-66-3 b b
Chloromethane 74-87-3 b b
1,2-Dibromo-3-chloropropane 96-12-8 pp b
1,2-Dibromoethane 106-93-4 b b
flibromomethane 74-95-3 b b
l,Z-Dichlorobenzene 95-50-1 b b
Dichlorodifluoromethane 75-71-8 b b
1,1-Dichloroethene 75-35-4 b b
cis-1,2-Dichloroethene 156-59-4 b b
trans-1,2-Dichloroethene 156-60-5 b b
November 1992
Direct
Analyte CAS No.a Purge-and-Trap Injection
1,1-0ichloropropene 563-58-6 b b
cis-1,3-dichloropropene 10061-01-5 b b
trans-1,3-dichloropropene 10061-02-6 b b
Ethyl benzene 100-41-4 b b
Hexachlorobutadiene 87-68-3 b b
Isopropylbenzene 98-82-8 b b
p-Isopropyltoluene 99-87-6 b b
Methylene chloride 75-09-2 b b
Naphthalene 91-20-3 b b
n-Propylbenzene 103-65-1 b b
Styrene 100-42-5 b b
Tetrachloroethene 127-18-4 b b
Toluene 108-88-3 b b
1,2,3-Trichlorobenzene 87-61-6 b b
1,2,4-Trichlorobenzene 120-82-1 b b
Trichloroethene 79-01-6 b b
Trichlorofluoromethane 75-69-4 b b
1,2,3-Trichloropropane 96-18-4 b b
1,2,4-Trimethylbenzene 95-63-6 b b
1,3,5-Trimethylbenzene 108-67-8 b b
Vinyl chloride 75-01-4 b b
o-Xylene 95-47-6 b b
m-Xylene 108-38-3 b b
p-Xylene 106-42-3 b b

b Adequate response by this technique.
pp Poor purging efficiency resulting in high EQLs.
i Inappropriate technique for this analyte.
pc Poor chromatographic behavior.
1.2 Method detection limits (MDLs} are compound dependent and vary with
purging efficiency and concentration. The MDLs for selected analytes are
presented in Table 1. The applicable concentration range of this method is
compound and instrument dependent but is approximately 0.1 to 200 µg/L.
Analytes that are inefficiently purged from water will not be detected when
present at low concentrations, but they can be measured with acceptable accuracy
and precision when present in sufficient amounts. Determination of some
structural isomers (i.e. xylenes} may be hampered by coelution.
November 1992
1.3 The estimated quantitation limit (EQL) of Method 8021A for an
individual compound is approximately 1 µg/kg (wet weight) for soil/sediment
samples, 0.1 mg/kg (wet weight) for wastes, and 1 µg/L for ground water (see
Table 3). EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size to avoid saturation of the detector.
1.4 This method is recommended for use only by analysts experienced in
the measurement of purgeable organics at the low µg/L level or by experienced
technicians under the close supervision of a qualified analyst.
1.5 The toxicity or carcinogenicity of chemicals used in this method has
not been precisely defined. Each chemical should be treated as a potential
health hazard, and exposure to these chemicals should be minimized. Each
laboratory is responsible for maintaining awareness of OSHA regulations regarding
safe handling of chemicals used in this method. Additional references to
laboratory safety are available for the information of the analyst (references
4 and 6).
1.6 The following method analytes have been tentatively classified as
known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride,
1,4-dichlorobenzene, 1,2-dichloroethane, hexachloro-butadiene, 1,1,2,2-
tetrachloroethane, 1,1,2-trichloroethane, chloroform, 1,2-dibromoethane,
tetrachloroethene, trichloroethene, and vinyl chloride. Pure standard materials
and stock standard solutions of these compounds should be handled in a hood. A
NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles
high concentrations of these toxic compounds.

detection of halogenated and aromatic volatile organic compounds. Samples can
be analyzed using direct injection or purge-and-trap (Method 5030). Ground water
samples must be analyzed using Method 5030 (where applicable). A temperature
program is used in the gas chromatograph to separate the organic compounds.
Detection is achieved by a photoionization detector {PIO) and an electrolytic
conductivity detector (HECD) in series.
2.2 Tentative identifications are obtained by analyzing standards under
the same conditions used for samples and comparing resultant GC retention times.
Confirmatory information can be gained by comparing the relative response from
the two detectors. Concentrations of the identified components are measured by
relating the response produced for that compound to the response produced by a
compound that is used as an internal standard.
3.0 INTERFERENCES
container septum during shipment and storage. A trip blank prepared from
November 1992
3.3 Sulfur dioxide is a potential interferant in the analysis for vinyl
chloride.

4 .1 Sample introduction apparatus - Refer to Method 5030 for the
4.2 Gas Chromatograph - capable of temperature programming; equipped
with variable-constant differential flow controllers, subambient oven controller,
photoionization and electrolytic conductivity detectors connected with a short
piece of uncoated capillary tubing, 0.32-0.5 mm ID, and data system.
4.2.1 Column - 60 m x 0.75 mm ID VOCOL wide-bore capillary column
with 1.5 µm film thickness (Supelco Inc., or equivalent).
4.2.2 Photoionization detector {PIO) {Tracor Model 703, or
equivalent).
4.2.3 Electrolytic conductivity detector (HECD) (Tracor Hall Model
700-A, or equivalent).
4.3 Syringes - 5 ml glass hypodermic with Luer-Lok tips.
4.4 Syringe valves - 2-way with Luer ends (Teflon or Kel-F).
4.5 Microsyringe - 25 µL with a 2 in. x 0.006 in. ID, 22° bevel needle
{Hamilton #702N or equivalent).
4.6 Microsyringes - 10, 100 µL.
4.7 Syringes - 0.5, 1.0, and 5 ml, gas tight with shut-off valve.
4.8 Bottles - 15 ml, Teflon lined with screw-cap or crimp top.
4.10 Refrigerator.
4.11 Volumetric flasks, Class A - Appropriate sizes with ground glass
stoppers.
5. 0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all inorganic reagents shall
conform to the specifications of the Committee on Analytical Reagents of the
American Chemical Society, where such specifications are available. Other grades
November 1992
may be used, provided it is first ascertained that the reagent is of sufficiently
determination.
5.3 Methanol, CH 30H - Pesticide quality or equivalent, demonstrated to
be free of analytes. Store away from other solvents.
5.4 Vinyl chloride, (99.9% pure), CH 2=CHCl. Vinyl chloride is available
from Ideal Gas Products, Inc., Edison, New Jersey and from Matheson, East
Rutherford, New Jersey, as well as from other sources. Certified mixtures of
vinyl chloride in nitrogen at 1.0 and 10.0 ppm (v/v) are available from several
sources.
5.5 Stock standards - Stock solutions may either be prepared from pure
standard materials or purchased as certified solutions. Prepare stock standards
in methanol using assayed liquids or gases, as appropriate. Because of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity should be prepared in a hood.
NOTE: If direct injection is used, the solvent system of standards must
match that of the sample. It is not necessary to prepare high
concentration aqueous mixed standards when using direct injection.
5.5.l Place about 9.8 ml of methanol in a 10 ml tared ground glass
about 10 minutes until all alcohol-wetted surfaces have dried. Weigh the
flask to the nearest 0.1 mg.
5.5.2 Add the assayed reference material, as described below.
5.5.2.1 Liquids: Using a 100 µL syringe, immediately add
two or more drops of assayed reference material to the flask; then
reweigh. The liquid must fall directly into the alcohol without
contacting the neck of the flask.
5. 5. 2. 2 Gases: To prepare standards for any compounds
that boil below 30°C (e.g. bromomethane, chloroethane,
ch l oromethane, di ch l orod i fl uoromethane, tri ch l orofl uoromethane,
vinyl chloride), fill a 5 ml valved gas-tight syringe with the
reference standard to the 5.0 ml mark. Lower the needle to 5 mm
above the methanol meniscus. Slowly introduce the reference
standard above the surface of the liquid. The heavy gas rapidly
dissolves in the methanol. This may also be accomplished by using
a lecture bottle equipped with a Hamilton Lecture Bottle Septum
(#86600). Attach Teflon tubing to the side-arm relief valve and
direct a gentle stream of gas into the methanol meniscus.
liter (mg/l) from the net gain in weight. When compound purity is assayed
November 1992
Teflon lined screw-cap or crimp top. Store, with minimal headspace, at -
10°C to -20°C and protect from light.
5. 5. 5 Prepare fresh stock standards every two months for gases.
Reactive compounds such as 2-chloroethyl vinyl ether and styrene may need
to be prepared more frequently. Al 1 other standards must be replaced
after six months. Both gas and liquid standards must be monitored closely
by comparison to the initial calibration curve and by comparison to QC
reference samples. It may be necessary to replace the standards more
frequently if either check exceeds a 25% difference.
5.6 Prepare secondary dilution standards, using stock standard
solutions, in methanol, as needed, that contain the compounds of interest, either
singly or mixed together. The secondary dilution standards should be prepared
at concentrat i ans such that the aqueous ca 1i brat ion standards prepared in Section
5.7 will bracket the working range of the analytical system. Secondary dilution
standards should be stored with ~inimal headspace for volatiles and should be
checked frequently for signs of degradation or evaporation, especially just prior
to preparing calibration standards from them.
5.7 Calibration standards, at a minimum of five concentration levels are
prepared in organic-free reagent water from the secondary dilution of the stock
standards. One of the concentration levels should be at a concentration near,
but above, the method detection limit. The remaining concentration levels should
correspond to the expected range of the concentrations found in real samples or
should define the working range of the GC. Standards (one or more) should
contain each analyte for detection by this method (e.g. some or all of the target
analytes may be included). In order to prepare accurate aqueous standard
solutions, the following precautions must be observed.
NOTE: Prepare calibration solutions for use with direct injection analyses
in water at the concentrations required.
5.7.1 Do not inject more than 20 µL of alcoholic standards into
100 ml of water.
5.7.2 Use a 25 µL Hamilton 702N microsyringe or equivalent
5.7.4 Mix aqueous standards by inverting the flask three times.
November 1992
standards.
5. 7. 7 Aqueous standards are not stable and should be discarded after
one hour, unless properly sealed and stored. The aqueous standards can
be stored up to 12 hours, if held in sealed vials with zero headspace.
5.8 Internal standards Prepare a spiking solution containing
fluorobenzene and 2-bromo-1-chloropropane in methanol, using the procedures
described in Sections 5.5 and 5.6. It is recommended that the secondary dilution
standard be prepared at a concentration of 5 mg/L of each internal standard
compound. The addition of 10 µL of such a standard to 5.0 ml of sample or
calibration standard would be equivalent to 10 µg/L.
performance of the ana lyt i cal system and the effectiveness of the method in
dealing with each sample matrix by spiking each sample, standard, and reagent
blank with two or more surrogate compounds. A combination of bromochloromethane,
2-bromo-1-chl oropropane, I, 4-di ch l orobutane and bromochl orobenzene is recommended
to encompass the range of the temperature program used in this method. From
stock standard solutions prepared as in Section 5.5, add a volume to give 750 µg
of each surrogate to 45 ml of organic-free reagent water contained in a 50 ml
volumetric flask, mix, and dilute to volume for a concentration of 15 ng/µL.
Add 10 µL of this surrogate spiking solution directly into the 5 ml syringe with
the internal standard spiking solution (Section 5.8).

Section 4. 1.
7. 0 PROCEDURE
7. 2. 1 Set up the gas chromatograph system so that the
photoionization detector (PIO) is in series with the electrolytic
conductivity detector (HECD).
November 1992
7.2.2 Oven settings:
Carrier gas (Helium) Flow rate: 6 ml/min.
Temperature program
Initial temperature: 10°C, hold for 8 minutes at
Program: 10°C to 180°C at 4°C/min
Final temperature: 180°C, hold until all expected
compounds have eluted.
7.2.3 The carrier gas flow is augmented with an additional 24 ml of
helium flow before entering the photoionization detector. This make-up
gas is necessary to ensure optimal response from both detectors.
7.2.4 These halogen-specific systems eliminate misidentifications
due to non-organohalides which are coextracted during the purge step. A
Tracor Hall Model 700-A detector was used to gather the single laboratory
accuracy and precision data presented in Table 2. The operating
conditions used to collect these data are:
Reactor tube: Nickel, 1/16 in OD
Reactor temperature: 810°C
Reactor base temper~ture: 250°C
Electrolyte: 100% n-Propyl alcohol
Electrolyte flow rate: 0.8 ml/min
Reaction gas: Hydrogen at 40 ml/min
Carrier gas plus make-up gas: Helium at 30 ml/min
7.2.5 A sample chromatogram obtained with this column is presented
in Figure 5. This column was used to deve 1op the method performance
statements in Section 9.0. Estimated retention times and MDls that can
be achieved under these conditions are given in Table 1. Other columns
or element specific detectors may be used if the requirements of Section
8.0 are met.
7.3 Calibration Refer to Method 8000 for proper calibration
techniques. Use Table 1 and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7.3.1 Calibration must take place using the same sample introduction
7. 3. 2 The procedure for i nterna 1 or extern a1 calibration may be
either Method 5030 (purge-and-trap method) or the direct injection method
(see Section 7.4.1.1). If the internal standard calibration technique is
used, add 10 µl of internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications
(e.g. aqueous process wastes) direct injection of the sample into
the GC system with a 10 µl syringe may be appropriate. The
November 1992
detection limit is very high (approximately 10,000 µg/L), therefore,
it is only permitted where concentrations in excess of 10,000 µg/L
are expected or for water-soluble compounds that do not purge. The
system must be calibrated by direct injection (bypassing the purge-
and-trap device).
7.4.2 Follow Section 7.6 in Method 8000 for instructions on the
time windows, and identification criteria. Include a mid-concentration
standard after each group of 10 samples in the analysis sequence.
7.4.3 Table 1 summarizes the estimated retention times on the two
detectors for a number of organic compounds analyzable using this method.
7.4.5 Calculation of concentration is covered in Method 8000.
of confirmation, analysis using a second GC column is recommended.
8.0 QUALITY CONTROL

8.2 Quality control required to validate the GC system operation is
found in Method 8000.
8.2.1 The quality control reference sample (Method 8000) should
contain each parameter of interest at a concentration of 10 mg/L in
methanol.
8.2.2 Table 2 gives method accuracy and precision as functions of
concentration for the analytes of interest.
8.3.l If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
surrogate solutions and internal standards. Also check
November 1992
concentration".

9.1 Method detection limits for these analytes have been calculated from
data collected by spiking organic-free reagent water at 0.1 µg/L. These data
are presented in Table 1.
9.2 This method was tested in a single laboratory using organic-free
reagent water spiked at 10 µg/L. Single laboratory precision and accuracy data
for each detector are presented for the method analytes in Table 2.
10.0 REFERENCES
1. Volatile Organic Compounds in Water by Purge-and-Trap Capillary Column Gas
Chromatography with Photoionization and Electrolytic Conductivity
Detectors in Series, Method 502.2; U.S. Environmental Protection Agency.
Environmental Monitoring and Support Laboratory: Cincinnati, OH,
September, 1986.
2. The Determination of Halogenated Chemicals in Water by the Purge and Trap
Method, Method 502.1; Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio 45268, September,
1986.
3. Volatile Aromatic and Unsaturated Organic Compounds in Water by Purge and
Trap Gas Chromatography, Method 503.1; Environmental Protection Agency,
Environmental Monitoring and Support Laboratory: Cincinnati, Ohio,
September, 1986.
4. Glaser, J.A.; Forest, D.L.; McKee, G.D.; Quave, S.A.; Budde, W.L. "Trace
Analyses for Wastewaters"; Environ. Sci. Technol. 1981, 15, 1426.
5. Bellar, T.A.; Lichtenberg, J.J. The Determination of Synthetic Organic
Compounds in Water by Purge and Sequential Trapping Capillary Column Gas
Chromatography; U.S. Environmental Protection Agency, Environmental
Monitoring and Support Laboratory: Cincinnati, Ohio, 45268.
November 1992
TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL) FOR
VOLATILE ORGANIC COMPOUNDS ON PHOTOIONIZATION DETECTION (PID) AND
HALL ELECTROLYTIC CONDUCTIVITY DETECTOR (HECD) DETECTORS
PID HECD PID HECD

Ret. Time 8 Ret. Time MDL MDL
Analyte minute minute µ.g/L µ.g/L
b
Dichlorodifluoromethane 8.47 0.05
Chloromethane 9.47 0.03
Vinyl Chloride 9.88 9.93 0.02 0.04
Bromomethane 11.95 1.1
Chloroethane 12.37 0 .1
Trichlorofluoromethane 13.49 0.03
1,1-Dichloroethene 16 .14 16 .18 NOC 0.07
Methylene Chloride 18.39 0.02
trans-1,2-Dichloroethene 19.30 19.33 0.05 0.06
1,1-Dichloroethane 20.99 0.07
2,2-Dichloropropane 22.88 0.05
cis-1,2-Dichloroethane 23.11 23.14 0.02 0.01
Chloroform 23.64 0.02
Bromochloromethane 24 .16 0.01
1,1,1-Trichloroethane 24. 77 0.03
1,1-Dichloropropene 25.21 25.24 0.02 0.02
Carbon Tetrachloride 25.47 0.01
Benzene 26.10 0.009
1,2-Dichloroethane 26.27 0.03
Trichloroethene 27.99 28.02 0.02 0.01
Bromodichloromethane 29.43 0.02
Dibromomethane 29.59 2.2
Toluene 31. 95 0.01
1,1,2-Trichloroethane 33.21 ND
Tetrachloroethene 33.88 33.90 0.05 0.04
Dibromochloromethane 34.73 0.03
1,2-Dibromoethane 35.34 0.8
Chlorobenzene 36.56 36.59 0.003 0.01
Ethyl benzene 36.72 0.005
1,1,1,2-Tetrachloroethane 36.80 0.005
m-Xylene 36.98 0.01
p-Xylene 36.98 0.01
a-Xylene 38.39 0.02
Styrene 38.57 0.01
Isopropylbenzene 39.58 0.05
Bromoform 39.75 1.6
1,1,2,2-Tetrachloroethane 40.35 0.01
1,2,3-Trichloropropane 40.81 0.4
November 1992
TABLE 1.
(Continued)
PIO HECD PIO HECD

Ret. Time 8 Ret. Time MDL MDL
Analyte minute minute µ.g/L µ.g/L
n-Propylbenzene 40.87 0.004

Bromobenzene 40.99 41.03 0.006 0.03
1,3,5-Trimethylbenzene 41.41 0.004
2-Chlorotoluene 41.41 41.45 ND 0.01
4-Chlorotoluene 41.60 41.63 0.02 0.01
tert-Butylbenzene 42.92 0.06
1,2,4-Trimethylbenzene 42.71 0.05
sec-Butyl benzene 43.31 0.02
p-Isopropyltoluene 43.81 0.01
1,3-Dichlorobenzene 44.08 44.11 0.02 0.02
1,4-Dichlorobenzene 44.43 44.47 0.007 0.01
n-Butylbenzene 45.20 0.02
1,2-Dichlorobenzene 45. 71 45.74 0.05 0.02
l,2-Dibromo-3-Chloropropane 48.57 3.0
1,2,4-Trichlorobenzene 51.43 51.46 0.02 0.03
Hexachlorobutadiene 51. 92 51. 96 0.06 0.02
Naphthalene 52.38 0.06
1,2,3-Trichlorobenzene 53.34 53.37 ND 0.03
Internal Standards
Fl uorobenzene 26.84
2-Bromo-1-chloropropane 33.08
a
Retention times determined on 60 m x 0.75 mm ID VOCOL capillary column.
Program: Hold at 10°C for 8 minutes, then program at 4°C/min to 180°C, and
hold until all expected compounds have eluted.
b
Dash (-) indicates detector does not respond.
c
ND = Not determined.
November 1992
TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
FOR VOLATILE ORGANIC COMPOUNDS IN WATERd
Photoionization Hall Electrolytic

Detector Conductivit~ Detector
Standard Standard
Recovery, 8 Deviation Recovery, 8 Deviation
1alyte % of Recovery % of Recovery
b
~nzene 99 1. 2
·omobenzene 99 1. 7 97 2.7
·omochloromethane 96 3.0
·omodichloromethane 97 2.9
·omoform 106 5.5
·omomethane 97 3.7
-Butyl benzene 100 4.4
~c-Butylbenzene 97 2.6
~rt-Butyl benzene 98 2.3
arbon tetrachloride 92 3.3
11orobenzene 100 1.0 103 3.7
1loroethane 96 3.8
, l oroform 98 2.5
, l oromethane 96 8.9
-Chlorotoluene NOC ND 97 2.6
-Chlorotoluene 101 1.0 97 3.1
,2-Dibromo-3-chloropropane 86 9.9
ibromochloromethane 102 3.3
,2-Dibromoethane 97 2.7
ibromomethane 109 7.4
,2-Dichlorobenzene 102 2.1 100 1. 5
,3-Dichlorobenzene 104 1. 7 106 4.3
,4-Dichlorobenzene 103 2.2 98 2.3
ichlorodifluoromethane 89 5.9
,1-Dichloroethane 100 5.7
,2-Dichloroethane 100 3.8
,1-Dichloroethene 100 2.4 103 2.9
is-1,2 Dichloroethene ND ND 105 3.5
rans-1,2-Dichloroethene 93 3.7 99 3.7
,2-Dichloropropane 103 3.8
,1-Dichloropropene 103 3.6 103 3.4
thylbenzene 101 1.4
exachlorobutadiene 99 9.5 98 8.3
sopropylbenzene 98 0.9
-Isopropyltoluene 98 2.4
November 1992
TABLE 2.
(Continued)
Photoionization Hall Electrolytic

Detector Conductivity Detector
Standard Standard
Recovery, a Deviation Recovery, 8 Deviation
Analyte % of Recovery % of Recover:
Methylene chloride 97 2.8

Naphthalene 102 6.3
n-Propylbenzene 103 2.0
Styrene 104 1.4
1,1,1,2-Tetrachloroethane 99 2.3
1,1,2,2-Tetrachloroethane 99 6.8
Tetrachloroethene 101 1.8 97 2.4
Toluene 99 0.8
1,2,3-Trichlorobenzene 106 1. 9 98 3.1
1,2,4-Trichlorobenzene 104 2.2 102 2.1
1,1,1-Trichloroethane 104 3.4
1,1,2-Trichloroethane 109 6.2
Trichloroethene 100 0.78 96 3.5
Trichlorofluoromethane 96 3.4
1,2,3-Trichloropropane 99 2.3
1,2,4-Trimethylbenzene 99 1.2
1,3,5-Trimethylbenzene 101 1.4
Vinyl chloride 109 5.4 95 5.6
a-Xylene 99 0.8
m-Xylene 100 1.4
p-Xylene 99 0.9
a
Recoveries and standard deviations were determined from seven samples and spiked a
10 µ.g/L of each analyte. Recoveries were determined by internal standard method. Interna
standards were: Fluorobenzene for PIO, 2-Bromo-1-chloropropane for HECD.
b
Detector does not respond.
c
ND = Not determined.
d
This method was tested in a single laboratory using water spiked at 10 µ.g/l (se
reference 8) .
November 1992
TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
FOR VARIOUS MATRICES 6
Matrix Factorb
Ground water 10
a Sample EQLs are highly matrix dependent. The EQLs listed herein
are provided for guidance and may not always be achievable.
b EQL = [Method detection limit (Table l}] X [Factor (Table 2)].
For non-aqueous samples, the factor is on a wet-weight basis.
November 1992
FIGURE 1.
PURGING DEVICE
........... ~w.o.o
Drfue•OD
int .. OD
ST...._..ST'la
a
0
I
•
a
i
November 1992
FIGURE 2.
TRAP PACKINGS AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
CD ,..
ILICI~
~1""1
OOfmQ.AM)
rltCWTWt
November 1992
FIGURE 3.
PURGE-ANO-TRAP SYSTEM - PURGE MODE
UOUIO INJICT10N ~
CQ 1 1#f OYEN
~~COl.JMH
SEL.ECT'lOH vAl vt
' -
VENT'
l PUll'GIHG NOTl:
DEV1CI AU UHU IETWEEN ~
AHO QC SHOUlD • HUTID
TO llr'C.
November 1992
FIGURE 4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE - DESORB MODE
ANAL 'tT1CAL OOUIMN

OPTIONAL~ OOWI•
SILIC'T1CN YAL YI
&
November 1992
FIGURE 5.
GAS CHROMATOGRAM OF VOLATILE ORGANICS
Lii ·zs
~ii~
ot =t'
"~
LZ "SY
~i=lf
at: "Z9
11;1
ISZ._
.,:.
~;:Q
££.•£
-----
~~
~H=dil
~d
> e•·n
a: 24"'ICW
a: ta ·u !l-OlU
-3 " ...
.J
~
CL SZ"OE
az·ez
~ Ea"LZ
~ 08-SZ
> ~ ~·:fl
•
; ;rg
-I
Q
•
! sa ·1~
2•"0Z
L
n ~ ID "St
.... ~ Y=!I
0• !
x % 19-St
: U"St
s •
"'W~ sz11 =n
.... ~ "Ct
~ ! 12:1
i i< sz'
•S"L
sI 8021A - 20 Revision I
November 1992
METHOD 8021A
HALOGENATED VOLATILES BY GAS CHROMATOGRAPHY USING PHOTOIONIZATION
AND ELECTROLYTIC CONDUCTIVITY DETECTORS IN SERIES:
CAPILLARY COLUMN TECHNIQUE
Start
7.4.5 Refer
7.2 Set to Method
chromatographic eooo for
conditions. caleulations.
7.3 Refex to 7.4.6 Are Reanalyze

Method 8000 analytical Yes sampl.e uing
fox interferences second GC
calibxation suspected? column.
techniques.
No
7.C.1 Xntroduce Dilute and

•••Pl• into QC 7 , 4o. 7 %• peak r•analysa
using direct response oft second
injection or scale? aliQuot of
purge-and· trap. sample.
No
7,,,4 Record
sample volume
int:roduoed Stop
into GC and
peak sizes.
November 1992
METHOD 8030
ACROLEIN, ACRYLONITRILE, ACETONITRILE
I.O SCOPE AND APPLICATION

I.I Method 8030 is used to determine the concentration of the following
three volatile organic compounds:
Acrolein (Propenal)
Acryl oni tril e
Acetonitrile
I.2 Table I lists chromatographic conditions and method detection limits
for acrolein and acrylonitrile in reagent water. Table 2 lists the practical
quantitation limit (PQL) for other matrices.
2.I Method 8030 provides gas chromatographic conditions for the detection
of the three volatile organic compounds. Samples can be analyzed using direct
injection or purge-and-trap (Method 5030) . Ground water samples must be
analyzed using Method 5030. A temperature program is used in the gas
chromatograph to separate the organic compounds. Detection is achieved by a
flame ionization detector (FID).
2.2 The method provides an optional gas chromatographic column that may
be helpful in resolving the analytes from interferences that may occur and for
analyte confirmation.
3.0 INTERFERENCES
3.I Refer to Methods 5030 and 8000.
container septum during shipment and storage. A field sample blank prepared
from reagent water and carried through sampling and subsequent storage and
handling can serve as a check on such contamination.
4.I Gas chromatograph
4.1.I Gas Chromatograph - Analytical system complete with gas
supplies, recorder, gases, and syringes. A data system for measuring peak
height and/or peak area is recommended.
8030 - I Revision I
December I987
4.1.2 Columns
4.1.2.1 Column 1 - 10 ft x 2 mm i.d. stainless steel or glass
packed with Porapak-QS (80/100 mesh) or equivalent.
packed with Chromosorb 101 (60/80 mesh) or equivalent.
4.1.3 Detector - Flame ionization (FID).
4.2 Sample introduction apparatus - Refer to Method 5030 for the
4.3 Syringes - A 5-ml Luerlok glass hypodermic and a 5-ml, gas-tight with
shutoff valve.
4.4 Volumetric flasks - 10-, 50-, 100-, 500-, and 1,000-ml with a ground-
glass stopper.
4.5 Microsyringes - 10- and 25-ul with a 0.006 in i.d. needle (Hamilton
702N or equivalent) and a 100-ul.
5.0 REAGENTS
5.1 .Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that a 11 reagents sha 11 conform to the
determination.
water using assayed liquids. Because acrolein and acrylonitrile are
lachrymators, primary dilutions of these compounds should be prepared in a
hood.
5.3.l Place about 9.8 ml of water in a 10-ml tared ground-glass-
stoppered volumetric flask. For acrolein standards the water must be
adjusted to pH 4-5 using hydrochloric acid {1:1) or sodium hydroxide
{ION), if necessary. Weigh the flask to the nearest 0.1 mg.
5.3.2 Using a 100-ul syringe, immediately add two or more drops of
fall directly into the water without contacting the neck of the flask.
the flask several times. Calculate the concentration in micrograms per
microliter {ug/ul) from the net gain in weight. When compound purity is
8030 - 2 Revision 1
December 1987
assayed to be 96% or greater, the weight may be used without correction to
Teflon lined screw-cap. Store, with minimal headspace, at 4°C and protect
from light.
5.3.5 Prepare fresh standards daily.
5.4 Secondary dilution standards - Using stock standard solutions,
prepare in water secondary dilution standards, as needed, that contain the
compounds of interest, either singly or mixed together. The secondary
dilution standards should be prepared at concentrations such that the aqueous
calibration standards prepared in Step 5.5 will bracket the working range of
the analytical system. Secondary dilution standards should be stored with
minimal headspace for volatiles and should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.
concentration levels are prepared in water from the secondary dilution of the
stock standards. One of the concentration levels should be at a concentration
near, but above, the method detection limit. The remaining concentration
levels should correspond to the expected range of concentrations found in real
samples or should define the working range of the GC. Each standard should
contain each analyte for detection by this method. In order to prepare
accurate aqueous standard so 1 ut ions, the following precautions must be
observed.
5.5.1 Use a 25-ul Hamilton 702N microsyringe or equivalent
deliver reproducible volumes of standards into water).
standards.
5.5.3 These standards must be prepared daily.
5.6 Internal standards (if internal standard calibration is used} - To
concentration levels for each parameter of interest as described in Step
5.5.
8030 - 3 Revision 1
December 1987
standards using the procedures described in Steps 5. 3 and 5. 4. It is
concentration of 15 ug/ml of each internal standard compound. The
addition of 10 ul of this standard to 5.0 ml of sample or calibration
standard would be equivalent to 30 ug/L.
adding 10 ul of internal standard spiking solution directly to the
syringe.
5.7 Surrogate standards - The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in dealing with
each sample matrix by spiking each sample, standard, and reagent water blank
with one or two surrogate compounds {e.g. compounds similar in analytical
behavior to the analytes of .interest but which are not expected to be present
in the sample) recommended to encompass the range of the temperature program
used in this method. From stock standard solutions prepared as in Step 5. 3,
add a volume to give 750 ug of each surrogate to 45 ml of water contained in a
50-ml volumetric flask, mix, and dilute to volume for a concentration of
15 ng/ul. Add 10 ul of this surrogate spiking solution directly into the 5-ml
syringe with every samp 1e and reference standard ana 1yzed. If the i nterna 1
standard calibration procedure is used, the surrogate compounds may be added
directly to the internal standard spiking solution {Step 5.6.2).
4.1.
7.0 PROCEDURE
by direct injection or purge-and-trap {Method 5030). Method 5030 may be used
di re ct 1y on ground water samples or 1ow-1 evel contaminated soils and
sediments. For high-level soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to purge-and-trap analysis.
7.2 Gas chromatography conditions {Recommended)
7.2.l Column 1 - Set helium gas flow at 30 ml/min flow rate. Set
column temperature at ll0°C for 1.5 minutes; then heat as rapidly as
possible to 150°C and hold for 20 minutes.
column temperature at 80°C for 4 minutes; then program at 50°C/mi n to
120°C and hold for 12 minutes.
7.3 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point
on the calibration curve.
8030 - 4 Revision 1
December 1987
7.3.l Calibration must take place using the same sample introduction
method that will be used to analyze actual samples {see Step 7.4.1).
7.3.2 The procedure for internal or external calibration may be
either Method 5030 (purge-and-trap method) or the direct injection method~
If the internal standard calibration technique is used, add 10 uL of the
internal standard to the sample prior to purging.
7.4.1.1 Direct injection - In very limited applications (e.g.
aqueous process wastes), direct injection of the sample into the GC
system with a 10 ul syringe may be appropriate. The detection limit
is very high (approximately 10,000 ug/L); therefore, it is only
permitted when concentrations in excess of 10,000 ug/L are expected
or for water-soluble compounds that do not purge. The system must be
calibrated by direct injection {bypassing the purge-and-trap device).
7.4.2 Follow Step 7.6 of Method 8000 for instructions on the
7.4.3 Table l summarizes the estimated retention times and detection
limits for a number of organic compounds analyzable using this method.
Figure 1 illustrates the chromatographic separation of acrolein and of
acrylonitrile using Column 1.
7.4.5 Calculation of concentration is covered in Step 7.8 of Method
8000.
7.4.7 If the response for a peak is off-scale, prepare a dilution of
the sample with water. The dilution must be performed on a second aliquot
of the sample which has been properly sealed and stored prior to use.
8.0 QUALITY CONTROL
8.2 Procedures to check the GC system operation are found in Method 8000,
Step 8.6.
8030 - 5 Revision l
December 1987
8.2.1 The quality control check sample concentrate (Method 8000,
Step 8.6) should contain each parameter of interest at a concentration of
25 ug/ml in water.
for this method. Table 4 gives single laboratory accuracy and precision
for the analytes of interest. The contents of both Tables should be used
to evaluate a laboratory's ability to perform and generate acceptable data
by this method.
spikes. Determine if recovery is within limits (limits established by
performing QC procedure outlined in Method 8000, Step 8.10).
Check to be sure there are no errors in cal cul at ions, surrogate
solutions and internal standards. Also, check instrument
performance.
Recalculate the data and/or reanalyze the extract if any of the
above checks reveal a problem.
Reextract and reanalyze the sample if none of the above are a
problem or flag the data as "estimated concentration."
9.1 In a single laboratory, the average recoveries and standard
deviations presented in Table 4 were obtained using Method 5030. Seven
replicate samples were analyzed at each spike level.
10.0 REFERENCES
1. Bellar, T.A. and J.J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
pp. 739-744, 1974.
2. Bellar, T.A. and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
Ori nki ng Waters and lndustri a1 Waters for Purgeabl e Vol at i1 e Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
Substances in Was tewaters, Category 11: Purge ab 1es and Category 12:
Acrolein, Acrylonitrile, and Dichlorodifluoromethane, Report for EPA
4. Going, J., et al., Environmental Monitoring Near Industrial Sites -
Acrylonitrile, Office of Toxic Substances, U.S. EPA, Washington, DC, EPA
560/6-79-003, 1979.
8030 - 6 Revision 1
December 1987
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, 15., pp. 58-63, 1983.
7. Kerns, E.H., et al. "Determination of Acrolein and Acrylonitrile in Water
by Heated Purge and Trap Technique," U.S. Environmental Protection
Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268, 1980.
8. "Evaluation of Method 603," Final Report for EPA Contract 68-03-1760 (in
preparation).
for Reagent Water"; ASTM: Philadelphia, PA, 1985; Dl193-77.
8030 - 7 Revision 1
December 1987
TABLE 1.
Retention time (min) Method detection

Compound Col. 1 Col. 2 l imita (ug/L}
Acrolein 10.6 8.2 0.7

Acryl onitril e 12.7 9.8 0.5
aBased on using purge-and-trap, Method 5030.
TABLE 2.
DETERMINATION OF PRACTICAL QUANTITATION
LIMITS (PQL) FOR VARIOUS MATRICEsa
Matrix Factorb
Ground water 10
Low-1 evel soil 10
High-level soil and sludge 1250
a Sample PQLs are highly matrix-dependent.

The PQLs listed herein are provided for
guidance and may not always be achievable.
b PQL = [Method detection limit (Table 1)] X
[Factor (Table 2)]. For non-aqueous
samples, the factor is on a wet-weight
basis.
8030 - 8 Revision 1
December 1987
TABLE 3.
CALIBRATION AND QC ACCEPTANCE CRITERIAa
Range Limit Range Range

for Q for S for x p' Ps
Parameter (ug/L) (ug/L) (ug/L) (%)
Acrolein 45.9-54.1 4.6 42.9-60.1 88-118

Acryl onitril e 41. 2-58.8 9.9 33.1-69.9 71-135
Q = Concentration measured in QC check sample, in ug/L.

S = Standard deviation of four recovery measurements, in ug/L.
x = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
a Criteria from 40 CFR Part 136 for Method 603 and were calculated assuming a
QC check sample concentration of 50 ug/L.
TABLE 4.
SINGLE LABORATORY ACCURACY AND PRECISION
Spike Average Standard Average

cone. recovery deviation percent Sample
Parameter (ug/L) (ug/L) (ug/L) recovery matrixa
Acrolein 5.0 5.2 0.2 104 AW

50.0 51.4 0.7 103 AW
5.0 4.0 0.2 80 POTW
50.0 44.4 0.8 89 POTW
5.0 0.1 0.1 2 IW
100.0 9.3 I. I 9 IW
Acrylonitrile 5.0 4.2 0.2 84 AW
50.0 51.4 I. 5 103 AW
20.0 20.1 0.8 100 POTW
100.0 101.3 1.5 101 POTW
10.0 9.1 0.8 91 IW
100.0 104.0 3.2 104 IW
aAW = ASTM Type II water.

POTW = Prechlorination secondary effluent from a municipal sewage treatment
plant.
IW = Industrial wastewater containing an unidentified acrolein reactant.
8030 - 9 Revision 1
December 1987
Figure 1.
Gas chromatogram of acrole1n and acrylon1tr1le.
Colwnn: Porapak·OS
Program. 110°C for 1.5 """· rapidly
heated 10 1so•c
Detector: FL1me loniUt1on
"'..J
c
t:
z
0
-'
>
cc
~
-··-----
1.a 30 45 eo 7.51.0 10.s 120. 135 15.0
RETCNTION TIME. M.._..
December 1987
METHOD 8030
ACROLEIN, ACRYLONITRILE, ACETONITRILE
7. 1
7.4.4
ln~roouce compounos
1nto ges Recore
chrometogrepn by volume purg~tj
01rect 1n1ect1on or or 1n)ccteo eno
curge-eno-tr•P oee)( s1lCS
(Metl'loo 50301
7.2 7.4.S
Celculete
Set ges concantr-et1on
chrometogr-eph (Section 7.8.
cono1t1on Mc thoo 8000)
7.3 7 .... 6
Cel1brete Analyze using

(refer- to secono GC
Me tnoo 8000) column
7.4.1
7 .... 7
lntroouc• volet11•
compounos into gea
chrometogreon by Ollute secono
Metnoo 5030 or el1QU0t Of
o1rect 1n1ect1on sample
7. 4. 2
Fol lo"'
Sect1on 7.6 Stop
in Method 8000
tor- anelysts
seouence. etc.
December 1987
METHOD 8031
ACRYLONITRILE BY GAS CHROMATOGRAPHY
.0 SCOPE AND APPLICATION

1.1 Method 8031 is used to determine the concentration of acrylonitrile
n water. This method may also be applicable to other matrices. The following
:ompounds can be determined by this method:
Acryl onitri le 107-13-1

1.2 The estimated quantitation limit of Method 8031 for determining the
:oncentration of acrylonitrile in water is approximately 10 µg/L.
1.3 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatographs and ski 11 ed in the
:o generate acceptable results with this method.

2.1 A measured sample volume is micro-extracted with methyl tert-butyl
ether. The extract is separated by gas chromatography and measured with a
Nitrogen/Phosphorus detector.
3.0 INTERFERENCES
3 .1 Method interferences may be caused by contaminants in sol vents,
reagents, glassware, and other sample processing hardware that leads to discrete
artifacts and/or elevated baselines in gas chromatograms. All of these materials
must be routinely demonstrated to be free from interferences under the conditions
of the analysis by running laboratory reagent blanks.
3.2 Samples can be contaminated by diffusion of volatile organics around
the septum seal into the samp 1e during handling and storage. A fie 1d b1ank
should be prepared from organic-free reagent water and carried through the
sampling and sample handling protocol to serve as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed. To reduce carryover, the
sample syringe must be rinsed out between samples with solvent. Whenever an
8031 - 1 Revision 0
November 1992
unusually concentrated sample is encountered, it should be followed by the
analysis of solvent to check for cross contamination.

4.1 Gas chromatograph system
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column injections and all requirec
accessories, including detector, analytical columns, recorder, gases, anc
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Column: Porapak Q - 6 ft., 80/10 Mesh, glass column, or
equivalent.
4.1.3 Nitrogen/Phosphorus detector.
4.2 Materials
4.2.l Grab sample bottles - 40 ml VOA bottles.
4.2.2 Mixing bottles - 90 ml bottle with a Teflon lined cap.
4.2.3 Syringes - 10 µL and 50 µL.
4.2.4 Volumetric flask (Class A} - 100 ml.
4.2.5 Graduated cylinder - 50 ml.
4.2.6 Pipet (Class A} - 5, 15, and 50 ml.
4.2.7 Vials - 10 ml.
4.3 Preparation
4.3.1 Prepare all materials to be used as described in Chapter 4 for
volatile organics.
5.0 REAGENTS
5.2 General
5.2.l Methanol, CH 30H - Pesticide quality, or equivalent.
8031 - 2 Revision O
November 1992
5.2.2 Organic-free reagent water. All references to water in this
1ethod refer to organic-free reagent water, as defined in Chapter One.
5.2.3 Methyl tert-butyl ether, CH 30t-C 4 H9 - Pesticide quality, or
?qui val ent.
5.2.4 Acrylonitrile, H2C:CHCN, 98%.
i.3 Stock standard solution
5.3.1 Stock standard solutions - Can be prepared from pure standard
1aterials or can be purchased as certified solutions. Commercially
>re pared stock standards can be used if they are verified against EPA
;tandards. If EPA standards are not available for verification, then
;tandards certified by the manufacturer and verified against a standard
1ade from pure material is acceptable.
5.3.2 The stock standard solution may be prepared by volume or by
>1eight. Stock solutions must be replaced after one year, or sooner if
:omparison with the check standards indicates a problem.
CAUTION: Acrylonitrile is toxic. Standard preparation should be
performed in a laboratory fume hood.
5.3.2.1 To prepare the stock standard solution by volume:
inject 10 µl of acrylonitrile (98%) into a 100 ml volumetric flask
with a syringe. Make up to volume with methanol.
5.3.2.2 To prepare the stock standard solution by weight:
Place about 9.8 ml of organic-free reagent water into a 10 ml
volumetric flask before weighing the flask and stopper. Weigh the
flask and record the weight to the nearest 0.0001 g. Add two drops
of pure acrylonitrile, using a 50 µl syringe, to the flask. The
liquid must fall directly into the water, without contacting the
inside wall of the flask. Stopper the flask and then reweigh.
Oil ute to volume with organic-free reagent water. Calculate the
concentration from the net gain in weight.
5.4 Working standard solutions
5.4.1 Prepare a minimum of 5 working standard solutions that cover
the range of analyte concentrations expected in the samples. Working
standards of 20, 40, 60, 80, and 100 µg/l may be prepared by injecting 10,
20, 30, 40, and 50 µl of the stock standard solution prepared in Section
5.3.2.1 into 5 separate 90 ml mixing bottles containing 40 ml of organic-
free reagent water.
5.4.2 Inject 15 ml of methy1 tert-buty1 ether into each mixing
bottle, shake vigorously, and let stand 5 minutes, or until layers have
separated.
5.4.3 Remove 5 ml of top layer by pipet, and place in a 10 ml vial.
5.4.4 Keep all standard solutions below 4°C until used.
8031 - 3 Revision 0
November 1992
Section 4.1.
7. 0 PROCEDURE
7.1 Sample Extraction
7.1.1 Pour 40 ml of the sample into a 90 ml mixing bottle. Pipet 15
ml of Methyl tert-butyl ether into the mixing bottle. Shake vigorously
for about 2 min. and let stand for about 5 min. Remove about 5 ml of the
top layer and store in a 10 ml vial.
7.2 Chromatographic Conditions (Recommended)
Carrier Gas (He) flow rate: 35 ml/min.
Column Temperature: 180° C, Isothermal
Injection port temperature: 250° c
Detector temperature: 250° c
Detector Current (DC): 18 volts
Gases: Hydrogen, 3 ml/min; Air, 290 ml/min.
7.3 Calibration of GC
7.3.1 On a daily basis, inject 3 µL of methyl tert-butyl ether
directly into the GC to flush the system. Al so purge the system with
methyl tert-butyl ether injections between injections of standards and
samples.
7.3.2 Inject 3 µL of a sample blank (organic-free reagent water
carried through the sample storage procedures and extracted with methyl
tert-butyl ether).
7.3.3 Inject 3 µL of at least five standard solutions: one should
be near the detection limit; one should be near, but below, the expected
concentrations of the analyte; one should be near, but above, the expected
concentrations of the analyte. The range of standard solution
concentrations used should not exceed the working range of the GC system.
7. 3. 4 Prepare a calibration curve using the peak areas of the
standards (retention time of acrylonitrile under the conditions of Section
7.2 is approximately 2.3 minutes). If the calibration curve deviates
significantly from a straight line, prepare a new calibration curve with
the existing standards, or, prepare new standards and a new calibration
curve. See Method 8000, Section 7.4.2, for additional guidance on
calibration by the external standard method.
7.4 Sample Analysis
7.4.1 Inject 3 µL of the sample extract, using the same
chromatographic conditions used to prepare the standard curve. Calculate
8031 - 4 Revision 0
November 1992
the concentration of acrylonitrile in the extract, using the area of the
peak, against the calibration curve prepared in Section 7.3.4.
3.0 QUALITY CONTROL

)rocedures.
8.2 Prior to preparation of stock solutions, methanol and methyl
tert-butyl ether reagents should be analyzed gas chromatographically under the
condit i ans described in Section 7. 2, to determine possible interferences with the
acrylonitrile peak. If the solvent blanks show contamination, a different batch
of solvents should be used.

9.1 Method 8031 was tested in a single laboratory over a period of days.
Duplicate samples and one spiked sample were run for each calculation. The GC
was calibrated daily. Results are presented in Table 1.
10.0 REFERENCES
1. K.L. Anderson, "The Determination of Trace Amounts of Acrylonitrile in
Water by Specific Nitrogen Detector Gas Chromatograph", American Cynamid
Report No. WI-88-13, 1988.
8031 - 5 Revision 0
November 1992
TABLE 1
SINGLE LABORATORY METHOD PERFORMANCE
CONCENTRATION
SAMPLE SPIKE (µg/L) 3 RECOVERY
A 60 100
B 60 105
c 40 86
D 40 100
E 40 88
F 60 94
Average 96
8031 - 6 Revision 0
November 1992
METHOD 8031
ACRYLONITRILE BY GAS CHROMATOGRAPHY
Sta.::ct
\/
7 1.1 Extract
40ml. 0£ sampl.e 7 3 2 An.al.yze
with methyl. 3u.l of sample
t-buty1 ethez: b1ank
;l.n 90anl. bottl.•.
\/ \/
7 3.3-7 3.4
7 • 2 Set Establ.ish
ch::c o:ma. tog::c a . p h i c calibration.
con.di t ion.a cu.z:ve "With. at
\/ \/
7 . 3 1 Fl.uah GC
system with 3 u. l. 7 . 4 Sa.rnpl.e
methyl. t-butyl. Analysis
e the::c
\/
Stop
8031 - 7 Revision 0
November 1992
METHOD 8032
ACRYLAMIDE BY GAS CHROMATOGRAPHY

1.1 Method 8032 is used to determine trace amounts of acrylamide monomer
in aqueous matrices. This method may be applicable to other matrices. The
following compounds can be determined by this method:
Compound Name CAS No.a
Acrylamide 79-06-01

1.2 The method detection limit (MDL) in clean water is 0.032 µg/L.
1.3 This method is restricted to use by, or under the supervision of,
analysts experienced in the use of gas chromatographs and ski 11 ed in the
to generate acceptable results with this method.

2.1 Method 8032 is based on bromination of the acrylamide double bond.
The reaction product (2,3-dibromopropionamide} is extracted from the reaction
mixture with ethyl acetate, after salting out with sodium sulfate. The extract
is cleaned up using a Florisil column, and analyzed by gas chromatography with
electron capture detection (GC/ECD).
2.2 Compound identification should be supported by at least one
additional qualitative technique. Analysis using a second gas chromatographic
column or gas chromatography/mass spectrometry may be used for compound
confirmation.
3.0 INTERFERENCES
3 .1 No interference is observed from sea water or in the presence of 8. 0%
of ammonium ions derived from ammonium bromide. Impurities from potassium
bromide are removed by the Florisil clean up procedure.
8032 - 1 Revision 0
November 1992
4.1 Gas chromatographic System
4.1.l Gas chromatograph suitable for on-column injections with all
required accessories, including detector, anal yt i cal columns, recorder,
gases, and syringes. A data system for measuring peak heights and/or peak
areas is recommended.
4.1.2 Column: 2 m x 3 mm glass column, 5% FFAP (free fatty acid
polyester) on 60-80 mesh acid washed Chromosorb W, or equivalent.
4.1.3 Detector: electron capture detector.
4.2.l Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
extracts.
equivalent.
equivalent).
4.2.4 Snyder column Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3 Separatory funnel - 150 ml.
4.4 Volumetric flask (Class A) - 100 ml, with ground glass stopper;
25 ml, amber, with ground glass stopper.
4.5 Syringe - 5 ml.
4.6 Microsyringes - 5 µL, 100 µL.
4.7 Pipets (Class A).
4.8 Glass column (30 cm x 2 cm).
4.9 Mechanical shaker.
5.0 REAGENTS
8032 - 2 Revision 0
November 1992
5.3 Solvents
5.3.1 Ethyl acetate, C2H5C0 2C2H5 . Pesticide quality, or equivalent.
5.3.2 Diethyl ether, C 2 H 5 0C 2 H~. Pesticide quality, or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.3.3 Methanol, CH 3 0H. Pesticide quality, or equivalent.
5.3.4 Benzene, C6 H6 . Pesticide quality, or equivalent.
5.3.5 Acetone, CH 3COCH 3 . Pesticide quality, or equivalent.
5. 4 Saturated bromine water. Prepare by shaking organic-free reagent
water with bromine and allowing to stand for 1 hour, in the dark, at 4°C. Use
the aqueous phase.
5.5 Sodium sulfate (anhydrous, granular), Na 2S04 . Purify by heating at
the sodium sulfate.
5.6 Sodium thiosulfate, Na 2S203 , 1 Maqueous solution.
5.7 Potassium bromide, KBr, prepared for infrared analysis.
5.8 Concentrated hydrobromic acid, HBr, specific gravity 1.48.
5.9 Acrylamide monomer, H2C:CHCONH 2 , electrophoresis reagent grade,
minimum 95% purity.
5.10 Dimethyl phthalate, C6 H4 (COOCH 3 ) 2 , 99.0% purity.
5.11 Florisil (60/100 mesh): Prepare Florisil by activating at 130°C for
at least 16 hours. Alternatively, store Florisil in an oven at 130°C. Before
use, cool the Florisil in a desiccator. Pack 5 g of the Florisil, suspended in
benzene, in a glass column (Section 4.8).
5.12 Stock standard solutions
5.12.1 Prepare a stock standard solution of acrylamide monomer
as specified in Section 5.12.1.1. When compound purity is assayed to be
96% or greater, the weight can be used without correction to calculate the
8032 - 3 Revision 0
November 1992
concentration of the stock standard. Commercially prepared standards can
be used at any concentration if they are certified by the manufacturer or
by an independent source.
5.12.1.1 Dissolve 105.3 mg of acrylamide monomer in
organic-free reagent water in a 100 ml volumetric flask, and dilute
to the mark with organic-free reagent water. Dilute the solution of
acrylamide monomer so as to obtain standard solutions containing
0.1 - 10 mg/L of acrylamide monomer.
5.13 Calibration standards
5.13.1 Dilute the acrylamide stock solution with organic-free
reagent water to produce standard solutions containing 0.1 - 5 mg/L of
acrylamide. Prior to injection the calibration standards are reacted and
extracted in the same manner as environmental samples (Section 7).
5.14 Internal standards
5.14.1 The suggested internal standard is dimethyl phthalate.
Prepare a solution containing 100 mg/L of dimethyl phthalate in ethyl
acetate. The concentration of dimethyl phthalate in the sample extracts
and calibration standards shou1d be 4 mg/L.

Section 4.1.
7. 0 PROCEDURE
7.1 Bromination
7.1.l Pipet 50 ml of sample into a 100 ml glass stoppered flask.
Dissolve 7.5 g of potassium bromide into the sample, with stirring.
7.1.2 Adjust the pH of the solution with concentrated hydrobromic
acid until the pH is between 1 and 3.
7.1.3 Wrap the flask with aluminum foil in order to exclude light.
Add 2.5 ml of saturated bromine water, with stirring. Store the flask and
contents in the dark, at 0°C, for at least 1 hour.
7 .1. 4 After reacting the solution for at least an hour, decompose
the excess of bromine by adding 1 Msodium thiosulfate solution, dropwise,
until the color of the solution is discharged.
7.1.5 Add 15 g of sodium sulfate, using a magnetic stirrer to effect
vigorous stirring.
8032 - 4 Revision 0
November 1992
7.2 Extraction
7.2.1 Transfer the solution into a 150 ml separatory funnel. Rinse
the reaction flask three times with 1 ml aliquots of organic-free reagent
water. Transfer the rinsings into the separatory funnel.
7.2.2 Extract the aqueous solution with two 10 ml portions of ethyl
acetate for 2 min each, using a mechanical shaker (240 strokes per min).
Dry the organic phase with 1 g of sodium sulfate.
7.2.3 Transfer the organic phase into a 25 ml amber volumetric
flask. Rinse the sodium sulfate with three 1.5 ml portions of ethyl
acetate and combine the rinsings with the organic phase.
7.2.4 Add exactly 100 µg of dimethyl phthalate to the flask and make
the solution up to the 25 ml mark with ethyl acetate. Inject 5 µ.l
portions of this solution into the gas chromatograph.
7.3 Florisil cleanup: Whenever interferences are observed, the samples
should be cleaned up as follows.
7.3.l Transfer the dried extract into a Kuderna-Danish evaporator
with 15 ml of benzene. Evaporate the solvent at 70°C under reduced
pressure, and concentrate the solution to about 3 ml.
7.3.2 Add 50 ml of benzene and subject the solution to Florisil
column chromatography at a flow rate of 3 ml/min. Elute the column first
with 50 ml of diethyl ether/benzene (1:4) at a flow rate of 5 ml/min, and
then with 25 ml of acetone/benzene ( 2: 1) at a fl ow rate of 2 ml/min.
Discard all of the first eluate and the initial 9 ml portion of the second
eluate, and use the remainder for the determination, using dimethyl
phthalate (4 rng/l) as an internal standard.
NOTE: Benzene is toxic, and should be only be used under a
ventilated laboratory hood.
7.4 Gas chromatographic conditions:
Nitrogen carrier gas flow rate: 40 ml/min
Column temperature: 165°C.
Injector temperature: 180°C
Detector temperature: 185°C.
Injection volume: 5 µl
7.5 Calibration:
7.5.1 Inject 5 µ.l of a sample blank (organic-free reagent water
carried through all sample storage, handling, bromination and extraction
procedures).
7.5.2 Prepare standard solutions of acrylamide as described in
Section 5.13.1. Brominate and extract each standard solution as described
in Sections 7.1 and 7.2.
8032 - 5 Revision 0
November 1992
7.5.2.1 Inject 5 µL of each of a minimum of five standard
solutions: one should be near the detection limit; one should be
near, but below, the expected concentrations of the analyte; one
should be near, but above, the expected concentrations of the
analyte.
7.5.2.2 Prepare a calibration curve using the peak areas
of the standards. If the calibration curve deviates significantly
from a straight line, prepare a new calibration curve with the
existing standards, or, prepare new standards and a new calibration
curve. See Method 8000, Section 7.4.3, for additional guidance on
calibration by the internal standard method.
7.5.2.3 Calculate the response factor for each standard
according to Equation 1.
(Ps) (M;s)
RF = Equation I
(P;s) (MA)
= Response factor
Peak height of acrylamide
Amount 'of internal standard injected (ng)
= Peak height of internal standard
= Amount of acrylamide injected (ng)
7.5.3 Calculate the mean response factor according to Equation 2.
n
L
i=1
RF
RF = Equation 2
n
RF Mean response factor

RF Response factors from standard analyses (calculated in
Equation I)
n Number of analyses
7.6.1 Inject 5 µL portions of each sample (containing 4 mg/L
internal standard) into the gas chromatograph. An example GC/ECD
chromatogram is shown in Figure 1.
7.6.2 The concentration of acrylamide monomer in the sample is given
by Equation 3.
[A] = Equation 3
(P;s) (RF) (V;) (Vs)
[A] Concentration of acrylamide monomer in sample (mg/L)
PA Peak height of acrylamide monomer
8032 - 6 Revision 0
November 1992
Amount of internal standard injected (ng)
Total volume of sample (ml)
Peak height of internal standard
Mean response factor from Equation 2
Injection volume (µL)
8.0 QUALITY CONTROL

procedures.

9.1 The following performance data have been generated under the
conditions described in this method:
9.1.1 The calibration curve for Method 8032 is linear over the range
0-5 µg/L of acrylamide monomer.
9.1.2 The limit of detection for an aqueous solution is 0.032 µg/L.
9.1.3 The yields of the brominated compound are 85.2 ± 3.3% and 83.3
± 0.9%, at fortification concentrations of 1.0 and 5.0 µg/L, respectively.
9.2 Table 1 provides the recoveries of acrylamide monomer from river
water, sewage effluent, and sea water.
9.3 The recovery of the bromination product as a function of the amount
of potassium bromide and hydrobromic acid added to the sample is shown in
Figure 2.
9.4 The effect of the reaction time on the recovery of the bromination
product is shown in Figure 3. The yield was constant when the reaction time was
more than 1 hour.
9.5 Figure 4 shows the recovery of the bromination product as a function
of the initial pH from 1 to 7.35. The yield was constant within this pH range.
The use of conventional buffer solutions, such as sodium acetate - acetic acid
solution or phosphate solution, caused a significant decrease in yield.
10. 0 REFERENCES
1. Hashimoto, A., "Improved Method for the Determination of Acryl amide
Monomer in Water by Means of Gas-Liquid Chromatography with an Electron-
capture Detector," Analyst, 101:932-938, 1976.
8032 - 7 Revision 0
November 1992
TABLE 1
RECOVERY OF ACRYLAMIDE FROM WATER SAMPLES AS
2,3-DIBROMOPROPIONAMIDE
Overall
Acrylamide Amount of 2,3-DBPA 8 /µg Bromination Recovery of Coefficient
Sample Monomer Recovery Acrylamide of
Matrix Spiked/ µg Calculated Foundb %b Monomer, %b Variation
Standard 0.05 0.162 0.138 85.2 --- 3.3

0.20 0.649 0.535 82.4 --- 1.0
0.25 0.812 0.677 83.3 --- 0.9
River Water 0.20 0.649 0.531 81.8 99.4 2.5
Sewage
Effluent 0.20 0.649 0.542 83.5 101.3 3.0
Sea Water 0.20 0.649 0.524 80.7 98.8 3.5
a
2,3-0ibromopropionamide
b
Mean of five replicate determinations
8032 - 8 Revision 0
November 1992
Figure 1
2
4
I 3
a 7
,_,___ BL.
0 2
• • I
Time/min
10 12 14 11
Typical gas chromatograms of the bromi nation product obtained from aqueous
acrylamide monomer solution:
A. Untreated
B. With Florisil cleanup
BL. Chromatogram of blank, concentrated five-fold before gas chromatographic
analysis.
Peaks:
1. 2,3-Dibromopropionamide
2. Dimethyl phthalate
4-7. Impurities from potassium bromide
Sample size = 100 ml; acrylamide monomer= 0.1 µg
8032 - 9 Revision 0
November 1992
Figure 2
100r-----------------------
.
1'
~
~ 50
0
u
~
cc
s 10 15 2\l 23
Amount cf KBr/g per 50 ml
a 2 • 6 8 IQ
.A,.,,ount of "18r/ml "'' 50 ml
Effect of (A) potassium bromide and (B) hydrobromic acid on the yield of
bromination. Sample size = 50 ml; acrylamide monomer = 0.25 µg
November 1992
Figure 3
1oor-----------------------......
0 2 l 4 24
' Time/h
Effect of reaction time on the bromination. Reaction conditions:

50 ml of sample;
0.25 µg of acrylamide monomer;
7.5 g of potassium bromide;
2.5 ml of saturated bromine water
Extraction conditions:
15 g of sodium sulfate;
extraction at pH 2;
solvent = 10 ml of ethyl acetate (X2)
November 1992
Figure 4
100
0 0 0 0 q a ()a
\
~
. \
-a
u
>
50
' \
•
\
\
''
~ \
'~
\
0 1 z 3 4
pH
5
• 7 I
Effect of initial pH on the bromination. Reaction and extraction conditions as

in Figure 3. The pH was adjusted to below 3 with concentrated hydrobromic acid,
and to 4-5 with dilute hydrobromic acid. Reaction at pH 6 was in distilled
water. pH 7.35 was achieved by careful addition of dilute sodium hydroxide
solution. The broken line shows the result obtained by the use of sodium acetate
- acetic acid buffer solution.
November 1992
METHOD 8032
ACRYLAMIDE BY GAS CHROMATOGRAPHY
7.1 Bfomination 7.2 Extraction
7.1.1 Dissolve 7.5 gr. KBf into 7.2.1 Transfer ftask soln. to
50 ml. sample in flask. sep. funnel along wilh rinses.
7.2.2 EX1ract soln. lwice w/elhyl

7.1.2 Adjust soln. pH with
acetate. Dry organic phase
concentrated HBf to between
using sodium sulfate.
1and3.
7.2.3 Transfer organic phase

7.1.3 Wrap soln. flask with
and rinses Into amber
aluminum. Add 2.5 ml. satd. glass flask.
bromine water, stir, store at
0Cfor1 hr.
7.2.4Add100 ug. dimethyl

phthalate to ftask, dilute to
7.1.4 Add 1 M sodium
mark. Inject 5 ul. Into GC.
lhiosulfate dropwise to flask to
decompose excess bromine.
7.3 Florisil Cleanup
7.1.5 Add 15 gr. sodium

sulfate, and stir.
7.3.1 Transfer dried eX1ract to
K·D assembly wlbenzene.
Conc:en1rare to 3 ml. at 70 c
under reduced Pf8SSUr&.
7.3.2 Add 50 ml. benzene to

soluUon. Pass soln. through
Florisil calum. Elute with
diethyl elherlbenzene, then
aoetanelbenzane. Collect
the second elution train (1ess
Initial 9 ml.) for analysis.
November 1992
METHOD 8032
continued
7.4 GC Conditions
7.5 calibration
7.5.1 Inject 5 ul. sample blank.
7.5.2 Brominate and extract std.

solns. similar to the samples.
.1 Inject 5 ul. of each of the
minimum 5 stds.
.2 Plot peak are vs. [ ].
.3 Calculate response factor
(RF) for each [ ].
7.5.3 calculate mean RF from

eqn.2.
7.6 GC Analysis
7.6.1 Inject 5 ul. sample containing

internal std. into GC.
7.6.2 calculate aaylamide monomer

concentration in sample using
eqn.3.
November 1992
METHOD 8040
PHENOLS

1.1 Method 8040 is used to determine the concentration of various phenolic
compounds. Table 1 indicates compounds that may be analyzed by this method
and lists the method detection limit for each compound in water. Table 2
lists the practical quantitation limit (PQL} for all matrices.
2.1 Method 8040 provides gas chromatographic conditions for the detection
of phenolic compounds. Prior to analysis, samples must be extracted using
appropriate techniques (see Chapter Two for guidance). Both neat and diluted
organic liquids (Method 3580, Waste Dilution) may be analyzed by direct
injection. A 2- to 5-ul sample is injected into a gas chromatograph using the
sol vent flush technique, and compounds in the GC effluent are detected by a
flame ionization detector (FID).
2. 2 Method 8040 al so pro vi des for the preparation of pent a fl uorobenzyl -
bromide (PFB) derivatives, with additional cleanup procedures for electron
capture gas chromatography. This is to reduce detection limits of some
phenols and to aid the analyst in the elimination of interferences.
3.0 INTERFERENCES
3.1 Refer to Methods 3500, 3600, and 8000.
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. A11 these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing calibration and reagent blanks. Specific selection of
reagents and purification of solvents by distillation in all-glass systems may
be required.
3.3 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
4.0 APPARATUS ANO MATERIALS
4.1.1 Gas Chromatograph - Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak areas and/or peak heights is
recommended.
8040 - 1 Revision 1
December 1987
4.1.2 Columns
4.1.2.l Column for underivatized phenols - 1.8 m x 2.0 mm i.d.
glass column packed with 1% SP-1240DA on Supelcoport 80/100 mesh or
equivalent.
4.1.2.2 Column for derivatized phenols - 1.8 m x 2 mm i.d.
glass column packed with 5% OV-17 on Chromosorb W-AW-DMCS 80/100
mesh or equivalent.
4.1.3 Detectors - Flame ionization (FID) and electron capture
(ECO).
4.2 Reaction vial - 20-ml, with Teflon lined cap.
4.3 Volumetric flask - 10-, 50-, and 100-ml, ground-glass stopper.
4.4.l Concentrator tube - 10-ml, graduated (Kontes K-570050-1025 or
extracts.
equivalent).
equivalent).
4.7 Microsyringe - 10-ul.
4.8 Syringe - 5-ml.
5.0 REAGENTS
determination.
8040 - 2 Revision l
December 1987
5.3 Hexane, CH3(CH2)4CH3. Pesticide quality or equivalent.
5.4 2-Propanol, (CH3)2CHOH. Pesticide quality or equivalent.
5.5 Toluene, C6H5CH3. Pesticide quality or equivalent.
5.6 Derivatization reagent - Add 1 ml pentafluorobenzyl bromide and 1 g
18-crown-6-ether to a 50-ml volumetric flask and dilute to volume with
2-propanol. Prepare fresh weekly. This operation should be carried out in a
hood. Store at 4°C and protect from light.
Pentafluorobenzyl bromide (alpha-Bromopentafluorotoluene),
97% minimum purity.
NOTE: This chemical is a lachrymator.
5.6.2 18-crown-6-ether (l,4,7,10,13,16-Hexaoxacyclooctadecane) -
98% minimum purity.
NOTE: This chemical is highly toxic.
5.7 Potassium carbonate (Powdered), K2C03.
5.8 Stock standard solutions
5.8.1 Prepare stock standard solution at a concentration of
1.00 ug/ul by dissolving 0.0100 g of assayed reference material in
2-propanol and diluting to volume in a 10-ml volumetric flask. Larger
vo 1umes can be used at the convenience of the ana 1yst. When compound
purity is assayed to be 96% or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.8.2 Transfer the stock standard solutions into bottles with
Teflon lined screw-caps. Store at 4°C and protect from light. Stock
standards should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards
from them.
5.8.3 Stock standard solutions must be replaced after one year, or
sooner if comparison with check standards indicates a problem.
concentration levels should be prepared through dilution of the stock
standards with 2-propanol. One of the concentration levels should be at a
concentration levels should correspond to the expected range of concentrations
found in real samples or should define the working range of the GC.
8040 - 3 Revision 1
December 1987
Calibration solutions must be replaced after six months, or sooner, if
concentrations for each analyte as described in Step 5.9.
5.10.2 To each calibration standard, add a known constant amount of
one or more internal standards, and dilute to volume with 2-propanol.
5.10.3 Analyze each calibration standard according to Section 7.0.
5.11 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (if necessary), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and water blank with phenolic surrogates (e.g.
2-fluorophenol and 2,4,6-tribromophenol) recommended to encompass the range of
the temperature program used in this method. Method 3500, Step 5. 3 .1.1,
details instructions on the preparation of acid surrogates. Deuterated
analogs of analytes should not be used as surrogates for gas chromatographic
analysis due to coelution problems.
Step 4.1. Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
7.0 PROCEDURE
7.1 Extraction
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a pH of
less than or equal to 2 with methylene chloride, using either Method 3510
or 3520. Solid samples are extracted using either Method 3540 or 3550.
Extracts obtained from application of either Method 3540 or 3550 should
undergo Acid-Base Partition Cleanup, using Method 3650.
7.1.2 Prior to gas chromatographic analysis, the extraction solvent
must be exchanged to 2-propanol. The exchange is performed during the
micro K-D procedures 1i sted in a11 of the extraction methods. The
exchange is performed as follows:
7.1.2.1 Following concentration of the extract to 1 ml using
the macro- Snyder column, allow the apparatus to cool and drain for
at least 10 minutes.
8040 - 4 Revision 1
December 1987
7 .1. 2. 2 Increase the temperature of the hot water bath to
95-100°C. Remove the Snyder column and rinse the flask and its
lower joint into the concentrator tube with 1-2 ml of 2-propanol. A
5-ml syringe is recommended for this operation. Add one or two
clean boiling chips to the concentrator tube and attach a two ball
micro-Snyder column. Prewet the column by adding about 0.5 ml of
2-propanol to the top. Place the K-D apparatus on the water bath so
that the concentrator tube is partially immersed in the hot water.
Adjust the vertical position of the apparatus and the water
temperature, as required, to complete concentration in 5-10 minutes.
At the proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When the
apparent volume of liquid reaches 2.5 ml, remove the K-D apparatus
and allow it to drain and cool for at least 10 minutes. Add an
additional 2 ml of 2-propanol, add one or two clean boiling chips to
the concentrator tube, and resume concentrating as before. When the
apparent volume of liquid reaches 0.5 ml, remove the K-D apparatus
and allow it to drain and cool for at least 10 minutes.
7.1.2.3 Remove the micro-Snyder column and rinse its lower
joint into the concentrator tube with a minimum amount of
2-propanol. Adjust the extract volume to 1.0 ml. Stopper the
concentrator tube and store refrigerated at 4°C if further
processing will not be performed immediately. If the extract will
be stored longer than two days, it should be transferred to a vial
with a Teflon lined screw-cap. If the extract requires no further
derivatization or cleanup, proceed with gas chromatographic
analysis.
7.2.1 Column for underivatized phenols - Set nitrogen gas flow at
30 ml/min fl ow rate. Set column temperature at 80°C and immediately
program an 8°C/min temperature rise to 150°C; hold until all compounds
have eluted.
7.2.2 Column for derivatized phenols - Set 5% methane/95% argon gas
flow at 30 ml/min flow rate. Set column temperature at 200°C isothermal.
7.3 Calibration - Refer to Method 8000 for proper calibration
techniques. Use Table I and especially Table 2 for guidance on selecting the
lowest point on the calibration curve.
7. 3 .1 The procedure for internal or external calibration may be
used for the underi vat i zed phenols. Refer to Method 8000 for a
description of each of these procedures. If derivatization of the
phenols is required, the method of external calibration should be used by
injecting five or more levels of calibration standards that have also
undergone derivatization and cleanup prior to instrument calibration.
8040 - 5 Revision 1
December 1987
7.4.1 Refer to Method 8000. If the internal standard calibration
technique is used, add 10 ul of internal standard to the sample prior to
injection.
7.4.2 Phenols are to be determined on a gas chromatograph equipped
with a flame ionization detector according to the conditions listed for
the 1% SP-1240DA column (Step 7.2.1). Table 1 summarizes estimated
retention times and sensitivities that should be achieved by this method
for clean water samples. Practical quantitation limits for other
matrices are list in Table 2.
7.4.3 Follow Step 7.6 in Method 8000 for instructions on the
7 .4.4 An example of a GC/FID chromatogram for certain phenols is
shown in Figure 1. Other packed or capillary (open-tubular) columns,
chromatographic conditions, or detectors may be used if the requirements
of Step 8.2 are met.
7.4.5 Record the sample volume injected and the resulting peak
sizes (in area units or peak heights).
7. 4. 6 Using either the i nterna 1 or extern a1 ca 1i brat ion procedure
(Method 8000), determine the identity and quantity of each component peak
in the samp 1e chromatogram which corresponds to the compounds used for
calibration purposes. See Step 7.8 of Method 8000 for calculation
equations.
7.4.7 If peak detection using the SP-1240DA column with the flame
ionization detector is prevented by interferences, PFB derivatives of the
phenols should be analyzed on a gas chromatograph equipped with an
electron capture detector according to the conditions listed for the 5%
OV-17 column (Step 7 .2.2). The derivatization and cleanup procedure is
outlined in Steps 7 .5 through 7 .6. Table 3 summarizes estimated
retention times for derivatives of some phenols using the conditions of
this method.
7.4.8 Figure 2 shows a GC/ECD chromatogram of PFB derivatives of
certain phenols.
7.4.9 Record the sample volume injected and the resulting peak
sizes (in area units or peak heights).
7.4.10 Determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes. The method of external calibration should be used
(see Method 8000 for guidance). The concentration of the individual
compounds in the sample is calculated as follows:
Concentration (ug/L) = [(A)(Vt)(B)(D)]/[(Vi)(X)(C)(E)]
8040 - 6 Revision 1
December 1987
where:
A = Mass of underivatized phenol represented by area of peak in sample
chromatogram, determined from calibration curve (see Method 8000
Step 7. 4. 2) , ng.
Vt = Total amount of column eluate or combined fractions from which V;
was taken, ul.
B =Total volume of hexane added in Step 7.5.5, ml.
D = Total volume of 2-propanol extract prior to derivatization, ml.
Vi = Volume injected, ul.
X = Volume of water extracted, ml, or weight of nonaqueous sample
extracted, g, from Step 7.1. Either the dry or wet weight of the
non aqueous sample may be used, depending upon the specific
application of the data.
C =Volume of hexane sample solution added to cleanup column (Method
3630, Step 7.2), ml.
E = Volume of 2-propanol extract carried through derivatization in Step
7. 5.1, ml.
7.5 Derivatization - If interferences prevent measurement of peak area
during analysis of the extract by flame ionization gas chromatography, the
phenols must be derivatized and analyzed by electron capture gas
chromatography.
7.5.1 Pipet a 1.0-ml aliquot of the 2-propanol stock standard
solution or of the sample extract into a glass reaction vial. Add 1.0 ml
derivatization reagent (Step 5.3). This amount of reagent is sufficient
to deri vat i ze a so 1ut ion whose tot a1 pheno 1i c content does not exceed
0.3 mg/ml.
7.5.2 Add approximately 3 mg of potassium carbonate to the solution
and shake gently.
7. 5. 3 Cap the mixture and heat it for 4 hours at 80°C in a hot
water bath.
7.5.4 Remove the solution from the hot water bath and allow it to
cool.
7.5.5 Add 10 ml hexane to the reaction vial and shake vigorously
for 1 minute. Add 3.0 ml water to the reaction vial and shake for
2 minutes.
7 .5.6 Decant the organic layer into a concentrator tube and cap
with a glass stopper. Proceed with cleanup procedure.
8040 - 7 Revision 1
December 1987
7.6 Cleanup
7.6.1 Cleanup of the derivatized extracts takes place using Method
3630 (Silica Gel Cleanup), in which specific instructions for cleanup of
the derivatized phenols appear.
7.6.2 Following column cleanup, analyze the samples using GC/ECD,
as described starting in Step 7.4.7.
8.0 QUALITY CONTROL
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method used. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8. 2 Procedures to check the GC system operation are found in Method
8000, Step 8.6.
8.2.1 The quality control check sample concentrate (Method 8000,
Step 8.6) should contain each analyte of interest at a concentration of
100 ug/mL in 2-propanol.
for this method. Table 5 gives method accuracy and precision as
functions of concentration for the analytes. The contents of both Tables
should be used to evaluate a laboratory's ability to perform and generate
acceptable data by this method.
spikes. Determine if the recovery is within limits (limits established by
performing QC procedures outlined in Method 8000, Step 8.10).
Check to be sure there are no errors in ca 1cul at ions,
9.1 The method was tested by 20 laboratories using water, drinking
water, surface water, and three industrial wastewaters spiked at six
concentrations over the range 12 to 450 ug/L. Single operator precision,
overall precision, and method accuracy were found to be directly related to
the concentration of the analyte and essentially independent of the sample
8040 - 8 Revision 1
December 1987
matrix. Linear equations to describe these relationships for a flame
ionization detector are presented in Table 5.
9.2 The accuracy and precision obtained will be affected by the sample
matrix, sample-preparation technique, and calibration procedures used.
10.0 REFERENCES
1. Development and Application of Test Procedures for Specific Organic
Toxic Substances in Wastewaters. Category 3 - Chlorinated Hydrocarbons
and Category 8 - Phenols. Report for EPA Contract 68-03-2625 (in
preparation).
3. "Determination of Phenols in Industrial and Municipal Wastewaters,"
Report for EPA Contract 68-03-2625 (in preparation).
4. "EPA Method Validation Study Test Method 604 (Phenols)," Report for EPA
5. Kawarahara, F.K. "Microdetermination of Derivatives of Phenols and
Mercaptans by Means of Electron Capture Gas Chromatography," Analytical
Chemistry, 40, 1009, 1968.
6. Provost, L.P. and R.S. Elder, "Interpretation of Percent Recovery Data,"
American Laboratory, ~' pp. 58-63, 1983.
7. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
Specifications, 7th ed.; American Chemical Society: Washington, DC,
1986.
8040 - 9 Revision 1
December 1987
TABLE 1.
FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS
Method
Retention time Detection
Compound (minutes) limit (ug/L)
2-sec-Butyl-4,6-dinitrophenol (DNBP)
2-Chlorophenol 1. 70 0.31
Cresols (methyl phenols)
2-Cyclohexyl-4,6-dinitrophenol
2,6-Dichlorophenol
2,4-Dinitrophenol 10.00 13.0
2-Methyl-4,6-dinitrophenol 10.24 16.0
2-Nitrophenol 2.00 0.45
Phenol 3.01 0.14
Tetrachlorophenols
Trichlorophenols
TABLE 2.
DETERMINATION OF PRACTICAL QUANTITATION
LIMITS (PQL) FOR VARIOUS MATRICEsa
Matrix Factorb
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Non-water miscible waste 100,000
asample PQLs are highly matrix-dependent. The PQLs listed herein are
bPQL ~ [Method detection limit (Table l)] X [Factor (Table 2)]. For non-
aqueous samples, the factor is on a wet-weight basis.
December 1987
TABLE 3.
ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES
Retention Method
time detection
Parent compound (min) 1imi t ( ug/L)

2-Chlorophenol 3.3 0.58
2,4-Dinitrophenol 46.9
2-Methyl-4,6-dinitrophenol 36.6
2-Nitrophenol 9 .1 0. 77
Phenol 1.8 2.2
December 1987
TABLE 4.
QC ACCEPTANCE CRITERIAa
Test Limit Range Range

cone. for s for x P, Ps
Parameter (ug/L) (ug/L) (ug/L) (%)
4-Chloro-3-methylphenol 100 16.6 56. 7-113.4 99-122

2-Chlorophenol 100 27.0 54.1-110.2 38-126
2,4-Dichlorophenol 100 25.1 59.7-103.3 44-119
2,4-Dimethylphenol 100 33.3 50.4-100.0 24-118
4,6-Dinitro-2-methylphenol 100 25.0 42.4-123.6 30-136
2,4-Dinitrophenol 100 36.0 31.7-125.1 12-145
2-Nitrophenol 100 22.5 56.6-103.8 43-117
4-Nitrophenol 100 19.0 22.7-100.0 13-110
Pentachlorophenol 100 32.4 56. 7-113.5 36-134
Phenol 100 14.1 32.4-100.0 23-108
2,4,6-Trichlorophenol 100 16.6 60 .8-110. 4 53-119
s = Standard deviation of four recovery measurements, in ug/L.

x = Average recovery for four recovery measurements, in ug/L.
P, Ps = Percent recovery measured.
acriteria from 40 CFR Part 136 for Method 604. These criteria are based
directly upon the method performance data in Table 5. Where necessary, the
limits for recovery have been broadened to assure applicability of the limits
to concentrations below those used to develop Table 5.
December 1987
TABLE 5.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATIONa

recovery, x' precision, sr' precision,
Parameter (ug/L) (ug/L) S' (ug/L)
4-Chloro-3-methylphenol 0.87C-l.97 O.llx-0.21 0.16x+l.41

2-Chlorophenol 0.83C-0.84 0.18x+0.20 0.2lx+0.75
2,4-Dichlorophenol 0.81C+0.48 0.17x-0.02 0.18x+0.62
2,4-Dimethylphenol 0.62C-l.64 0.30x-0.89 0.25x+0.48
4,6-Dinitro-2-methylphenol 0.84C-l.Ol 0.15x+l.25 0.19x+5.85
2,4-Dinitrophenol 0. 80C-l. 58 0.27x-l.15 0.29x+4.51
2-Nitropheno 1 0.81C-0.76 0.15x+0.44 0.14x+3.84
4-Nitrophenol 0.46C+O .18 0.17x+2.43 0.19x+4.79
Pentachlorophenol 0.83C+2.07 0.22x-0.58 0.23x+0.57
Phenol 0. 43C+O .11 0.20x-0.88 0. l 7x+O. 77
2,4,6-Trichlorophenol 0.86C-0.40 O.lOx+0.53 0.13x+2.40
x' = Expected recovery for one or more measurements of a sample

containing a concentration of C, in ug/L.
sr' = Expected single analyst standard deviation of measurements at an
average concentration of x, in ug/L.
S' = Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in ug/L.
C = True value for the concentration, in ug/L.
x = Average recovery found for measurements of samples containing a
concentration of C, in ug/L.
aFrom 40 CFR Part 136 for Method 604.
December 1987
Figure 1.
Gas chromatogram of phenols.
Column: 1% SP·12400A on Sui>elcoport

Program: 80°C 0 Minutes 8°!Minut1 to 1S0°C
Oettctor: Flame lon1zat1on
0c:
• 0
10 i
0 0 1..
c:
f
• i
Q i
•r-.' 1 >
i -
·c
Q
i... :I- ti
~ 0 cO
i .
0
::c ~
.. :.
.. 00 .s: 2
.w
~ c;i• N
~
cO
• • r-4
f"•i
0
..
c:
l
!
i 0
l-
.,c:
l...
~
•
0 8 12 11 20 28
RETENTION TIME (MINUTES)
December 1987
Gn chromatogram of PFB deriv.iivn of phenols.
Column: 5% OV·17 on O\romotorb W·AW

Tempernurt: 2QOOC
Dftec:tor: Electron Caotu-1
~
i
l..
-
~
N
I-.
.
i I
-
1
l
0 4
• 12 20
RETENTION TIME (MINUTES)
24 28 32
December 1987
METHOD 8040
PHENOLS
st.,.t
7. 3. t
7.t.t Choose
eop,.o- Uae ••thod ot
or l•t.• ••t.,.ec:t- ••te,.nel cellb,.•t.lon
lon p,.oc:edu,.e by lnlec:tlno >/- 5
lrete,. to level• or c1llb,.•t.lon
cnapte,. 21 •t.•nda,.d•
7.t.2 E•c:hanoe 7 ·"'

ext,.•c:t-
ton •olvent to
2-o,.opanol Pe,.tor• GC
du,. lng 1111 c:ro enelys1s laee
K-0 procedu,.•• Method 80001
7.2
7 ·"'
Set o••
cr,,.·0111•tog,.ephy
Anelyz:e ustng
GC/FIO
c:ondtttons
7.3
Rete,. to
Method eooo
for P'"OP•'"
c•l1b,.•t1on
tec:hnloues
December 1987
METHOD 8040
(Continued)
7.6
Cleenup ustng
Method 3630
7 .... 9 7.~
Reco,.d
••111111• 1toluiae P,.cpe,.e
tnjccted end d•,.1vet1z•t1on
o••k •1zc•
7.•.10 Oetc,.- 7.4.7

111tne
1dent1ty end
Quent1tY or Anelyze PFS
••ch dc,.1v•t1YCI
co111::ioncnt ocek us1ng GC/ECO
7 .... 10
Celculetc
concent,.•t1on
Stoo
December 1987
METHOD 8061
PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
WITH ELECTRON CAPTURE DETECTION (GC/ECD)

I.I Method 8061 is used to determine the identities and concentrations
of various phthalate esters in liquid, solid and sludge matrices. The following
compounds can be determined by this method:
Benzyl benzoate (I.S.) 120-51-4

Bis(2-ethylhexyl) phthalate 117-81-7
Butyl benzyl phthalate 85-68-7
Di-n-butyl phthalate 84-74-2
Diethyl phthalate 84-66-2
Dimethyl phthalate 131-11-3
Di-n-octyl phthalate 117-84-0

1.2 Table 1 lists the method detection limits (MDL) for the target
analytes in a water matrix. The MDLs for the components of a specific sample may
differ from those 1i sted in Tab 1e 1 because MD Ls depend on the nature of
interferences in the sample matrix. Table 2 lists the estimated quantitation
limits (EQL) for other matrices.
1.3 When this method is used to analyze for any or all of the target
analytes, compound identification should be supported by at least one additional
qualitative technique. This method describes conditions for parallel column,
dual electron capture detector analysis which fulfills the above requirement.
Retention time information obtained on two megabore fused-silica open tubular
columns is given in Table 1. Alternatively, gas chromatography/mass spectrometry
could be used for compound confirmation.
1.4 The following compounds, bis(2-n-butoxyethyl) phthalate, bis(2-
ethoxyethyl) phthalate, bis(2-methoxyethyl) phthalate, bis(4-methyl-2-pentyl)
phthalate, diamyl phthalate, dicyclohexyl phthalate, dihexyl phthalate,
diisobutyl phthalate, dinonyl phthalate, and hexyl 2-ethylhexyl phthalate can
also be analyzed by this method and may be used as surrogates.
1.5 This method is restricted to use by or under the supervision of
analysts experienced in the use of gas chromatographs and skilled in the
to generate acceptable results with this method.
8061 - 1 Revision 0
November 1992
2.1 A measured volume or weight of sample (approximately 1 liter for
liquids, 10 to 30 grams for solids and sludges) is extracted by using the
appropriate sample extraction technique specified in Methods 3510, 3540, and
3550. Method 3520 is not recommended for the extraction of aqueous samples
because the longer chain esters (dihexyl phthalate, bis(2-ethylhexyl) phthalate,
di-n-octyl phthalate, and dinonyl phthalate) tend to adsorb to the glassware and
consequently, their extraction recoveries are <40 percent. Aqueous samples are
extracted at a pH of 5 to 7, with methylene chloride, in a separatory funnel
(Method 3510). Alternatively, particulate-free aqueous samples could be filtered
through membrane disks that contain C18 -bonded silica. The phthalate esters are
retained by the silica and, later eluted with acetonitrile. Solid samples are
extracted with hexane/acetone (1:1) or methylene chloride/acetone (1:1) in a
Soxhlet extractor (Method 3540) or with an ultrasonic extractor (Method 3550).
After cleanup, the extract is analyzed by gas chromatography with electron
capture detection (GC/ECD).
2.2 The sensitivity of Method 8061 usually depends on the level of
interferences rather than on instrumental limitations. If interferences prevent
detection of the analytes, cleanup of the sample extracts is necessary. Either
Method 3610 or 3620 alone or follqwed by Method 3660, Sulfur Cleanup, may be used
to eliminate interferences in the analysis. Method 3640, Gel Permeation Cleanup,
is applicable for samples that contain high amounts of lipids and waxes.
3.0 INTERFERENCES
3.2 Interferences coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are referenced or provided
as part of this method, unique samples may require additional cleanup approaches
to achieve desired sensitivities for the target analytes.
3.3 Glassware must be scrupulously clean. All glassware require
treatment in a muffle furnace at 400 °C for 2 to 4 hrs, or thorough rinsing with
pesticide-grade solvent, prior to use. Refer to Chapter 4, Section 4.1.4, for
further details regarding the cleaning of glassware. Volumetric glassware should
not be heated in a muffle furnace.
If Soxhlet extractors are baked in the muffle furnace, care must be taken
to ensure that they are dry (breakage may result if any water is left in the
side-arm). Thorough rinsing with hot tap water, followed by deionized water and
acetone is not an adequate decontamination procedure. Even after a Soxhlet
extractor was refluxed with acetone for three days, with daily solvent changes,
the concentrations of bis(2-ethylhexyl) phthalate were as high as 500 ng per
washing. Storage of glassware in the laboratory introduces contamination, even
if the glassware is wrapped in aluminum foil. Therefore, any glassware used in
Method 8061 should be cleaned immediately prior to use.
3.4 Florisil and alumina may be contaminated with phthalate esters and,
therefore, use of these materials in sample cleanup should be employed
cautiously. If these materials are used, they must be obtained packaged in glass
8061 - 2 Revision 0
November 1992
(plastic packaging wi 11 contribute to contamination with phtha late esters).
Washing of these materials prior to use with the solvent(s) used for elution
during extract cleanup was found helpful, however, heating at 320 °C for Florisil
and 210 °C for alumina is recommended. Phthalate esters were detected in
Florisil cartridge method blanks at concentrations ranging from 10 to 460 ng,
with 5 phthalate esters in the 105 to 460 ng range. Complete removal of the
phthalate esters from Florisil cartridges does not seem possible, and it is
therefore desirable to keep the steps involved in sample preparation to a
minimum.
3.5 Paper thimbles and filter paper must be exhaustively washed with the
solvent that will be used in the sample extraction. Soxhlet extraction of paper
thimbles and filter paper for 12 hrs with fresh solvent should be repeated for
a minimum of three times. Method blanks should be obtained before any of the
precleaned thimbles or filter papers are used. Storage of precleaned thimbles
and filter paper in precleaned glass jars covered with aluminum foil is
recommended.
3.6 Glass wool used in any step of sample preparation should be a
specially treated pyrex wool, pesticide grade, and must be baked at 400°C for
4 hrs. immediately prior to use.
3.7 Sodium sulfate must be obtained packaged in glass (plastic packaging
will contribute to contamination with phthalate esters), and must be purified by
heating at 400 °C for 4 hrs. in a shallow tray, or by precleaning with methylene
chloride (Section 5.3). To avoid recontamination, the precleaned material must
be stored in glass-stoppered glass bottles, or glass bottles covered with
precleaned aluminum foil. The storage period should not exceed two weeks. To
minimize contamination, extracts should be dried directly in the glassware in
which they are collected by adding small amounts of precleaned sodium sulfate
until an excess of free flowing material is noted.
3.8 The presence of elemental sulfur will result in large peaks which
often mask the region of the compounds eluting before dicyclohexyl phthalate
(Compound No. 14) in the gas chromatograms shown in Figure 1. Method 3660 is
suggested for removal of sulfur.
3.9 Waxes and lipids can be removed by Gel Permeation Chromatography
(Method 3640). Extracts containing high concentrations of lipids are viscous,
and may even solidify at room temperature.

4.1 Gas chromatography
4.1.1 Gas chromatograph, analytical system complete with gas
chromatograph suitable for on-column and split/splitless injections and
all required accessories, including detector, analytical columns,
recorder, gases, and syringes. A data system for measuring peak heights
and/or peak areas is recommended.
8061 - 3 Revision 0
November 1992
4.1.1.1 Eight inch injection tee (Supelco, Inc., Catalog
No. 2-3665, or equivalent) or glass Y splitter for megabore columns
(J&W Scientific, "press-fit", Catalog No. 705-0733, or equivalent).
4.1.2 Columns
4.1.2.1 Column 1, 30 m x 0.53 mm ID, 5% phenyl/95% methyl
silicone fused-silica open tubular column (08-5, J&W Scientific, or
equivalent), 1.5 µm film thickness.
4.1.2.2 Column 2, 30 m x 0.53 mm ID, 14% cyanopropyl
phenyl silicone fused-silica open tubular column (08-1701, J&W
Scientific, or equivalent), 1.0 µm film thickness.
4.1.3 Detector - Dual electron capture detector (ECO)
4.2 Glassware, see Methods 3510, 3540, 3550, 3610, 3620, 3640, and 3660
for specifications.
4.3 Kuderna-Danish (K-0) apparatus.
4.3.1 Concentrator t~be - 10 ml graduated (Kontes K-570050-1025 or
extracts.
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or equiva-
lent). Attach to concentrator tube with springs, clamps, or equivalent.
equivalent).
equivalent).
4.4 Boiling chips, approximately 10/40 mesh. Heat to 400 °C for 30 min,
or Soxhlet-extract with methylene chloride prior to use.
4.5 Water bath, heated, with concentric ring cover, capable of
temperature control (± 2°C).
5.0 REAGENTS
8061 - 4 Revision 0
November 1992
5.3 Sodium sulfate (granular, anhydrous), Na 2S0 4 • Purify by heating at
400 °C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
the sodium sulfate.
5.4 Solvents:
5.4.1 Hexane, C6 H14 - Pesticide quality, or equivalent.
5.4.2 Methylene chloride, CH 2 Cl 2 - Pesticide quality, or equivalent.
5.4.3 Acetone, CH 3COCH 3 - Pesticide quality, or equivalent.
5.4.4 Acetonitrile, CH 3CN - HPlC grade.
5.4.5 Methanol, CH 3 0H - HPlC grade.
5.4.6 Diethyl Ether, C 2 H 5 0C 2 H~ - Pesticide quality, or equivalent.
Must be free of peroxides, as indicated by test strips (EM Quant, or
test strips. After cleanup, 20 ml of ethyl alcohol preservative must be
added to each liter of ether.
5.5 Stock standard solutions:
5.5.1 Prepare stock standard solutions at a concentration of
1000 mg/l by dissolving 0.0100 g of assayed reference material in hexane,
and diluting to volume in a 10 ml volumetric flask. When compound purity
is assayed to be 96 percent or greater, the weight can be used without
correction to calculate the concentration of the stock standard.
Commercially prepared stock standard solutions can be used at any
concentration if they are certified by the manufacturer or by an
independent source.
5.5.2 Transfer the stock standard solutions into glass vials with
Teflon lined screw-caps or crimp tops. Store at 4 °C and protect from
light. Stock standard solutions should be checked periodically by gas
chromatography for signs of degradation or evaporation, especially just
prior to preparation of calibration standards.
5.5.3 Stock standard solutions must be replaced after 6 months, or
5. 6 Ca 1i brat ion standards: Ca 1i brat ion standards are prepared at a
minimum of five concentrations for each parameter of interest through dilution
of the stock standard solutions with hexane. One of the concentrations should
be at a concentration near, but above, the method detection limit. The remaining
in real samples, or should define the working range of the GC. Calibration
solutions must be replaced after 1 to 2 months, or sooner if comparison with
calibration verification standards indicates a problem.
8061 - 5 Revision 0
November 1992
affected by method or matrix interferences. Benzyl benzoate has been tested and
found appropriate for Method 8061.
5.7.1 Prepare a spiking solution of benzyl benzoate in hexane at
5000 mg/L. Addition of 10 µL of this solution to 1 ml of sample extract
is recommended. The spiking concentration of the internal standard should
be kept constant for all samples and calibration standards. Store the
internal standard spiking solution at 4 °C in glass vials with Teflon
lined screw-caps or crimp tops. Standard solutions should be replaced
when ongoing QC (Section 8) indicates a problem.
5.8 Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup (when used), analytical system, and the effectiveness of
the method in dealing with each sample matrix by spiking each sample, standard,
and blank with surrogate compounds. Three surrogates may be used for Method 8061
in addition to those listed in Section 1.4: diphenyl phthalate, diphenyl
isophthalate, and dibenzyl phthalate. However, the compounds listed in Section
1.4 are recommended.
5.8.l Prepare a surrogate standard spiking solution, in acetone,
which contains 50 ng/µL of each compound. Addition of 500 µL of this
solution to 1 L of water or 30 g solid sample is equivalent to 25 µg/L of
water or 830 µg/kg of solid sample. The spiking concentration of the
surrogate standards may be adjusted accordingly, if the final volume of
extract is reduced below 2 ml for water samples or 10 ml for solid
samples. Store the surrogate spiking solution at 4 °C in glass vials with
Teflon lined screw-caps or crimp tops. The solution must be replaced
after 6 months, or sooner if ongoing QC (Section 8) indicates problems.

Section 4. 1.
7. 0 PROCEDURE
7.1 Extraction:
extraction procedure. In general, water samples are extracted at a pH of
5 to 7 with methylene chloride in a separatory funnel (Method 3510).
Method 3520 is not recommended for the extraction of aqueous samples
because the longer chain esters (dihexyl phthalate bis(2-ethylhexyl)
phthalate, di-n-octyl phthalate, and dinonyl phthalate) tend to adsorb to
the glassware and consequently, their ex~raction recoveries are
<40 percent. Solid samples are extracted with hexane/acetone (1:1) or
methylene chloride/acetone (1:1) in a Soxhlet extractor (Method 3540) or
with an ultrasonic extractor (Method 3550). Immediately prior to
8061 - 6 Revision 0
November 1992
extraction, spike 500 µl of the surrogate standard spiking solution
(concentration= 50 ng/µl) into 1 l aqueous sample or 30 g solid sample.
7.1.2 Extraction of particulate-free aqueous samples using
c,8-extraction disks (optional):
7 .1.2.1 Disk preconditioning: Place the C18 -extraction disk
into the filtration apparatus and prewash the disk with 10 to 20 ml
of acetonitrile. Apply vacuum to pull the solvent through the disk.
Maintain vacuum to pull air through for 5 min. Follow with 10 ml of
methanol. Apply vacuum and pull most of the methanol through the
disk. Release vacuum before the disk gets dry. Follow with 10 ml
organic-free reagent water. Apply vacuum and pull most of the water
through the disk. Release the vacuum before the disk gets dry.
7 .1. 2. 2 Sample preconcent ration: Add 2. 5 ml of methano 1 to
the 500 ml aqueous sample in order to get reproducible results.
Pour the sample into the filtration apparatus. Adjust vacuum so
that it takes approximately 20 min to process the entire sample.
After all of the sample has passed through the membrane disk, pull
air through the disk for 5 to 10 min. to remove any residual water.
7.1.2.3 Sample elution: Break the vacuum and place the tip
of the filter base into the test tube that is contained inside the
suction flask. Add 10 ml of acetonitrile to the graduated funnel,
making sure to rinse the walls of the graduated funnel with the
solvent. Apply vacuum to pass the acetonitrile through the membrane
disk.
7.1.2.4 Extract concentration (if necessary): Concentrate
the extract to 2 ml or less, using either the micro Snyder column
technique (Section 7.1.2.4.1) or nitrogen blowdown technique
(Section 7.1.2.4.2).
7.1.2.4.1 Micro Snyder Column Technique
7.1.2.4.1.1 Add one or two clean boiling chips to
the concentrator tube and attach a two ball micro Snyder
co 1umn. Prewet the co 1umn by adding about 0. 5 ml of
acetonitrile to the top of the column. Place the K-D
apparatus in a hot water bath ( 15-20 °C above the
boiling point of the solvent) so that the concentrator
tube is partially immersed in the hot water and the
entire lower rounded surface of the flask is bathed with
hot vapor. Adjust the vertical position of the
apparatus and the water temperature, as required, to
complete the concentration in 5-10 minutes. At the
proper rate of distillation the balls of the column will
actively chatter, but the chambers will not flood. When
the apparent volume of liquid reaches 0.5 ml, remove the
K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes. Remove the Snyder
column and rinse the flask and its lower joints with
8061 - 7 Revision 0
November 1992
about 0. 2 ml of sol vent and add to the concentrator
tube. Adjust the final volume to 1.0-2.0 ml with
solvent.
7.1.2.4.2 Nitrogen Blowdown Technique
7.1.2.4.2.1 Place the concentrator tube in a warm
water bath (approximately 35 °C) and evaporate the
sol vent volume to the required level using a gentle
stream of clean, dry nitrogen (filtered through a column
of activated carbon).
CAUTION: Do not use plasticized tubing between
the carbon trap and the sample.
7.1.2.4.2.2 The internal wall of the tube must be
rinsed down several times with acetonitrile during the
operation. During evaporation, the solvent level in the
tube must be positioned to prevent water from condensing
into the sample (i.e., the solvent level should be below
the level of the water bath). Under normal operating
conditions, the extract should not be allowed to become
dry. '
7.2 Solvent Exchange: Prior to Florisil cleanup or gas chromatographic
analysis, the methylene chloride and methylene chloride/acetone extracts obtained
in Section 7.1.1 must be exchanged to hexane, as described in Sections 7.2.1
through 7.2.3. Exchange is not required for the acetonitrile extracts obtained
in Section 7.1.2.4.
7.2.l Add one or two clean boiling chips to the flask and attach a
three ball Snyder column. Concentrate the extract as described in Section
7.1.2.4.1, using 1 ml of methylene chloride to prewet the column, and
completing the concentration in 10-20 minutes. When the apparent volume
of liquid reaches 1-2 ml, remove the K-D apparatus from the water bath and
allow it to drain and cool for at least 10 minutes.
7.2.2 Momentarily remove the Snyder column, add 50 ml of hexane, a
new boiling chip, and attach the macro Snyder column. Concentrate the
extract as described in Section 7.1.2.4.1, using 1 ml of hexane to prewet
the Snyder column, raising the temperature of the water bath, if
necessary, to maintain proper distillation, and completing the
concentration in 10-20 minutes. When the apparent volume of liquid
reaches 1-2 ml, remove the K-D apparatus and allow it to drain and cool
for at least 10 min.
joint into the concentrator tube with 1 to 2 ml hexane. A 5 ml syringe is
recommended for this operation. Adjust the extract volume to 2 ml for
water samples, using either the micro Snyder column technique (Section
7.1.2.4.1) or nitrogen blowdown technique (Section 7.1.2.4.2), or 10 ml
for solid samples. Stopper the concentrator tube and store at 4 °C if
further processing will be performed immediately. If the extract will be
8061 - 8 Revision 0
November 1992
stored for two days or longer, it should be transferred to a glass vial
with a Teflon lined screw-cap or crimp top. Proceed with the gas
chromatographic analysis.
7.3 Cleanup/Fractionation:
7.3.1 Cleanup may not be necessary for extracts from a relatively
clean sample matrix. If polychlorinated biphenyls (PCBs) and
organochlorine pesticides are known to be present in the sample, use the
procedure outlined in Methods 3610 or 3620. When using column cleanup,
collect Fraction 1 by eluting with 140 ml (Method 3610) or 100 ml
{Method 3620) of 20-percent diethyl ether in hexane. Note that, under
these conditions, bis(2-methoxyethyl) phthalate, bis(2-ethoxyethyl)
phthalate, and bis(2-n-butoxyethyl) phthalate are not recovered from the
Florisil column. The elution patterns and compound recoveries are given
in Table 3.
7.3.2 Methods 3610 and 3620 also describe procedures for sample
cleanup using Alumina and Florisil Cartridges. With this method,
bis(2-methoxyethyl) phthalate, bis(2-ethoxyethyl) phthalate, and
bis(2-n-butoxyethyl) phthalate are recovered quantitatively.
7.4 Gas chromatographic conditions (recommended):
7.4.1 Column 1 and Column 2 (Section 4.1.2):
Carrier gas (He) = 6 ml/min.
Injector temperature = 250 °C.
Detector temperature = 320 °C.
Column temperature:
Initial temperature = 150 °C, hold for 0.5 min.
Temperature program = 150 °C to 220 °C at 5 °C/min.,
followed by 220 °C to 275 °C at 3
°C/min.
Final temperature = 275 °C hold for 13 min.
7.4.2 Table 1 gives the retention times and MDls that can be
achieved by this method for the 16 phthalate esters. An example of the
separations achieved with the DB-5 and DB-1701 fused-silica open tubular
columns is shown in Figure 1.
7.5 Calibration:
7.5.1 Refer to Method 8000 for proper calibration techniques. Use
Tables 1 and 2 for guidance on selecting the lowest point on the
calibration curve.
7. 5. 2 The procedure for internal or external calibration may be
used. Refer to Method 8000 for the description of each of these
procedures.
8061 - 9 Revision 0
November 1992
technique is used, add 10 µL of internal standard solution at 5000 mg/L
to the sample prior to injection.
7.6.2 Follow Method 8000 for instructions on the analysis sequence,
identification criteria.
7. 6. 3 Record the sample volume injected and the resulting peak
areas.
7.6.4 Using either the internal or the external calibration
procedure (Method 8000), determine the identity and the quantity of each
component peak in the sample chromatogram which corresponds to the
compounds used for calibration purposes.
7.6.5 If the response of a peak exceeds the working range of the
system, dilute the extract and reanalyze.
7.6.6 Identify compo,unds in the sample by comparing the retention
times of the peaks in the sample chromatogram with those of the peaks in
standard chromatograms. The retention time window used to make
identifications is based upon measurements of actual retention time
variations over the course of 10 consecutive injections. Three times the
standard deviation of the retention time can be used to calculate a
suggested window size.
8.0 QUALITY CONTROL

the extraction method utilized. If extract cleanup was performed, follow the QC
specified in Method 3600 and in the specific cleanup method.
8. 2 Quality contro 1 required to eva 1uate the GC system operation is found
in Method 8000.
should contain the test compounds at 5 to 10 ng/µL.
8.3 Calculate the recoveries of the surrogate compounds for all samples,
method blanks, and method spikes. Determine if the recoveries are within limits
established by performing QC procedures outlined in Method 8000.
8.3.1 If the recoveries are not within limits, the following are
required:
8.3.1.1 Make sure there are no errors in calculations,
surrogate solutions and internal standards. Also check instrument
performance.
November 1992
8.3.1.2 Recalculate the data and/or reanalyze the extract
if any of the above checks reveal a problem.
8.3.1.3 Reextract and reanalyze the sample if none of the
above are a problem, or flag the data as "estimated concentration."
8. 4 An internal standard peak area check must be performed on a11
samples. The internal standard must be evaluated for acceptance by determining
whether the measured area for the internal standard deviates by more than 30
percent from the average area for the internal standard in the calibration
standards. When the internal standard peak area is outside that 1imit, all
samples that fall outside the QC criteria must be reanalyzed.
8.5 GC/MS confirmation: Any compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration is sufficient for detection by GC/MS
as determined by the laboratory-generated detection limits.
8.5.1 The GC/MS would normally require a minimum concentration of 10
ng/µL in the final extract for each single-component compound.
8.5.2 The sample extract and associated blank should be analyzed by
GC/MS as per Section 7.0 of Method 8270. Normally, analysis of a blank is
not required for confirmation analysis, however, analysis for phthalates
is a special case because of the possibility for sample contamination
through septum punctures, etc.
8.5.3 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a
concentration that would demonstrate the ability to confirm the phthalate
esters identified by GC/ECD.
8.6 Include a mid-concentration calibration standard after each group of
20 samples in the analysis sequence. The response factors for the
mid-concentration calibration must be within± 15 percent of the average values
for the multiconcentration calibration.
8.7 Demonstrate through the analyses of standards that the Florisil
fractionation scheme is reproducible. When using the fractionation schemes given
in Methods 3610 or 3620, batch-to-batch variations in the composition of the
alumina or Florisil material may cause variations in the recoveries of the
phthalate esters.

9.1 The MDL is defined in Chapter One. The MDL concentrations listed in
Table 1 were obtained using organic-free reagent water. Details on how to
determine MDLs are given in Chapter One. The MDL actually achieved in a given
analysis will vary, as it is dependent on instrument sensitivity and matrix
effects.
9.2 This method has been tested in a single laboratory by using different
types of aqueous samples and solid samples which were fortified with the test
compounds at two concentrations. Single-operator precision, overall precision,
November 1992
and method accuracy were found to be related to the concentration of the
compounds and the type of matrix. Results of the single-laboratory method
evaluation are presented in Tables 6 and 7.
9.3 The accuracy and precision obtained is determined by the sample
matrix, sample preparation technique, cleanup techniques, and calibration
procedures used.
10.0 REFERENCES
1. Glazer, J.A.; Feerst, G.D.; McKee, G.D.; Quave, S.A., and Budde, W.L.,
11
"Trace Analyses for Wastewaters, Environ. Sci. and Technol. 15: 1426,
1981.
2. Lopez-Avila, V., Baldin, E., Benedicto, J., Milanes, J., and Beckert,
W.F., "Application of Open-Tubular Columns to SW-846 GC Methods", EMSL-Las
Vegas, 1990.
3. Beckert, W.F. and Lopez-Avila, V., "Evaluation of SW-846 Method 8060 for
Phthalate Esters", Proceedings of Fifth Annual Testing and Quality
Assurance Symposium, USEPA~ 1989.
November 1992
TABLE 1.
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS FOR THE PHTHALATE ESTERSa
Retention time 8
Chemical (min) MDLb
Abstract
Compound Registry Liquid
No. Compound name No. Column 1 Column 2 (ng/L)
1 Dimethyl phthalate 131-11-3 7.06 6.37 640

2 Diethyl phthalate 84-66-2 9.30 8.45 250
3 Diisobutyl phthalate 84-69-5 14.44 12.91 120
4 Di-n-butyl phthalate 84-74-2 16.26 14.66 330
5 Bis(4-methyl-2-pentyl) phthalate 146-50-9 18. 77 16.27 370
6 Bis(2-methoxyethyl) phthalate 117-82-8 17.02 16.41 510
7 Diamyl phthalate 131-18-0 20.25 18.08 110
8 Bis(2-ethoxyethyl) phthalate 605-54-9 19.43 18.21 270
9 Hexyl 2-ethylhexyl phthalate 75673-16-4 21.07 18.97 130
10 Dihexyl phthalate 84-75-3 24.57 21.85 68
11 Butyl benzyl phthalate 85-68-7 24.86 23.08 42
12 Bis(2-n-butoxyethyl) phthalate 117-83-9 27.56 25.24 84
13 Bis(2-ethylhexyl) phthalate 117-81-7 29.23 25.67 270
14 Dicyclohexyl phthalate 84-61-7 28.88 26.35 22
15 Di-n-octyl phthalate 117-84-0 33.33 29.83 49
16 Dinonyl phthalate 84-76-4 38.80 33.84 22
c
IS Benzyl benzoate 120-51-4 12. 71 11.07
c
SU-1 Diphenyl phthalate 84-62-8 29.46 28.32 c
SU-2 Diphenyl isophthalate 744-45-6 32.99 31.37 c
SU-3 Dibenzyl phthalate 523-31-9 34.40 32.65
November 1992
Table 1. (continued)
a Column 1 is a 30 m x 0.53 mm ID DB-5 fused-silica open tubular column (1.5 µm film thickness).
Column 2 is a 30 m 0.53 mm ID DB-1701 fused-silica open tubular column (1.0 µm film thickness).
Temperature program is 150°C (0.5 min hold) to 220°C at 5°C/min, then to 275°C (13 min hold) at
3°C/min. An 8-in Supelco injection tee or a J&W Scientific press fit glass inlet splitter is used
to connect the two columns to the injection port of a gas chromatograph. Carrier gas helium at
6 ml/min; makeup gas nitrogen at 20 ml/min; injector temperature 250°C; detector temperature
320°C.
b MDL is the method detection limit. The MDL was determined from the analysis of seven replicate
aliquots of organic-free reagent water processed through the entire analytical method (extraction,
Florisil cartridge cleanup, and GC/ECD analysis using the single column approach: DB-5 fused-
sil ica capillary column). MDL= t, _1 0 9 > x SD where t n- 1 99 > is the student's
t value appropriate for a 99 percent con~1dence interva~ ah~· a standard deviation with n-1 degrees
of freedom, and SD is the standard deviation of the seven replicate measurements. Values measured
were not corrected for method blanks.
c Not applicable.
November 1992
TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQL) FOR VARIOUS MATRICESa
Matrix Factorb
Groundwater 10
Low-concentration soil by ultrasonic extraction 670
with GPC cleanup
High-concentration soil and sludges by ultrasonic 10,000
extraction
a
Sample EQLs are highly matrix dependent. The EQLs listed herein are
b
EQL = [Method detection limit (Table 1)] X [Factor (Table 2)]. For
nonaqueous samples, the factor is on a wet weight basis.
November 1992
TABLE 3.
AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING METHODS 3610 AND 3620
Compound Alumina8 Florisil Alumina Florisil

column column 8 cartridgeb cartridged
Dimethyl phthalate 64.5 40.0 101 89.4

Diethyl phthalate 62.5 57.0 103 97.3
Diisobutyl phthalate 77.0 80.0 104 91.8
Di-n-butyl phthalate 76.5 85.0 108 102
Bis(4-methyl-2-pentyl) phthalate 89.5 84.5 103 105
Bis(2-methoxyethyl) phthalate 70.5 0 64. lc 78.3e
Diamyl phthalate 75.0 81.5 103 94.5
Bis(2-ethoxyethyl) phthalate 67.0 0 111 93.6
Hexyl 2-ethylhexyl phthalate 90.5 105 101 96.0
Dihexyl phthalate 73.0 74.5 108 96.8
Benzyl butyl phthalate 87.0 90.0 103 98.6
Bis(2-n-butoxyethyl) phthalate 62.5 0 108 91.5
Bis(2-ethylhexyl) phthalate 91.0 82.0 97.6 97.5
Dicyclohexyl phthalate 84.5 83.5 97.5 90.5
Di-n-octyl phthalate 108 115 112 97.l
Dinonyl phthalate 71.0 72.5 97.3 105
a 2 determinations; alumina and Florisil chromatography performed according

to Methods 3610 and 3620, respectively.
b 2 determinations, using 1 g alumina cartridges; Fraction 1 was eluted with
5 ml of 20-percent acetone in hexane. 40 µg of each component was spiked
per cartridge.
c 36. 8 percent was recovered by elution with an additional 5 ml of
20-percent acetone in hexane.
d 2 determinations, using 1 g Florisil cartridges; Fraction l was eluted
with 5 ml of 10-percent acetone in hexane. 40 µg of each component was
spiked per cartridge.
e 14.4 percent was recovered by elution with an additional 5 ml of
10-percent acetone in hexane.
November 1992
TABLE 6.
ACCURACY AND PRECISION DATA FOR METHOD 3510 AND METHOD 806la
Spike Concentration Spike Concentration

{20 ggLL} {60 ggLL}
Estuarine Estuarine
Compound water Leachate Groundwater water Leachate Groundwater
Dimethyl phthalate 84.0 (4.1) 98.9 (19.6) 87.1 (8.1) 87.1 (7.5) 112 (17.5) 90.9 (4.5)
Diethyl phthalate 71.2 (3.8) 82.8 (19.3) 88. 5 (15. 3) 71.0 (7. 7) 88.5 (17.9) 75.3 (3.5)
Diisobutyl phthalate 76.0 (6.5) 95.3 (16.9) 92. 7 (17 .1) 99.1 (19.0) 100 (9.6) 83. 2 (3. 3)
Di-n-butyl phthalate 83.2 (6.5) 97.5 (22.3) 91.0 (10.7) 87.0 (8.0) 106 (17.4) 87. 7 ( 2. 7)
Bis(4-methyl-2-pentyl) phthalate 78.6 (2.6) 87.3 (18.2) 92.6 (13.7) 97 .4 (15.0) 107 (13.3) 87.6 (2.9)
Bis(2-methoxyethyl) phthalate 73.8 (1.0) 87. 2 ( 21. 7) 82.4 (4.4) 82.5 (5.5) 99.0 (13.7) 76.9 (6.6)
Diamyl phthalate 78. 2 (7. 3) 92.l (21.5) 88.8 (7.5) 89.2 (2.8) 112 (14.2) 92.5 (1.8)
Bis(2-ethoxyethyl) phthalate 75.6 (3.3) 90.8 (22.4) 86.4 (5.8) 88.7 (4.9) 109 (14.6) 84.8 (5.9)
Hexyl 2-ethylhexyl phthalate 84. 7 ( 5. 3) 91.1 (27.5) 81.4 (17 .6) 107 (16.8) 117 (11.4) 80. 1 ( 4 .1)
Dihexyl phthalate 79.8 (7.2) 102 (21.5) 90.9 (7 .6) 90.1 (2.4) 109 ( 20. 7) 88.9 (2.4)
Benzyl butyl phthalate 84 .1 ( 6. 4) 105 (20.5) 89.6 (6.1) 92.7 (5.6) 117 ( 24. 7) 93.0 (2.0)
Bis(2-n-butoxyethyl) phthalate 78.5 (3.5) 92.3 (16.1) 89.3 (3.6) 86.1 (6.2) 107 (15.3) 92.4 (0.6)
Bis(2-ethylhexyl) phthalate 81.4 (4.1) 93.0 (15.0) 90.5 (4.9) 86.5 (6.9) 108 (15.1) 91.1 (3.0)
Dicyclohexyl phthalate 77.4 (6.5) 88.2 (13.2) 91.7 (15.2) 87.7 (9.6) 102 (14.3) 71.9 (2.4)
Oi-n-octyl phthalate 74.9 (4.9) 87.5 (18.7) 87.2 (3. 7) 85.1 (8.3) 105 (17.7) 90.4 (2.0)
Oinonyl phthalate 59. 5 (6 .1) 77 .3 (4.2) 67.2 (8.0) 97.2 (7.0) 108 (17.9) 90. 1 ( 1.1)
Surrogates:
Diphenyl phthalate 98. 5 (2. 6) 113 (14.9) 110 (3.3) 110 (12.4) 95.l (7.2) 107 (2.4)
Oiphenyl isophthalate 95.8 (1.9) 112 (11.7) 109 (3.3) 104 (5.9) 97.l ( 7. 1) 106 (2.8)
Dibenzyl phthalate 93.9 (4.4) 112 (14.0) 106 (3.8) 111 (5.9) 93.3 (9.5) 105 (2.4)
a The number of determinations was 3. The values given in parentheses are the percent relative standard deviations of
the average recoveries.
November 1992
TABLE 7.
ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOD 8061 8
Spike Concentration Spike Concentration

{l mgLkg} {3 !!9L9l
Estuarine Municipal Sandy loam Estuarine Municipal Sandy loam
Compound sediment sludge soil sediment sludge soil
c
Dimethyl phthalate 77.9 (42.8) 52.1 (35.5) 136 (9.6) 64.8 (11. 5) 70.2 (2.0)
Diethyl phthalate 68.4 (1. 7) 68.6 (9.1) 54.7 (6.2) 60.2 (12.5) 72.8 (10.0) 67.0 (15.1)
Diisobutyl phthalate 103 (3.1) 106 (5.3) 70.3 (3. 7) 74.8 (6.0) 84.0 (4.6) 79.2 (0.1)
Di-n-butyl phthalate 121 (25.8) 86.3 (17. 7) 72.6
c
(3. 7) 74.6 (3.9) 113 (5.8) 70.9 (5.5)
Bis(4-methyl-2-pentyl) phthalate 108 (57.4) 97.3 (7.4) 104 ( 1. 5) 150 (6.1) 83. 9 (11.B}
Bis(2-methoxyethyl) phthalate 26.6 (26.8) 72. 7 (8.3) 0 19.5 (14.8) 59.9 (5.4) 0
Diamyl phthalate c
95.0 (10.2} 81.9 (7 .1) 81.9
c
(15.9) 77 .3 (4.0) 116 (3. 7) 82.1 (15.5)
Bis(2-ethoxyethyl) phthalate c
66.6 (4.9) 21.7 (22.8) 57.5 (9.2) 84.7 (8.5)
Hexyl 2-ethylhexyl phthalate 114 (I0.5) 57.7 (2.8) 72.7 (11.3) 26.6 (47.6) 28.4 (4.3)
Oihexyl phthalate 103 (3.6) 96.4 (IO. 7) 77.9 (2.4) 75.5 (6.8) 80.3 (4. 7) 79.5 (2. 7)
Benzyl butyl phthalate 113 (12.8) 82.8 (7.8) 56.5
c
(5.1) 72.9 (3.4) 76.8 (10.3) 67.3 (3.8)
Bis(2-n-butoxyethyl) phthalate 114
c
(21.l} 74.0 (15.6) 38.3 (25.1) 98.0 (6.4) 62.0 (3.4)
Bis(2-ethylhexyl) phthalate 76.6 (10.6) 99.2 (25.3) 59.5 (18.3) 85.8 (6.4) 65.4 (2.8)
Dicyclohexyl phthalate c
36.6 (48.8) 65.8 (15.7) 92.8 (35.9) 33.9 (66.1) 68.5 (9.6) 62.2 (19.1)
Di-n-octyl phthalate c
93.3 (14.6) 84.7 (9.3) c
36.8 (16.4) 88.4 (7.4) 115 (29.2)
Dinonyl phthalate 80 .0 ( 41. l) 64. 2 (17. 2) 156 (8.6) 115 (13.2)
a The number of determinations was 3. The values given in parentheses are the percent relative standard deviations of the
average recoveries. All samples were subjected to Florisil cartridge cleanup.
b The estuarine sediment extract (Florisil, Fraction 1) was subjected to sulfur cleanup (Method 3660 with
tetrabutylammonium sulfite reagent).
c Not able to determine because of matrix interferant.
November 1992
Figure 1
08-5
30 m x 0.53 mm ID
1.S-µmFilm
IS 11 12 SU-1 SU-2 SU-3
6 8 14
15
5 13
16
10
4 7 9
2
3
08-1701
30 m x 0.53 mm ID
SU-2 SU-3 1.0-µ.m Film
IS 6
8
12 SU-1 15 f f ,6
13
11
4 7 10
14
2
5
3
9
+
I
0 10 20 30 40
TIME (min)
GC/ECD chromatograms of a composite phthalate esters standard (concentration

10 ng/µL per compound) analyzed on a DB-5 and a DB-1701 fused-silica open
tubular column. Temf,erature program: 150°C {0.5 min hold) to 220°C at
5°C/min, then to 275 C (13 min hold) at 3°C/min.
November 1992
METHOD 8061
PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
WITH ELECTRON CAPTURE DETECTION (GC/ECD)
7 .1 Extracllon
7.3 CleanuplFradlonallon
7.1.1 Refer to Chapa 2 for

guidance on choosing 7.3.1 Cleanup may not be
an ex1raction procedure. necessary for extrads wilh
Recommendation& given. clean sample ma11'ices.
Fraction c:clledion and
melhods outlined for OCher
compd. groups of interest
7.1.2 Detenmne spike safTl)le
recoYer}' and cle1ectlon limit
for each new sample matrix
and a given ex1raction 7.3.2 Florisil Cartridge Cleanup
procedure. .1 Check each lot of Florisil
carTidges for analyte
retXNer'f by eluting and
analyzing a composite std.
7 .1 .3 Aqueous sample extraction .2 Wash and adjust solvent
with C18 disks: now lhrough cartridges .
.1 Precondition disks USlng .3 Place a.illure tubes or s mi .
solVent !rain. vol. ftaska for eluate
.2 Concentrate sample oolleelion .
anatytes on disk. .4 Transfer appropriate extract
.3 Elute safTllle analytes volume on cartridge.
with acetoni1rlle. .5 Elute the cartridges and
.4 Concentrate extract dilute ID marK on ftasK.
.1 Miao-Snyder Column
Transfer eluate to glass
Technique vials for concentration.
.2 Nitrogen Blowdown
Technique
.1 Evaporate solvent to
desired level 7.3.3 Collect 2 fractions if PCBs
and organochlorine peslic:ides
.2 Rinse tube walls
frequently and avoid are known to be present
evaporating ID dryness.
7.4 Gas Chromatograph

7.2 Solvent Exchange to Hexane
7.4.1 SetGC operating parameters.

7.2.1 Evaporate extract volume to
1-2 ml. using K-0 assembly.
7.4.2 Table 1 and Figure 1 show
MOL.s and analyte retenlicn
7.2.2 Add hexane to K-0 assembly limes.
and evaporate to 1-2 ml.
7.2.3 Riru K-0 components and

adjust volume to desired level.
November 1992
METHOD 8061
(CONTINUED)
7 .5 Calibration
7.5.1 See Melhod 8000 for

calibration technique.
7.5.2 Refer to Method 8000 for

intemal/extsmal std.
procedure.
7.6 GC Analysis
7.6.1 Reier to Melhod 8000.
7.6.2 Follow Section 7.6 in

Melhod 8000 for
instructions on analysis
sequence, dilutions,
retention time windows,
and identification ai'9ria.
7.6.3 Record injection volume

and sample peak areas.
7.6.4 Identify and quantify each

component peak using Iha
internal Of external Sid.
procedure.
7.6.5 Dilute extrad& whlctt

show analyte leYeis
outside of lhe calibration
range.
7.6.6 Identify compouids in the

sample by comparing
retanbon limes in lhe
sampe and lhe standard
chrcmatograms.
November 1992
METHOD 8070
NITROSAMINES

I.I This method covers the determination of certain nitrosamines. The
following parameters can be determined by this method:
Parameter CAS No.
N-Nitrosodimethylamine 62-75-9
N-Nitrosodiphenylamine 86-30-6
N-Nitrosodi-n-propylamine 621-64-7
1.2 This is a gas chromatographic (GC) method applicable to the

determination of the parameters listed above in municipal and industrial
discharges. When this method is used to analyze unfamiliar samples for any or
all of the compounds above, compound identifications should be supported by at
least one additional qualitative technique. This method describes analytical
conditions for a second gas chromatographic column that can be used to confirm
measurements made with the primary column. Method 8270 provides gas
chromatograph/mass spectrometer ( GC/MS) conditions appropriate for the
qualitative and quantitative confirmation of results for N-ni trosodi -n-
propyl amine. In order to confirm the presence of N-nitrosodi-phyenylamine, the
cleanup procedure specified in Step 7.3.3 or 7.3.4 must be used. In order to
confirm the presence of N-nitrosodimethylamine by GC/MS, chromatographic
column I of this method must be substituted for the co 1umn recommended in
Method 8270. Confirmation of these parameters using GC-high resolution mass
spectrometry or a Thermal Energy Analyzer is also recommended practice.
1.3 The method detection limit (MDL) for each parameter is listed in
Table 1. The MDL for a specific wastewater may differ from those listed,
depending upon the nature of interferences in the sample matrix. Table 2 lists
the Practical Quantitation Limits (PQLs) for various matrices.
1.4 Any modification of this method, beyond those expressly permitted,
shall be considered as major modifications subject to application and approval
of alternate test procedures.
1.5 The toxicity or carcinogenicity of each reagent used in this method
has not been precisely defined. However, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to these
chemicals must be reduced to the lowest possible level by whatever means
available. The laboratory is responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of the chemicals
specified in this method. A reference file of material data handling sheets
8070 - I Revision 0
December 1987
should also be made available to all personnel involved in the chemical
analysis.
1.6 These nitrosamines are known carcinogens. Therefore, utmost care must
be exercised in the handling of these materials. Nitrosamine reference
standards and standard solutions should be handled and prepared in a
ventilated glove box within a properly ventilated room.
1.7 N-Nitrosodiphenylamine is reported to undergo transnitrosation
reactions. Care must be exercised in the heating or concentrating of solutions
containing this compound in the presence of reactive amines.
2.1 A measured volume of sample, approximately one liter, is solvent
extracted with methylene chloride using a separatory funnel . The methylene
chloride extract is washed with dilute HCl to remove free amines, dried, and
concentrated to a volume of 10 ml or less. Gas chromatographic conditions are
described which permit the separation and measurement of the compounds in the
extract after it has been exchanged to methanol.
of ppb levels of nitrosamines. Prior to use of this method, appropriate sample
extraction techniques must be used. Both neat and diluted organic liquids
(Method 3580, Waste Dilution) may be analyzed by direct injection. A 2- to
5-ul aliquot of the extract is injected into a gas chromatograph (GC) using
the solvent flush technique, and compounds in the GC effluent are detected by
a nitrogen-phosphorus detector (NPD) or a Thermal Energy Analyzer and the
reactive Hall detector.
3.0 INTERFERENCES
3. 2 Matrix interferences may be caused by contaminants that are
coextracted from the sample. The extent of matrix interferences will vary
considerably from source to source, depending upon the nature and diversity of
the industrial complex or municipality being sampled. The cleanup procedures
(Methods 3610 or 3620) can be used to overcome many of these interferences,
but unique samples may require additional cleanup approaches to achieve the
MDL listed in Table 1.
3.3 Nitrosamines contaminate many types of products commonly found in the
laboratory. The analyst must demonstrate that no nitrosamine residues
contaminate the sample or solvent extract under the conditions of analysis.
Plastics, in particular, must be avoided because nitrosamines are commonly
used as plasticizers and are easily extracted from plastic materials. Serious
nitrosamine contamination may result at any time if consistent quality control
is not practiced.
3.4 The sensitive and selective Thermal Energy Analyzer and the reductive
Hall detector may be used in place of the nitrogen-phosphorus detector when
8070 - 2 Revision 0
December 1987
interferences are encountered. The Thermal Energy Analyzer offers the highest
selectivity of the non-mass spectrometric detectors.
may yield discrete artifacts and/or elevated baselines causing
misinterpretation of gas chromatograms. All these materials must be
demonstrated to be free from interferences, under the conditions of the
analysis, by analyzing calibration and reagent blanks. Specific selection of
reagents and purification of solvents by distillation in all-glass systems may
be required.
3.6 Interferences coextracted from samples will vary considerably from
source to source, depending upon the waste being sampled. Although general
cleanup techniques are recommended as part of this method, unique samples may
require additional cleanup.
equivalent). Calibration must be checked at the volumes employed in the
test. Ground glass stopper is used to prevent evaporation of extracts.
equivalent).
4.1.4 Synder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.2 Boiling chips - Approximately 10/40 mesh. Heat to 400°C for
30 minutes or Soxhlet extract with methylene chloride.
4.4 Balance - Analytical, capable of accurately weighing 0.0001 g.
4.5 Vials - 10- to 15-ml, amber glass with Teflon lined screw-cap.
4.6 Gas chromatograph - An analytical system complete with temperature
programmable gas chromatograph suitable for on-column injection and all
required accessories including syringes, analytical columns, gases, detector,
and strip-chart recorder. A data system is recommended for measuring peak
areas.
4.6.1 Column 1 - 1.8 m x 4 mm i.d. Pyrex glass, packed with
Chromosorb W AW, (80/100 mesh) coated with 10% Carbowax 20 M/2% KOH or
equivalent. This column was used to develop the method performance
8070 - 3 Revision 0
December 1987
statements in Section 9.0. Guidelines for the use of alternate column
packings are provided in Step 7.3.2.
4.6.2 Column 2 - 1.8 m x 4 mm i.d. Pyrex glass, packed with
Supelcoport (100/120 mesh) coated with 10% SP-2250.
4.6.3 Detector - Nitrogen-Phosphorus, reductive Hall or Thermal
Energy Analyzer. These detectors have proven effective in the analysis of
wastewaters for the parameters listed in the scope. A nitrogen-phosphorus
detector was used to develop the method performance statements in Section
9.0. Guidelines for the use of alternate detectors are provided in Step
7.3.2.
5.0 REAGENTS
determination.
5.2 ASTM Type II Water (ASTM 01193-77 (1983)}. All references to water in
5.3 Methanol, CH30H. Pesticide quality or equivalent.
5.4 Stock standard solutions (1000 mg/L) - Stock standard solutions can
be prepared from pure standard materials or purchased as certified solutions.
5.4.1 Prepare stock standard solutions by accurately weighing
0.1000 ± 0.0010 g of pure material. Dissolve the material in pesticide
quality methanol and dilute to volume in a 100-ml volumetric flask. Larger
volumes can be used at the convenience of the analyst. If compound purity
is certified at 963 or greater, the weight can be used without correction
to cal cul ate the concentration of the stock standard. Commercially
prepared stock standards can be used at any concentration if they are
certified by the manufacturer or by an independent source.
5.4.2 Transfer the stock standard solutions into bottles with Teflon
lined screw-caps. Store at 4°C and protect from light. Stock standard
solutions should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them.
5.4.3 Stock standard solutions must be replaced after six months, or
sooner if comparison with check standards indicate a problem.
5.5 Calibration standards - A minimum of five levels should be prepared
through dilution of the stock standards with i sooctane. One of the
concentration levels should be at a concentration near, but above, the method
8070 - 4 Revision 0
December 1987
detection limit. The rema1n1ng concentration levels should correspond to the
expected range of concentrations found in real samples or should define the
working range of the GC. Calibration solutions must be replaced after six
months, or sooner if comparison with check standards indicates a problem.
concentration levels for each analyte of interest as described in Step
5.5.
one or more internal standards, and dilute to volume with isooctane.
5.7 Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent blank with one or two surrogates (e.g.
nitrosamines are not expected to be in the sample) recommended to encompass
the range of the temperature program used in this method. Method 3500, Step
5. 3 .1.1, details instructions on the preparation of base/neutral surrogates.
Deuterated analogs of analytes should not be used as surrogates for gas
chromatographic analysis due to coelution problems.
4.1. Extracts must be stored at 4°C and analyzed within 40 days of
extraction.
7.0 PROCEDURE
7.1 Extraction
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using either Method 3540 or 3550.
must be exchanged to methanol. The exchange is performed during the K-D
procedures listed in a11 of the extraction methods. The exchange is
performed as follows.
7.1.2.1 Following K-D of the methylene chloride extract to 1 ml
using the macro-Snyder column, allow the apparatus to cool and drain
for at.least 10 minutes. 8070 _ 5 Revision 0
December 1987
7. 1. 2. 2 Momentarily remove the Snyder column, add 50 ml of
methanol, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 ml of methanol to prewet the Snyder
column. Pl ace the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust the
vertical position of the apparatus and the water temperature, as
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the K-D apparatus and allow it to drain and cool
for at least 10 minutes. The extract will be handled differently at
this point, depending on whether or not cleanup is needed. If
cleanup is not required, proceed to Step 7.1.2.3. If cleanup is
needed, proceed to Step 7.1.2.4.
7.1.2.3 If cleanup of the extract is not required, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with 1-2 ml of methanol. A 5-ml syringe is
recommended for this operation. Adjust the extract volume to
10.0 ml. Stopper the concentrator tube and store refrigerated at 4°C
if further processing will not be performed immediately. If the
extract will be stored longer than two days, it should be transferred
to a vial with a Teflon lined screw-cap. Proceed with gas
chromatographic analysis.
7.1.2.4 If cleanup of the extract is required, remove the
Snyder column and rinse the flask and its lower joint into the
concentrator tube with a minimum amount of methylene chloride. A
5-ml syringe is recommended for this operation. Add a clean boiling
chip to the concentrator tube and attach a two ba 11 micro-Snyder
column. Prewet the column by adding about 0.5 ml of methanol to the
top. Place the micro K-D apparatus on the water bath (80°C) so that
the concentrator tube is partially immersed in the hot water. Adjust
required, to complete concentration in 5-10 minutes. At the proper
rate of distillation the balls of the column will actively chatter,
but the chambers will not flood. When the apparent volume of liquid
reaches 0.5 ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 minutes.
7.1.2.5 Remove the micro-Snyder column and rinse the flask and
its lower joint into the concentrator tube with 0.2 ml of methylene
chloride. Adjust the extract volume to 2.0 ml and proceed with
either Method 3610 or 3620.
7.1.3 If N-nitrosodiphenylamine is to be measured by gas
chromatography, the analyst must first use a cleanup column to eliminate
diphenylamine interference (Methods 3610 or 3620). If N-nitrosodiphenyl-
amine is of no interest, the analyst may proceed directly with gas
chromatographic analysis (Step 7.3).
8070 - 6 Revision O
December 1987
7.2 Cleanup
7.2.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix. The cleanup procedure recommended in this method has been
used for the analysis of various clean waters and industrial effluents. If
particular circumstances demand the use of an alternative cleanup
procedure, the analyst must determine the elution profile and demonstrate
that the recovery of each compound of interest is no less than 85%.
Diphenylamine, if present in the original sample extract must be separate
from the nitrosami nes if N-nitrosodi phenyl amine is to be determined by
this method.
7. 2. 2 Proceed with either Method 3610 or 3620, using the 2-ml
methylene chloride extracts obtained from Step 7.1.2.5.
7.2.3 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.
7.3 Gas Chromatography
7.3.1 N-nitrosodiphenylamine completely reacts to form diphenylamine
at the normal operating temperatures of a GC injection port (200 to
250°C). Thus, N-nitrosodiphenylamine is chromatographed and detected as
diphenylamine. Accurate determination depends on removal of diphenylamine
that may be present in the original extract prior to GC (see Step 7.3).
7.3.2 Table 1 summarizes the recommended operating conditions for
the gas chromatograph. This table includes retention times and MDLs that
were obtained under these conditions. Examples of the parameter
separations achieved by these columns are shown in Figures 1 and 2. Other
packed columns, chromatographic cond it i ans, or detectors may be used if
the requirements of Step 8.2 are met. Capillary (open-tubular) columns may
also be used if the relative standard deviations of responses for
replicate injections are demonstrated to be less than 6% and the
requirements of Step 8.2 are met.
7.4 Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point
on the calibration curve.
7.4.2 If cleanup is performed on the samples, the analyst should
process a series of standards through the cleanup procedure and then
analyze the samples by GC. This will confirm elution patterns and the
absence of interferents from the reagents.
7. 5 .1 Refer to Method 8000. If the internal standard calibration
8070 - 7 Revision 0
December 1987
technique is used, add 10 ul of internal standard to the sample prior to
injection.
7. 5.2 Follow Step 7.6 in Method 8000 for instructions on the
time windows, and identification criteria. Include a midlevel check
standard after each group of 10 samples in the analysis sequence.
7.5.3 Examples of GC/NPD chromatograms for nitrosamines are shown in
Figures 1 and 2.
7.5.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7. 5. 5 Using either the i nterna 1 or extern a1 ca 1 i brat ion procedure
(Method 8000), determine the identity and quantity of each analyte peak in
the sample chromatogram. See Step 7.8 of Method 8000 for calculation
equations.
7.5.6 If peak detection and identification are prevented due to
interferences, the hexane extract may undergo cleanup using either Method
3610 or 3620.
8.0 QUALITY CONTROL
the extraction method utilized. If extract cleanup was performed, follow the
QC in Method 3600 and in the specific cleanup method.
8.2 Procedures to check the GC system operation are found in Method 8000,
Step 8.6.
8.2.1 The quality control (QC) reference sample concentrate (Method
8000, Step 8.6) should contain each analyte of interest at 20 ug/ml.
of concentration for the analytes of interest. The contents of both
performing QC procedures outlined in Method 8000, Step 8.10).
o Check to be sure there are no errors in ca 1cul at ions,
8070 - 8 Revision 0
December 1987
o Recalculate the data and/or reanalyze the extract if any
o Reextract and reanalyze the sample if none of the above
concentration."
9.1 This method has been tested for linearity of recovery from spiked
reagent water and has been demonstrated to be applicable for the concentration
range from 4 x MDL to 1000 x MDL.
9.2 In a single laboratory (Southwest Research Institute), using spiked
wastewater samples, the average recoveries presented in Table 2 were obtained.
Each spiked sample was analyzed in triplicate on three separate occasions. The
standard deviation of the percent recovery is also included in Table 2.
9.3 The U.S. Environmental Protection Agency is in the process of
conducting an interlaboratory method study to fully define the performance of
this method.
10.0 REFERENCES
1. Fed. Reqist. 1984, 49, 43234; October 26.
2. Fine, D.H.; Lieb, D.; Rufeh, R. "Principle of Operation of the Thermal
Energy Analyzer for the Trace Analysis of Volatile and Non-volatile N-
nitroso compounds"; Journal of Chromatography 1975, 107, 351.
3. Fine, D.H.; Hoffman, F.; Rounbehler, D.P.; Belcher, N.M. N-nitroso
Compounds - Analysis and Formation Lyon; Walker, E.A.; Bogovski, P.;
Griciute, L., Eds.; International Agency for Research on Cancer (IARC
Scientific Publications No. 14), pp 43-50, 1976.
4. "Determination of Nitrosamines in Industrial and Municipal Wastewaters 11 ;
Report for EPA Contract 68-03-2606, in preparation.
5. ASTM Annual Book of Standards, Part 31; "Standard Practice for
Preparation of Sample Containers and for Preservation"; ASTM:
Philadelphia, PA, 1980; D3694.
6. Buglass, A.J.; Challis, B.C.; Osborn, M.R. N-Nitroso Compounds in the
Environment; Bogovski, P.; Walker, E.A., Eds.; International Agency for
Research on Cancer (IARC Scientific Publication No. 9), pp 94-100, 1974.
7. Burgess, E.M.; Lavanish, J.M. "Photochemical Decomposition of N-
nitrosamines"; Tetrahedon Letters 1964, 1221.
8. Druckrey, H.; Preussman, R.; Ivankovic, S.; Schmahl, D. "Organotrope
Carcinogene Wirkungen bei 65 Verschiedenen N-Nitroso-Verbindungen an BD-
Ratten"; "L_ Krebsforsch 1967, 69, 103.
8070 - 9 Revision 0
December 1987
9. Fiddler, W. "The Occurrance and Determination of N-nitroso Compounds";
Toxicol. ~ Pharmacol. 1975, .31, 352.
10. "Carcinogens - Working with Carcinogens"; Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206; August, 1977.
11. "OSHA Safety and Health Standards, General Industry"; Occupational Safety
and Health Administration, OSHA 2206, revised January, 1976 (29CFR1910).
12. Safety in Academic Chemistry Laboratories, 3rd ed.; American Chemical
Society Publication, Committee on Chemical Safety, 1979.
13. Lijinsky, W. "How Nitrosamines Cause Cancer"; New Scientist 1977, 73,
216.
14. Mirvish, S.S. "N-Nitroso compounds: Their Chemical and in vivo Formation
and Possible Importance as Environmental Carcinogens"; ~ Toxicol.
Environ. Health 1977, l, 1267.
15. "Reconnaissance of Environmental Levels of Nitrosamines in the Central
United States"; U.S. Environmental Protection Agency. National
Enforcement Investigations Center, Report No. EPA-330/1-77-001, 1977.
16. "Atmospheric Nitrosamine Assessment Report"; U.S. Envirnmental Protection
Agency. Office of Air Quality Planning and Standards. Research Triangle
Park, NC, 1976.
17. "Scientific and Technical Assessment Report on Nitrosamines"; U.S.
Environmental Protection Agency. Office of Research and Development.
Report No. EPA-660/6-7-001, 1976.
18. Handbook of Analytical Quality Control in Water and Wastewater
Laboratories; U.S. Environmental Protection Agency. Environmental
Environmental Research Information: Cincinnati, OH, March 1983, EPA-
600/4-79-019.
19. ASTM Annual Book of Standards, Part 31; "Standard Practice for Sampling
Water"; ASTM: Philadelphia, PA, 1980; D3370.
20. Methods for Chemical Analysis of Water and Wastes; U.S. En vi ronmenta l
Protection Agency. Office of Research and Development. En vi ronmenta l
600/4-79-020.
21. Burke, J.A. "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects"; J.:. of the Assoc. of Official Anal. Chemists 1965, 48,
1037.
December 1987
22. "Method Detection Limit and Analytical Curve Studies EPA Methods 606,
607, 608"; U.S. Environmental Protection Agency. Environmental Monitoring
and Support Laboratory, Cincinnati, OH, special letter report for EPA
Contract 68-03-2606.
December 1987
TABLE 1.
Retention Time Method

(minutes) Detection Limit
Parameter Column 1 Column 2 ( ug/L)
N-Nitrosodimethylamine 4.1 0.88 0.15
N-Nitrosodi-n-propylamine 12.1 4.2 0.46
N-Nitrosodiphenylaminea 12.8b 6.4C 0.81
Column 1 conditions: Chromosorb WAW(80/100 mesh) coated with 10% Carbowax

20 M/2% KOH packed in a 1.8 m x 4 mm i.d. glass column with helium carrier
gas at a flow rate of 40 ml/min column temperature Isothermal, at ll0°C,
except as otherwise indicated.
Column 2 conditions: Supelcoport (100/120 mesh) coated with 10% SP-2250
packed in a 1.8 m x 4 mm i.d. glass column with helium carrier gas at a
flow rate of 40 ml/min column temperature, Isothermal at 120°C, except as
otherwise indicated.
aMeasured as diphenylamine.
bDetermined isothermally at 220°C.
CDetermined isothermally at 210°C.
TABLE 2.
SINGLE OPERATOR ACCURACY AND PRECISION
Average Standard Spike Number

Percent Deviation Range of Matrix
Parameter Recovery % (ug/L) Analyses Types
N-Nitrosodimethylamine 32 3.7 0.8 29 5
N-Nitrosodiphenylamine 79 7.1 1.2 29 5
N-Nitrosodi-n-propylamine 61 4.1 9.0 29 5
December 1987
FIGURE I.
GAS CHROMATOGRAM OF NITROSAMINES
Column: 10% Carbowax 20M + 2"

KOH on Chromosorb W-A W
Temperature: 110°
Detector: Phosphorus/ Nitrogen
2 4 6 8 10 12 14
Retention ti,,,., minute•
December 1987
FIGURE 2.
GAS CHROMATOGRAM OF N-NITROSODIPHENYLAMINE AS DIPHENYLAMINE
Column: 10% Carbowu 20M + 2% KOH on

Chromosorb W-A W
Temperature: 220°C.
Detector: Phosphorus/ Nitrogen
0 2 4 6 8 10 12 14 16 18
Retention time. minutes
December 1987
METHOD 8070
NITROSAMINES
Start
7 .1.1 CllooH 7.1.3 Parfora

appropriate colaaa cleanp
extractioa a1iag Method 3810
procadare or 3820
7.3.2 Ider to
Table 1 for
7.1.2 Perfora racoaaaadad
eolveat exchange oreratiag
uiag aetllaaol coadit oaa for tlla
cc
7.1.2.4 Perfora
aicro-1-D procedure 7.4 Refer to Method
uin' Hthyhae 8000 for proper
chloride; perfora calibration
Mothod 3810 or tochaiqau
3120; proceed vitll
CC analy1il
7.1.2.3 Adjut
extract vol••• aad 7.6.1 Ider to
procHd vitll Metllod 1000 for
aaaly1i1 or atora 1aidaac1 oa OC
ia appropriate aaalyli•
aauer
7.6.4/7.6.6 lecord
eaaph volue
iajected ud
ranl ti•I peall
•ize; p•rfora
appropriate
calcalatiou
(Metllod 8000, Step
7.8)
Stop
December 1987
METHOD 8080A
ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
BY GAS CHROMATOGRAPHY

I.I Method 8080 is used to determine the concentration of various
)rganochlorine pesticides and polychlorinated biphenyls (PCBs). The following
:ompounds can be determined by this method:
Aldrin 309-00-2
a-BHC 319-84-6
{3-BHC 319-85-7
6-BHC 319-86-8
y-BHC (Lindane) 58-89-9
Chlordane (technical) 12789-03-6
4,4'-DDD 72-54-8
4,4'-DDE 72-55-9
4,4'-DDT 50-29-3
Dieldrin 60-57-1
Endosulfan I 959-98-8
Endosulfan II 33212-65-9
Endosulfan sulfate 1031-07-8
Endrin 72-20-8
Endrin aldehyde 7421-93-4
Heptachlor 76-44-8
Heptachlor epoxide 1024-57-3
4,4'-Methoxychlor 72-43-5
Toxaphene 8001-35-2
Aroclor-1016 12674-11-2
Aroclor-1221 1104-28-2
Aroclor-1232 11141-16-5
Aroclor-1242 53469-21-9
Aroclor-1248 12672-29-6
Aroclor-1254 11097-69-1
Aroclor-1260 11096-82-5

1.2 Table 1 lists the method detection limit for each compound in
organic-free reagent water. Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
8080A - I Revision I
November 1992
of ppb concentrations of certain organochlorine pesticides and PCBs. Prior to
the use of this method, appropriate sample extraction techniques must be used.
Both neat and diluted organic liquids (Method 3580, Waste Dilution) may be
analyzed by direct injection. A 2 to 5 µ.L sample is injected into a gas
chromatograph (GC) using the solvent flush technique, and compounds in the GC
effluent are detected by an electron capture detector (ECO) or an electrolytic
conductivity detector (HECO).
2.2 The sensitivity of Method 8080 usually depends on the concentration
of interferences rather than on instrumental 1imitations. If interferences
prevent detection of the analytes, Method 8080 may also be performed on samples
that have undergone cleanup. Method 3620, Florisil Column Cleanup, by itself or
followed by Method 3660, Sulfur Cleanup, may be used to eliminate interferences
in the analysis.
3.0 INTERFERENCES
3.2 Interferences by phthalate esters can pose a major problem in
pesticide determinations when using the electron capture detector. These
compounds generally appear in the chromatogram as 1arge 1ate-eluting peaks,
especially in the 15% and 50% fractions from the Florisil cleanup. Common
flexible plastics contain varying amounts of phthalates. These phthalates are
easily extracted or leached from such materials during laboratory operations.
Cross contamination of clean glassware routinely occurs when plastics are handled
during extraction steps, especially when solvent-wetted surfaces are handled.
Interferences from phthalates can best be minimized by avoiding contact with any
plastic materials. Exhaustive cleanup of reagents and glassware may be required
to eliminate background phthalate contamination. The contamination from
phthalate esters can be completely eliminated with a microcoulometric or
electrolytic conductivity detector.

4.1.l Gas Chromatograph: Analytical system complete with gas
chromatograph suitable for on-column injections and all required
accessories, including detectors, column supplies, recorder, gases, and
syringes. A data system for measuring peak heights and/or peak areas is
recommended.
4.1.2 Columns
4.1.2.1 Column 1: Supelcoport (100/120 mesh) coated with
1.5% SP-2250/1.95% SP-2401 packed in a 1.8 m x 4 mm ID glass column
or equivalent.
November 1992
4.1.2.2 Column 2: Supelcoport (100/120 mesh) coated with
3% OV-1 in a 1.8 m x 4 mm ID glass column or equivalent.
4.1.3 Detectors: Electron capture (ECO) or electrolytic
conductivity detector (HECD).
4.2 Kuderna-Danish (K-D) apparatus:
4.2.1 Concentrator tube: 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.2.2 Evaporation fl ask: 500 ml (Kontes K-570001-500 or
equivalent.
4.2.3 Snyder column: Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column: Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3 Boiling chips: Solvent extracted, approximately 10/40 mesh (silicon
4.4 Water bath: Heated, with concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.5 Volumetric flasks, Class A: sizes as appropriate with ground-glass
stoppers.
4.6 Microsyringe: 10 µL.
4.7 Syringe: 5 ml.
4.8 Vials: Glass, 2, 10, and 20 ml capacity with Teflon-lined screw caps
or crimp tops.
4.9 Balances: Analytical, 0.0001 g and Top loading, 0.01 g.
5.0 REAGENTS
November 1992
5.3 Solvents
5.3.1 Hexane, C6H14 - Pesticide quality or equivalent.
5.3.2 Acetone, CH 3 COCH 3 - Pesticide quality or equivalent.
5.3.3 Toluene, C6 H5CH3 - Pesticide quality or equivalent.
5.3.4 Isooctane, (CH 3 '3CCH 2CH(CH3 ) 2 - Pesticide quality or equivalent.
5.4 Stock standard solutions:
5.4.1 Prepare stock standard solutions at a concentration of
1000 mg/L by dissolving 0.0100 g of assayed reference material in
isooctane and diluting to volume in a 10 ml volumetric flask. A small
volume of toluene may be necessary to put some pesticides in solution.
Larger volumes can be used at the convenience of the analyst. When
compound purity is assayed to be 96% or greater, the weight can be used
without correction to calculate the concentration of the stock standard.
Commercially prepared stock standards can be used at any concentration if
they are certified by the manufacturer or by an independent source.
5.4.2 Transfer the stock standard solutions into vials with Teflon-
1ined screw caps or crimp tops. Store at 4°C and protect from light.
Stock standards should be checked frequently for signs of degradation or
evaporation, especially just prior to preparing calibration standards from
them.
5.4.3 Stock standard solutions must be replaced after one year, or
concentrations for each parameter of interest are prepared through dilution of
the stock standards with isooctane. One of the concentrations should be at a
in real samples or should define the working range of the GC. Calibration
solutions must be replaced after six months, or sooner, if comparison with check
standards indicates a problem.
5.6.l Prepare calibration standards at a minimum of five
concentrations for each analyte of interest as described in Section 5.5.
one or more internal standards, and dilute to volume with isooctane.
November 1992
5.7 Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of the method in dealing with each sample matrix by spiking each sample,
standard, and organic-free reagent water blank with pesticide surrogates.
Because GC/ECD data are much more subject to interference than GC/MS, a secondary
surrogate is to be used when sample interference is apparent. Two surrogate
standards (tetrachloro-m-xylene {TCMX) and decachlorobiphenyl) are added to each
sample; however, only one need be calculated for recovery. Proceed with
corrective action when both surrogates are out of limits for a sample (Section
8. 3). Method 3500 indicates the proper procedure for preparing these surrogates.

Section 4.1. Extracts must be stored under refrigeration and analyzed within 40
days of extraction.
7. 0 PROCEDURE
7.1 Extraction:
extraction procedure. In general, water samples are extracted at a
neutral, or as is, pH with methylene chloride, using either Method 3510 or
3520. Solid samples are extracted using Method 3540, 3541, or 3550.
must be exchanged to hexane. The exchange is performed during the K-D
procedures listed in all of the extraction methods. The exchange is
performed as follows.
7.1. 2 .1 Fo 11 owing K-D of the methylene ch 1ori de extract to
1 ml using the macro-Snyder column, allow the apparatus to cool and
drain for at least 10 min.
7.1.2.2 Increase the temperature of the hot water bath to
about 90°C. Momentarily remove the Snyder column, add 50 ml of
hexane, a new boiling chip, and reattach the macro-Snyder column.
Concentrate the extract using 1 ml of hexane to prewet the Snyder
column. Pl ace the K-D apparatus on the water bath so that the
concentrator tube is partially immersed in the hot water. Adjust
required, to complete concentration in 5-10 min. At the proper rate
of distillation the balls of the column will actively chatter, but
the chambers will not flood. When the apparent volume of liquid
reaches I ml, remove the K-D apparatus and allow it to drain and
cool for at least 10 min.
7.1.2.3 Remove the Snyder column and rinse the flask and
its lower joint into the concentrator tube with 1-2 ml of hexane.
A 5 ml syringe is recommended for this operation. Adjust the
extract volume to 10.0 ml. Stopper the concentrator tube and store
November 1992
refrigerated at 4°C, if further processing will not be performed
immediately. If the extract will be stored longer than two days, it
should be transferred to a vial with a Teflon-lined screw cap or
crimp top. Proceed with gas chromatographic analysis if further
cleanup is not required.
7.2 Gas chromatography conditions (Recommended):
7.2.l Column 1:
Carrier gas (5% methane/95% argon) flow rate: 60 ml/min
Column temperature: 200°C isothermal
When analyzing for the low molecular weight PCBs (PCB 1221-PCB
1248), it is advisable to set the oven temperature to 160°C.
7.2.2 Column 2:
Carrier gas (5% methane/95% argon) flow rate: 60 ml/min
Column temperature: 200°C isothermal
When analyzing for the low molecular weight PCBs (PCB 1221-PCB
1248), it is advisable to set the oven temperature to 140°C.
7.2.3 When analyzing for most or all of the analytes in this method,
adjust the oven temperature and co 1umn gas fl ow to provide sufficient
resolution for accurate quantitation of the analytes. This will normally
result in a retention time of 10 to 12 minutes for 4,4'-DDT, depending on
the packed column used.
7. 3 Ca 1i brat ion: Refer to Method 8000 for proper ca 1i brat ion techniques.
Use Table 1 and especially Table 2 for guidance on selecting the lowest point on
7.3.2 Because of the low concentration of pesticide standards
injected on a GC/ECD, column adsorption may be a problem when the GC has
not been used for a day. Therefore, the GC column should be primed or
deactivated by injecting a PCB or pesticide standard mixture approximately
20 times more concentrated than the mid-concentration standard. Inject
this prior to beginning initial or daily calibration.
technique is used, add 10 µl of internal standard to the sample prior to
injection.
November 1992
NOTE: A 72 hour sequence is not required with this method.
7.4.3 Examples of GC/ECD chromatograms for various pesticides and
PCBs are shown in Figures 1 through 5.
7.4.4 Prime the column as per Section 7.3.2.
7.4.5 DDT and endrin are easily degraded in the injection port if
the injection port or front of the column is dirty. This is the result of
buildup of high boiling residue from sample injection. Check for
jegradation problems by injecting a mid-concentration standard containing
only 4,4'-DDT and endrin. Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-DDD} and endrin (endrin ketone and endrin aldehyde).
If degradation of either DDT or endrin exceeds 20%, take corrective action
before proceeding with calibration, by following the GC system maintenance
outlined in of Method 8000. Calculate percent breakdown as follows:
Total DDT degradation peak area (DOE + DOD)
% breakdown x 100
for 4,4'-DDT Total DDT peak area (DDT + ODE + ODD)
Total endrin degradation peak area
(endrin aldehyde + endrin ketone)
% breakdown = x 100
for Endrin Total endrin peak area (endrin +
endrin aldehyde + endrin ketone)
7.4.6 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).
7.4.7 Using either the internal or external calibration procedure
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7 .4.8 If peak detection and identification are prevented due to
interferences, the hexane extract may need to undergo cleanup using Method
3620. The resultant extract(s) may be analyzed by GC directly or may
undergo further cleanup to remove sulfur using Method 3660.
7.5 Cleanup:
7.5.1 Proceed with Method 3620, followed by, if necessary, Method
3660, using the 10 ml hexane extracts obtained from Section 7.1.2.3.
7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous sections and in Method 8000.
7.5.3 If only PCBs are to be measured in a sample, the sulfuric
acid/permanganate cleanup (Method 3665), followed by Silica Cleanup
(Method 3630) or Florisil Cleanup (Method 3620), is recommended.
BOBOA - 7 Revision 1
November 1992
7.6 Calculations (excerpted from U.S. FDA, PAM):
7.6.1 Calculation of Certain Residues: Residues which are mixtures
of two or more components present problems in measurement. When they are
found together, e.g., toxaphene and DDT, the problem of quant itat ion
becomes even more difficult. In the following sections suggestions are
offered for handling toxaphene, chlordane, PCB, DDT, and BHC. A 10%
DC-200 stationary phase column was used to obtain the chromatograms in
Figures 6-9.
7.6.2 Toxaphene: Quantitative calculation of toxaphene or Strabane
is difficult, but reasonable accuracy can be obtained. To calculate
toxaphene on GC/ECD: (a) adjust sample size so that toxaphene major peaks
are 10-30% full-scale deflection {FSD); {b) inject a toxaphene standard
that is estimated to be within ±10 ng of the sample; {c) construct the
baseline of standard toxaphene between its extremities; and {d) construct
the baseline under the sample, using the distances of the peak troughs to
baseline on the standard as a guide (Figures 7, 8, and 9). This procedure
is made difficult by the fact that the relative heights and widths of the
peaks in the sample will probably not be identical to the standard. A
toxaphene standard that has been passed through a Florisil column will
show a shorter retention time for peak X and an enlargement of peak Y.
7.6.3 Toxaphene and DDT: If DDT is present, it will superimpose
itself on toxaphene peak V. To determine the approximate baseline of the
DDT, draw a line connecting the trough of peaks U and V with the trough of
peaks Wand X and construct another line parallel to this line which will
just cut the top of peak W (Figure 61). This procedure was tested with
ratios of standard toxaphene-DDT mixtures from 1:10 to 2:1 and the results
of added and calculated DDT and toxaphene by the "parallel lines" method
of baseline construction were within 10% of the actual values in all
cases.
7. 6. 3 .1 A series of toxaphene residues have been
calculated using total peak area for comparison to the standard and
also using area of the last four peaks only in both sample and
standard. The agreement between the results obtained by the two
methods justifies the use of the latter method for calculating
toxaphene in a sample where the early eluting portion of the
toxaphene chromatogram is interfered with by other substances.
7.6.3.2 The baseline for methoxychlor superimposed on
toxaphene (Figure 8b) was constructed by overlaying the samples on
a toxaphene standard of approximately the same concentration (Figure
8a) and viewing the charts against a lighted background.
7.6.4 Chlordane is a technical mixture of at least 11 major
components and 30 or more minor ones. Gas chromatography-mass
spectrometry and nuclear magnetic resonance analytical techniques have
been applied to the elucidation of the chemical structures of the many
chlordane constituents. Figure 9a is a chromatogram of standard chlor-
dane. Peaks E and F are responses to trans- and cis-ch~ordane, respec-
tively. These are the two major components of technical chlordane, but
the exact percentage of each in the technical material is not completely
November 1992
defined and is not consistent from batch to batch. Other labelled peaks
in Figure 9a are thought to represent: A, monochlorinated adduct of
pentachlorocyclopentadiene with cyclopentadiene; B, coelution of
heptachlor and a-chlordene; C, coelution of ~-chlordene and y-chlordene;
D, a chlordane analog; G, coelution of cis-nonachlor and "Compound K," a
chlordane isomer. The right "shoulder" of peak Fis caused by trans-
nonachlor. ·
7.6.4.l The GC pattern of a chlordane residue may differ
considerably from that of the technical standard. Depending on the
sample substrate and its history, residues of chlordane can consist
of almost any combination of constituents from the technical
chlordane, plant and/or animal metabolites, and products of
degradation caused by exposure to en vi ronmenta l factors such as
water and sunlight. Only limited information is available on which
residue GC patterns are likely to occur in which samples types, and
even this information may not be applicable to a situation where the
route of exposure is unusual. For example, fish exposed to a recent
spill of technical chlordane will contain a residue drastically
different from a fish whose chlordane residue was accumulated by
ingestion of smaller fish or of vegetation, which in turn had
accumulated residues because chlordane was in the water from
agricultural runoff.
7.6.4.2 Because of this inability to predict a chlordane
residue GC pattern, it is not possible to prescribe a single method
for the quantitation of chlordane residues. The analyst must judge
whether or not the residue's GC pattern is sufficiently similar to
that of a technical chlordane reference material to use the latter
as a reference standard for quantitation.
7.6.4.3 When the chlordane residue does not resemble
technical chlordane, but instead consists primarily of individual,
identifiable peaks, quantitate each peak separately against the
appropriate reference materials and report the individual residues.
(Reference materials are available for at least 11 chlordane
constituents, metabolites or degradation products which may occur in
the residue.)
7.6.4.4 When the GC pattern of the residue resembles that
of technical chlordane, quantitate chlordane residues by comparing
the total area of the chlordane chromatogram from peaks A through F
(Figure 9a) in the sample versus the same part of the standard
chromatogram. Peak G may be obscured in a sample by the presence of
other pesticides. If G is not obscured, include it in the
measurement for both standard and sample. If the heptachlor epoxide
peak is relatively small, include it as part of the total chlordane
area for calculation of the residue. If heptachlor and/or
heptachlor epoxide are much out of proportion as in Figure 6j,
calculate these separately and subtract their areas from total area
to give a corrected chlordane area. (Note that octachlor epoxide,
a metabolite of chlordane, can easily be mistaken for heptachlor
epoxide on a nonpolar GC column.)
November 1992
7.6.4.5 To measure the total area of the chlordane
chromatogram, proceed as in Section 7.6.2 on toxaphene. Inject an
amount of technical chlordane standard which will produce a
chromatogram in which peaks E and F are approximately the same size
as those in the sample chromatograms. Construct the baseline
beneath the standard from the beginning of peak A to the end of peak
F as shown in Figure 9a. Use the distance from the trough between
peaks E and F to the baseline in the chromatogram of the standard to
construct the baseline in the chromatogram of the sample. Figure 9b
shows how the presence of toxaphene causes the base 1i ne under
chlordane to take an upward angle. When the size of peaks E and F
in standard and sample chromatograms are the same, the distance from
the trough of the peaks to the baselines should be the same.
Measurement of chlordane area should be done by total peak area if
possible.
NOTE: A comparison has been made of the total peak area
integration method and the addition of peak heights
method for several samples containing chlordane. The
peak heights A, B, C, D, E, and F were measured in
millimeters from peak maximum of each to the baseline
constructed under the total chlordane area and were then
added together. These results obtained by the two
techniques are too close to ignore this method of "peak
height addition" as a means of calculating chlordane.
The technique has inherent difficulties because not all
the peaks are symmetrical and not all are present in the
same ratio in standard and in sample. This method does
offer a means of ca 1cul at i ng results if no means of
measuring total area is practical.
7 .6.5 Polychlorinated bi phenyl s (PCBs): Quantitation of residues of
PCB involves problems similar to those encountered in the quantitation of
toxaphene, Strabane, and chlordane. In each case, the chemical is made up
of numerous compounds. So the chromatograms are multi-peak. Also in each
case, the chromatogram of the residue may not match that of the standard.
7.6.5.1 Mixtures of PCBs of various chlorine contents were
so 1d for many years in the U.S. by the Monsanto Co. under the
tradename Aroclor (1200 series and 1016). Though these Aroclors are
no 1anger marketed, the PCBs remain in the environment and are
sometimes found as residues in foods, especially fish.
7.6.5.2 PCB residues are quantitated by comparison to one
or more of the Aroclor materials, depending on the chromatographic
pattern of the residue. A choice must be made as to which Aroclor
or mixture of Aroclors will produce a chromatogram most similar to
that of the residue. This may also involve a judgment about what
proportion of the different Aroc l ors to combine to produce the
appropriate reference material.
7. 6. 5. 3 Quant it ate PCB residues by comparing tot a1 area or
height of residue peaks to total area of height of peaks frorr
appropriate Aroclor(s) reference materials. Measure total area or
November 1992
height response from common baseline under all peaks. Use only
those peaks from the sample that can be attributed to
chlorobiphenyls. These peaks must also be present in the
chromatogram of the reference materials. Mixtures of Aroclors may
be required to provide the best match of GC patterns of sample and
reference.
7.6.6 DDT: DDT found in samples often consists of both o,p'- and
p, p' -DDT. Residues of ODE and DOD are al so frequently present. Each
isomer of DDT and its metabolites should be quantitated using the pure
standard of that compound and reported as such.
7.6.7 Hexachlorocyclohexane (BHC, from the former name, benzene
hexachloride): Technical grade BHC is a cream-colored amorphous solid
with a very characteristic musty odor; it consists of a mixture of six
chemically distinct isomers and one or more heptachloro-cyclohexanes and
octachloro-cyclohexanes.
7.6.7.1 Commercial BHC preparations may show a wide
variance in the percentage of individual isomers present. The
elimination rate of the isomers fed to rats was 3 weeks for the a-,
y-, and o-isomers and 14 weeks for the ,8-isomer. Thus it may be
possible to have any combination of the various isomers in different
food commodities. BHC found in dairy products usually has a large
percentage of ,8-isomer.
7.6.7.2 Individual isomers (a, ,8, y, and cS) were injected
into gas chromatographs equipped with flame ionization,
microcoulometric, and electron capture detectors. Response for the
four isomers is very nearly the same whether flame ionization or
microcoulometric GLC is used. The a-, y-, and o-isomers show equal
electron affinity. IJ-BHC shows a much weaker electron affinity
compared to the other isomers.
7.6.7.3 Quantitate each isomer (a, /J, y, and o)
separately against a standard of the respective pure isomer, using
a GC column which separates all the isomers from one another.
8.0 QUALITY CONTROL

8 .1 Refer to Chapter One for specific quality control procedures.
the extraction method utilized. If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
8.2 Quality control required to evaluate the GC system operation is found
in Method 8000.
should contain each single-component parameter of interest at the
fo 11 owing concentrations in acetone or other water miscible sol vent:
4,4'-DDD, 10 mg/L; 4,4'-DDT, 10 mg/L; endosulfan II, 10 mg/L; endosulfan
sulfate, 10 mg/L; endrin, 10 mg/L; and any other single-component
November 1992
pesticide, 2 mg/L. If this method is only to be used to analyze for PCBs,
chlordane, or toxaphene, the QC check sample concentrate should contain
the most representative multi-component parameter at a concentration of 50
mg/L in acetone.
of concentration for the ana lytes of interest. The contents of both
performing QC procedures outlined in Method 8000).
8.3.l If recovery is not within limits, the following is required.
• Check to be sure there are no errors in calculations,
concentration".
8.4 GC/MS confirmation: Any compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration is sufficient for detection by GC/MS
as determined by the laboratory generated detection limits.
8.4.1 The GC/MS would normally require a minimum concentration of 10
ng/µL in the final extract, for each single-component compound.
8.4.2 The pesticide extract and associated blank should be analyzed
by GC/MS as per Section 7.0 of Method 8270.
8.4.3 The confirmation may be from the GC/MS analysis of the
base/neutral-acid extractables extracts (sample and blank). However, if
the compounds are not detected in the base/neutral-acid extract even
though the concentration is high enough, a GC/MS analysis of the pesticide
extract should be performed.
8.4.4 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a level
that would demonstrate the ability to confirm the pesticides/PCBs
identified by GC/ECD.

9.1 The method was tested by 20 laboratories using organic-free reagent
November 1992
six concentrations. Concentrations used in the study ranged from 0.5 to 30 µg/L
for single-component pesticides and from 8.5 to 400 µg/L for multi-component
parameters. Single operator precision, overall precision, and method accuracy
were found to be directly related to the concentration of the parameter and
essentially independent of the sample matrix. Linear equations to describe these
relationships for an electron capture detector are presented in Table 4.
matrix, sample-preparation technique, optional cleanup techniques, and
calibration procedures used.
10. 0 REFERENCES
1. U.S. EPA, "Development and Application of Test Procedures for Specific
Organic Toxic Substances in Wastewaters, Category 10: Pesticides and
PCBs, 11 Report for EPA Contract 68-03-2605.
2. U.S. EPA, "Interim Methods for the Sampling and Analysis of Priority
Pollutants in Sediments and Fish Tissue~" Environmental Monitoring and
Support Laboratory, Cincinnati, OH 45268, October 1980.
3. Pressley, T.A., and J.E. Longbottom, "The Determination of Organohalide
Pesticides and PCBs in Industrial and Municipal Wastewater: Method 617,"
U.S. EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006, 1982.
4. "Determination of Pesticides and PCB's in Industrial and Municipal
Wastewaters, U.S. Envi ronmenta 1 Protection Agency," Environmental
Monitoring and Support Laboratory, Cincinnati, OH 45268, EPA-600/4-82-023,
June 1982.
5. Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, §, 9, 1971.
6. Burke, J.A., "Gas Chromatography for Pesticide Residue Analysis; Some
Practical Aspects," Journal of the Association of Official Analytical
Chemists, 48, 1037, 1965.
7. Webb, R.G. and A.C. McCall, "Quantitative PCB Standards for Electron
Capture Gas Chromatography," Journal of Chromatographic Science, 11, 366,
1973.
8. Millar, J.D., R.E. Thomas and H.J. Schattenberg, "EPA Method Study 18,
Method 608: Organochlorine Pesticides and PCBs," U.S. EPA/EMSL, Research
Triangle Park, NC, EPA-600/4-84-061, 1984.
11. U.S. Food and Drug Administration, Pesticide Analytical Manual, Vol. 1,
June 1979.
November 1992
12. Sawyer, L.D., JAOAC, 56, 1015-1023 (1973), §1 272-281 (1978), §1 282-291
(1978).
13. Stewart, J. "EPA Verification Experiment for Validation of the SOXTEC 9 PCB
Extraction Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN,
37831-6138; October 1988.
November 1992
TABLE 1.
GAS CHROMATOGRAPHY OF PESTICIDES ANO PCBs 8
Retention time (min) Method

Detection
Analyte Col. 1 Col. 2 1imit (µg/L}
Aldrin 2.40 4.10 0.004

a-BHC 1.35 1.82 0.003
P-BHC I. 90 l.97 0.006
o-BHC 2.15 2.20 0.009
y-BHC (Lindane) I. 70 2.13 0.004
Chlordane (technical} e e 0.014
4,4'-DDD 7.83 9.08 0.011
4,4'-DDE 5.13 7.15 0.004
4,4'-DDT 9.40 11.75 0.012
Dieldrin 5.45 7.23 0.002
Endosulfan I 4.50 6.20 0.014
Endosul fan II 8.00 8.28 0.004
Endosulfan sulfate 14.22 10.70 0.066
Endrin 6.55 8.10 0.006
Endrin aldehyde 11.82 9.30 0.023
Heptachlor 2.00 3.35 0.003
Heptachlor epoxide 3.50 5.00 0.083
Methoxychlor 18.20 26.60 0.176
Toxaphene e e 0.24
PCB-1016 e e nd
PCB-1221 e e nd
PCB-1232 e e nd
PCB-1242 e e 0.065
PCB-1248 e e nd
PCB-1254 e e nd
PCB-1260 e e nd
8
U.S. EPA. Method 617. Organochlorine Pesticides and PCBs. Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
e = Multiple peak response.
nd = not determined.
November 1992
TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES 8
Matrix Factorb
Ground water 10
Low-concentration soil by sonication with GPC cleanup 670
High-concentration soil and sludges by sonication 10,000
a Sample EQLs are highly matrix-dependent. The EQLs listed herein are
b EQL = [Method detection limit (Table l)] X [Factor (Table 2)]. For
non-aqueous samples, the factor is on a wet-weight basis.
November 1992
TABLE 3.
QC ACCEPTANCE CRITERIA8
Test Limit Rang~ Range

cone. for s for x p' ps
Analyte (µg/L) (µg/L) (µg/L) (%)
Aldrin 2.0 0.42 I. 08-2. 24 42-122

a-BHC 2.0 0.48 0.98-2.44 37-134
{3-BHC 2.0 0.64 0.78-2.60 17-147
6-BHC 2.0 0.72 1.01-2.37 19-140
y-BHC 2.0 0.46 0.86-2.32 32-127
Chlordane 50 10.0 27.6-54.3 45-119
4,4'-DDD 10 2.8 4.8-12.6 31-141
4,4'-DDE 2.0 0.55 1.08-2.60 30-145
4,4'-DDT 10 3.6 4.6-13.7 25-160
Dieldrin 2.0 0.76 1.15-2.49 36-146
Endosulfan I 2.0 0.49 1.14-2.82 45-153
Endosulfan II 10 6.1 2.2-17.1 D-202
Endosulfan Sulfate 10 2.7 3.8-13.2 26-144
Endrin 10 3.7 5.1-12.6 30-147
Heptachlor 2.0 0.40 0.86-2.00 34-111
Heptachlor epoxide 2.0 0.41 1.13-2 .63 37-142
Toxaphene 50 12.7 27.8-55.6 41-126
PCB-1016 50 10.0 30.5-51.5 50-114
PCB-1221 50 24.4 22.1-75.2 15-178
PCB-1232 50 17.9 14.0-98.5 10-215
PCB-1242 50 12.2 24.8-69.6 39-150
PCB-1248 50 15.9 29.0-70.2 38-158
PCB-1254 50 13.8 22.2-57.9 29-131
PCB-1260 50 10.4 18.7-54.9 8-127
s Standard deviation of four recovery measurements, in µg/L.

-
x = Average recovery for four recovery measurements, in µg/L.
P, PS = Percent recovery measured.
D = Detected; result must be greater than zero.
8
Criteria from 40 CFR Part 136 for Method 608. These criteria are based directly
upon the method performance data in Table 4. Where necessary, the limits for
recovery have been broadened to assure applicability of the limits to
concentrations below those used to develop Table 4.
8080A - 17 Revision l
November 1992
TABLE 4.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION 8

Analyte (µg/L) (µg/L) S' (µg/L)
Aldrin 0.81C+0.04 0 .16x-O .04 0.20x-O.Ol

a-BHC 0.84C+0.03 0 .13x+O. 04 0.23x-O.OO
~-BHC 0.81C+0.07 o.22x+o.02 o.33x-o.9s
o-BHC 0.81C+0.07 0 .18x+O. 09 o.2sx+o.03
y-BHC 0.82C-0.05 o.12x+o.06 o.22x+o.04
Chlordane 0.82C-0.04 0.13x+O .13 o.18x+o.1s
4,4'-DDD 0.84C+0.30 o.2ox-o.1s o.21x-o.14
4,4'-DDE 0.85C+0.14 o.13x+o.oG o.2sx-o.og
4,4'-DDT 0.93C-0.13 o.11x+o.39 o.31x-o.21
Dieldrin 0.90C+0.02 o.12x+o.19 0.16x+O .16
Endosulfan I 0.97C+0.04 O.lOx+0.07 O.lBx+0.08
Endosulfan II 0.93C+0.34 o.4Ix-o.Gs o.41x-o.20
Endosulfan Sulfate 0.89C-0.37 o.13x+o.33 o.24x+o.3s
Endrin 0.89C-0.04 o.2ox+o.2s o.24x+o.2s
Heptachlor 0.69C+0.04 o.06x+o.13 o.16x+o.os
Heptachlor epoxide 0.89C+0.10 0 .18x-O .11 o.2sx-o.os
Toxaphene 0.80C+l.74 o.o9x+3.20 o.2ox+o.22
PCB-1016 0.81C+0.50 o.13x+o.1s O.lSx+0.45
PCB-1221 0.96C+0.65 o.29x-o.16 o.3sx-o.G2
PCB-1232 0.91C+l0.79 o.21x-l.93 o.31x+3.so
PCB-1242 0.91C+10.79 o.21x-I.93 o.31x+3.so
PCB-1248 0.91C+l0.79 o.21x-L93 o.31x+3.so
PCB-1254 0.91C+l0.79 o.21x-I.93 o.31x+3.so
PCB-1260 0.91C+l0.79 o.21x-l.93 o.31x+3.so
x' Expected recovery for one or more measurements of a sample

containing concentration C, in µg/L.
Sr
I
= Expected single analyst ~tandard deviation of measurements at an
average concentration of x, in µg/L.
S' = Expected interlaboratory standard deviation of measurements at an
average concentration found of x, in µg/L.
c = True value for the concentration, in µg/L.
- Average recovery found for measurements of samples containing a
x =
concentration of C, in µg/L.
November 1992
Figure 1
Gas Chromatogram of Pesticides
Co4wml'\: 1.5'4 SP·22SO.

°"
1.11'4 5'·2'()1 Swoetco.-or'l
T.....,.r1n.t1: 200DC:
~': Electron C.On.n
~ :I
• I
·~ ..,c 8c ...8
.. It
:~
• c
J
1
-I
I..,
\_. L.....___J \.
•
0 I 12 11
Rl"T'INi'ION TIME (MINUTISI
November 1992
Figure 2
Gas Chromatogram of Chlordane
Coh'"'": 1.IJ. 5'·2250-

1.11\ SP·2•01 °" "'"ICOOOf"l
T1moer1twrt 20e 0 c
Dfttnor: EiectTon C.otwrt
0 • I
9'ITINTION TIMI (MINUTISl
12
,.
November 1992
Figure 3
Gas Chromatogram of Toxaphene
C..wmn: 1.1~ 5'·22SO.

1.11~ 5'·2~1 Oft $wMICODOri
T""'*lt'U'•· moc
Detector: llectntn C.OtYtt
2
• 10 ,,
RITINTION TIMI CMINUTIS>
11 22 21
November 1992
Figure 4
Gas Chromatogram of Aroclor 1254
Coh1"'ft: 1.5~ 5'·2250-

1.15~ 5'·2'°1 Oft 5'...ICOOOM
Tet'ftoer1n.rt: 20()0<:
Oeunor: llec"rrOft C.Ot1.1rw
ij
2 • 10 ,. 11 22
llllTINTION TIMI CMINUTIS>
November 1992
Figure 5
Gas Chromatogram of Aroclor 1260
Co4UtM: , .... 5'·2250.

, . ., P·2401 Oft S..•cooOf'I
T.._.rtftlrt; 200°C
0..C.r: 11.Wft C.tvr1
2
• 10 " ,•
RmNTION TIMI CMiNUTIS>
22
November 1992
Figure 6
·I•
, I
I
' .
r·
, I
I)
I
_). __ \._
•o•oood/~M••~
I I
1·: I
.,
ii
I'
I
II I
'-Ll I
k
I
;j
'I I ~
:_ _JL
!/ 11 r.
1
--
Fi&. 8-Sa..Une CGnlU'UCUon for tome ryplcal pa chromat.apblc: peaks.
a, symmetrical Mpuated nae baMltne: b ancS c. owrlapptns flac basellne;
d, sepanced (pen dou not ncun co bl..Unebec_...n peak•); .. 1ep1rared
1lopin1 baseline; f, aepanced (pen 1•• below· baseltne bMween peaks);
a. •- and Y ·BHC slopinl baMliM; h. •··I··
and Y-BHC lloptn1 bueltne;
1. c:blordane flat ba. .Une: J. b9plac:blOI' and bep11cblor epoxute super-
t11"4>0aed on ca.&ordane; k. cbalr•IMped peaks, uuymmeutcal peak: 1.
p.p'-DOT lupel"lmpOMcl - ,........_
November 1992
Figure 7
J ..._~"""'---·-·
,
--------- -··--·. ··-----------
File 7a-8aMliM coa1trucuon for multiple residues wtth »tandarcl
toxaphene•
•
'
Pi,. 7b ....... COMCnlCU• f• lllllldple rnidlllS wtlb tm..

.-.... cca ... ..,·~ udp.p'-DDT.
November 1992
Figure 8
Fts. a-a...aaae ctlt9lr\ICIS• fir addple readue•: rfC9 bran wttb Bite,
• 1' .,cor.... ~ ...
8080A - 26
Revision 1
November 1992
Figure 9
j I I :\
I· ,. 11 : I ~,
:. :~. i '1
v\ • )
j.___;J.~~li"!:.'_____:~~--~--~--A...;;•~-----
Fl&. •-BaMbne c:annncilon for multiple re1ldue1: standard chlordane.
ii
I!
I
I
I
I
I~
I
J "'
-----------------------------------------------
November 1992
METHOD 8080A
ORGANOCHLORINE PESTICIDES AND POLYCHLORINATED BIPHENYLS
BY GAS CHROMATOGRAPHY
Start
Choose 7 .3.2 Prime or

apgrogriate d•aet:ivat:e the
extraction QC column p:cior
pz:oc•duxe. to daily
celibrat:.ion.
7. 1. 2
Bxchanwe 7. 4 Perf'orm
•xtraction GC analy•i•.
aolvant to
hexane.
7 . 5. 1 Cleanup
7.2 Set Yes uaing Method
chromatographic 36 20 and 3660
conditions. if necessary.
7.3 Rerer to
K•Chod eooo ? • • calcnalat•
for proper concentration•.
calibration
techniq:u••·
No
Stop
November 1992

200161by PDF

Uploaded by

Copyright:

Available Formats

200161by PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

200161by PDF

Uploaded by

Copyright:

Available Formats

SW8463C

TEST METHODS FOR EVALUATING

THIS PACKET CONTAINS THE OFFICIAL PROPOSED UPDATE II FOR

• Proposed Methods for Update II, dated November 1992

• Proposed Chapters Two, Three, Four, and Seven

If you have any problems, telephone the Methods Information

* Method 8270 - GC/MS for Semivolatile Organics: Capillary Column Technique

* Indicates partial rev1s1on

PART I METHODS FOR ANALYTES AND PROPERTIES

CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS

CHAPTER ONE, REPRINTED -- QUALITY CONTROL

PART III SAMPLING

CHAPTER TWELVE -- LAND TREATMENT MONITORING

Revision 2 methods (methods which have been revised in the proposed

Method Number Chapter Number Method Number Current Revision

0010 Ten None {new method) 0

3640 Four (4.2.2) None (new method) 0

METHOD INDEX - 1 Revision 1

Method Number Chapter Number Method Number Current Revision

7040 Three 7040 0

METHOD INDEX - 2 Revision 1

Method Number Chapter Number Method Number Current Revision

7610 Three None (new method) 0

METHOD INDEX - 3 Revision 1

Method Number Chapter Number Method Number Current Revision

8270 Four (4.3.2) 8270 1 (PR)

9036 Five None (new method) 0

9250 Five None (new method) 0

METHOD INDEX - 4 Revision 1

Method Number Chapter Number Method Number Current Revision

HCN Test Method Seven None (new method) I (PR)

(PR) Indicates a Partial Revision

METHOD INDEX - 5 Revision I

TRIP BLANK: Usually an organic or aqueous solution that is as free of

Field Duplicate I Field Duplicate II

Replicate IA Replicate 18 Replicate IIA Replicate IIB

ENVIRONMENTAL An environmental sample or field sample is a repre-

Analytical instrumentation shall be calibrated in accordance

1.2.2.3.3 Additional QC Requirements for Inorganic Analysis

Standard curves used in the determination of inorganic analytes

Standard deviations and relative standard deviations shall be

1.2.2.3.4 Additional Quality Control Requirements for Organic

The following requirements shall be applied to the analysis of

The calibration of each instrument sha 11 be verified at

The tune of each GC/MS system used for the determination of

b) the region of the standard curve where there is a significant

where t(n-1 1- am 0.99) = 6.965 for three replicates as determined

Lab Name: Contract:

Lab Code: Case No.: SAS No.: SDG No.:

EPA Sample No. Lab Sample ID.

Were ICP interelement corrections applied? Yes/No

Were ICP background corrections applied? Yes/N·o

Lab Name: Contract:

Matrix (soil/water): Lab Sample ID:

Concentration Units (ug/L or mg/kg dry weight):

Lab Name: Contract:

Lab Code: Case No.: SAS No.: SDG No.:

Initial Calibration Source:

Continuing Calibration Source: