An American National Standard

Designation: D 3856 95 (Reapproval 2000)

Standard Guide for

Good Laboratory Practices in Laboratories Engaged in
Sampling and Analysis of Water1
This standard is issued under the fixed designation D 3856; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope D 2777 Practice for Determination of Precision and Bias of

1.1 This guide provides information on consensus good Applicable Methods of Committee D-19 on Water3
laboratory practices for laboratories that provide services in the D 3370 Practices for Sampling Water from Closed Con-
sampling and analysis of water. As consensus standards, these duits3
are the minimum criteria that all laboratories should consider in D 3694 Practices for Preparation of Sample Containers and
establishing their good laboratory practices. for Preservation of Organic Constituents4
1.2 This guide is designed to be used by those responsible D 4210 Practice for Intralaboratory Quality Control Proce-
for the selection, operation, or control of laboratory organiza- dures and a Discussion on Reporting Low-Level Data3
tions engaged in sampling and analysis of water. D 4375 Terminology for Basic Statistics in Committee D-19
1.3 This guide presents features of organization, facilities, on Water3
resources, and operations which affect the usefulness of the D 4447 Guide for the Disposal of Laboratory Chemicals
data generated. and Samples5
1.4 This guide presents criteria for selection and control of D 4840 Guide for Sampling Chain-of-Custody Procedures3
the features described in 1.3 and also makes recommendations D 4841 Practice for Estimation of Holding Time for Water
for the correction of unacceptable performance. Samples Containing Organic and Inorganic Constituents3
1.5 This guide describes methodology and practices in- D 5172 Guide for Documenting the Standard Operating
tended to be completely consistent with the International Procedures Used for Analysis of Water3
Organization for Standardization (ISO) 9000 series of stan- D 5847 Practice for Writing Quality Control Specifications
dards and Guide 25 1990 (1). 2 for Standard Test Methods for Water Analysis4
1.6 The values stated in inch-pound units are to be regarded E 456 Terminology Relating to Quality and Statistics 6
as the standard. The values given in parentheses are for E 548 Guide for General Criteria Used for Evaluating
information only. Laboratory Competence6
1.7 This standard does not purport to address all of the 3. Terminology
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- 3.1 For definitions of terms used in this guide, refer to
priate safety and health practices and determine the applica- Terminologies D 1129, D 4375, and E 456, Guide E 548, and
bility of regulatory limitations prior to use. ASTM MNL 7 (2).

2. Referenced Documents 4. Summary of Guide

2.1 ASTM Standards: 4.1 This guide describes the criteria, guidelines, and recom-
D 1129 Terminology Relating to Water3 mendations for physical and human resources and data valida-
D 1193 Specification for Reagent Water3 tion for the operation of a laboratory.

1
This guide is under the jurisdiction of ASTM Committee D19 on Water and is
the direct responsibility of Subcommittee D19.02 on General Specifications and
Technical Resources.
Current edition approved Oct. 10, 1995. Published December 1995. Last
previous edition D 3856 88.
2 4
The boldface numbers in parentheses refer to the list of references at the end of Annual Book of ASTM Standards, Vol 11.02.
5
this guide. Annual Book of ASTM Standards, Vol 11.04.
3 6
Annual Book of ASTM Standards, Vol 11.01. Annual Book of ASTM Standards, Vol 14.02.

Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D 3856 95 (Reapproval 2000)
4.2 Although, philosophically, this guide is intended to 6.3.3 There should be a document control system to track
apply to all analyses of water, there may be certain test the currency and completeness of procedures.
methods to which parts of this guide are not applicable due to 6.4 MetrologySystems for making measurements should
the nature of the samples, for example, microbiological analy- have the following:
ses. 6.4.1 Written calibration procedures, including traceability
and schedule.
5. Significance and Use 6.4.2 Written preventive maintenance procedures with
5.1 Data on the composition and characteristics of water are scheduled intervals.
frequently used to evaluate the health and safety to humans and 6.4.3 Records available to document any repair or service of
the environment. equipment, replacement or change of reagents, or modification
5.2 Moreover, such data are frequently used for process of procedures.
control or to ascertain compliance with regulatory statutes that 6.5 Data Recording The laboratory should keep records
place limits on acceptable compositions and characteristics of of sample source disposition and analyses to provide informa-
waters. tion on sample collection and preservation, analytical proce-
5.3 Laboratories that conduct water sampling and generate dures and results, and the persons responsible for the sampling
analytical data, and those persons who have the responsibility and analysis. All laboratory data sheets should be dated and
for selecting a laboratory to perform water quality studies, need signed by the analyst and his supervisor or a suitable colleague.
to use criteria, guidelines, and recommendations that have been 6.6 Data Validation To assess and demonstrate a suitable
developed by consensus and are well accepted in making this level of analytical performance, the laboratory should keep
selection. records of audit procedures, reference sample programs, and
5.4 Demonstration and documentation by a laboratory that interlaboratory tests. One criterion for measurement of analyti-
there was judicious selection and control of organization, cal performance should be the precision and bias data con-
facilities, resources, and operations will enhance the credibility tained in the analytical method being used. Where applicable,
of the data produced and promote its acceptance. quality control charts as described in Practice D 4210 should
be used.
6. Aspects of Quality Assurance 6.7 Trouble Shooting The organization should provide the
authority and the responsibility to a designated person or
6.1 GeneralThe function of a laboratory is to provide persons for investigation of out-of-control results and for
analytical results and related information which are adequate informing the laboratory management of any problems that
for the intended use. This function is achieved through effec- occur.
tive use of a quality assurance program. Every laboratory 6.7.1 A current log should be kept of analytical deficiencies
should develop a written quality assurance program, plan, or and the action taken to correct them.
manual that demonstrates the effectiveness of its procedures
and practices in assuring this quality. In addition to addressing 7. Organization
any applicable regulatory requirements, the program should 7.1 GeneralThe production of reliable data is effected
consider the following: through the effort of everyone involved with the service. It is
6.2 Organizational StructureA table of the organization paramount, therefore, that personnel have a clear understand-
should be available which shows the lines of authority, areas of ing of their duties and responsibilities and their relationship to
responsibility, and job functions. The laboratory should also the product produced. Management has the responsibility for
provide a description of its capabilities. Laboratory manage- defining function and goals as applied to the individual. A
ment should demonstrate and foster a positive quality assur- formal document describing objectives, staff functions and
ance attitude and provide the analytical staff with a written responsibilities, should be distributed and explained to all staff
policy to carry out a defined quality assurance program. members.
6.2.1 Human Resources The key personnel of the orga- 7.1.1 The personnel in a laboratory will vary with the
nization should be described by means of personal rsums specific functions that are to be served, but minimal qualifica-
presenting the education and work experience appropriate to tions and duties generally will be as described in 7.2 through
the table of organization and the qualifications of the position. 7.3.5.11.
For each employee, provision should be made for update of 7.2 Human Resources/Personnel Duties and Responsibili-
records to reflect additional education, work experience, and ties:
continuing training. 7.2.1 The Director The director should have a working
6.2.2 Physical ResourcesThe laboratory facilities should knowledge of the laboratory and its scope of activities. The
provide a working environment that is clean, comfortable, and director should have earned a baccalaureate degree in science
safe. The instrumentation and equipment must be suitable for or engineering from an accredited college or university or the
the operational needs of the laboratory. equivalent (Note 1) and have at least five years experience in
6.3 Methodology Written procedures should be readily laboratory work.
available to personnel.
NOTE 1The purpose of the equivalent requirement is to allow the
6.3.1 Written sample collection, handling and storage re- assignment of persons who have comparable skills obtained through
quirements should be followed. qualified training which did not result in the award of a baccalaureate
6.3.2 Analytical procedures should be written. degree. Interpretation of the term equivalent will necessarily require

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 D 3856 95 (Reapproval 2000)
careful judgment by the user of these guidelines. Certification by 7.2.3.1 Where appropriate, technical staff members should
professional boards is to be encouraged. have formal training in the sampling and analytical methodol-
The laboratory director or manager should be a full-time ogy, and quality control, as applied to the specific sample types
employee that operates the laboratory with at least the respon- and concentration levels of analytes which are of interest to the
sibilities outlined in 7.2.1.1-7.2.1.6. laboratory.
7.2.1.1 Establishment of long-term program plans and 7.2.3.2 Technical staff may be required to satisfactorily
shorter term work plans and assignments to meet the program complete analytical tests to qualify initially and to periodically
objectives. requalify throughout their work career. Qualification should be
7.2.1.2 Operation and maintenance of the physical plant based on the generation of analytical results with precision and
(building, equipment, instrumentation, services, etc.). bias recovery within limits known to be possible for the
particular method and which meet the data users requirements.
7.2.1.3 Selection, training, and development of personnel.
7.2.4 Laboratory Support StaffThe support staff are non-
7.2.1.4 Overview and approval of methods of sampling and
analyses. technical workers who perform routine field and laboratory
services in support of the professional and technical staff. In
7.2.1.5 Development and implementation of a quality assur- the field, they may collect samples, and they may transport,
ance (QA) program to monitor and maintain the quality of
handle and maintain records of collection and storage, includ-
laboratory performance. In larger laboratories, this function is
ing chain of custody. The support staff also maintains sampling
frequently delegated to an individual or organization separate
and other field equipment.
from the laboratory operation. This includes ensuring staff
participation in appropriate interlaboratory quality control 7.2.4.1 In the laboratory, they wash glassware, operate
activities, intercalibration checks, performance audit programs, laboratory reagent water systems, autoclaves, drying ovens,
etc. Such interlaboratory checks are the most effective measure and incubators. The support staff also receives, stores, and
of comparative performance and should demonstrate the worth ships samples, materials, and laboratory equipment.
of a good quality assurance program to upper management or 7.2.5 Offce Support StaffThe office staff are nontechnical
regulator agencies. A QA program also provides each labora- clerical or secretarial personnel who are trained either on the
tory staff member with a copy of the quality assurance plan for job or by formal schooling in keyboarding, filing, recordkeep-
the laboratory, which documents responsibilities and kind and ing, communications by telephone or personal visits, payroll,
frequency of quality control checks. The plan should also travel, or some combination thereof.
specify the monitoring and overview responsibilities of man- 7.2.5.1 The laboratory or office support staff may be an
agement. integral part of the laboratory or may be provided as part of the
7.2.1.6 Establishment of a development and operational administrative function in a larger organization.
performance appraisal system for the staff and an individual 7.3 Physical Resources and Related Operating Procedures:
career development plan for each staff member. Performance 7.3.1 GeneralThe laboratory environment can signifi-
standards should be developed and agreed to jointly by each cantly affect the results of water analyses; therefore, the
staff member and their supervisor. The director should be laboratory facility should be carefully designed and periodi-
responsible for assuring a periodic review of performance of all cally inspected and reevaluated. In general, the physical
staff members by supervisors, for rewarding good quality conditions in the laboratory should comply with the applicable
performance, and for implementing and encouraging on-the- U.S. OSHA requirements, or their equivalent, and other safety
job or off-site training. This joint development of performance and legal requirements. For further information see Laboratory
standards is key to obtaining an understanding between the Planning for Chemistry and Chemical Engineering (3).
worker and the supervisor, as to what is expected for satisfac-
7.3.2 Equipment and SuppliesThe specific instrumenta-
tory performance. It also paves the way for rewarding out-
tion, equipment, materials, and supplies needed for the perfor-
standing performance or identifying unsatisfactory perfor-
mance of a standard test method are usually described in the
mance. These standards should be used to evaluate
written standard. If the laboratory proposes to perform a new
performance frequently but informally, and formally on a less
analytical procedure, it must be prepared to acquire the
frequent (annual or semiannual) basis.
necessary instrumentation, supplies and space, and to conduct
7.2.2 Senior Staff The senior professional staff of the an appropriate training period prior to its routine use.
laboratory conduct the difficult and non-routine sampling and
7.3.3 Laboratory EnvironmentThe laboratory should be
analyses, resolve analytical problems, and modify and develop
kept as free from environmental contamination as possible in
analytical procedures.
order to protect the samples and instrumentation. Specific
7.2.2.1 Senior staff supervise and assist the technical staff in procedures should be established for monitoring the quality of
analyses, other laboratory operations and training. the laboratory reagent water per Specification D 1193. By
7.2.2.2 Senior staff members should have earned a bacca- doing so, the laboratory ensures the opportunity to produce
laureate degree in science or engineering from an accredited quality data. The production of valid data not only depends on
college or the equivalent (see Note 1) and have at least two the collection of representative samples, but also on maintain-
years experience at the bench level in a water laboratory. ing such samples as closely as possible to their original
7.2.3 Technical Staff The technical staff are personnel condition through careful handling and storage. If the sample
who perform routine and specialized sampling and analyses. cannot be analyzed at once, it should be preserved and stored

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 D 3856 95 (Reapproval 2000)
as required for the analytes of interest. Recommended proce- finish that is easily cleaned or disinfected, or both. Floors
dures for collecting, transporting and handling water and should be covered with good quality tiles or other heavy duty
wastewater samples are described in this guide or in Practices material, which can be maintained by wet-mopping or scrub-
D 3370 and D 3694. Recommended chain of custody proce- bing machine and application of a skid-proof wax. Bacterio-
dures are described in Guide D 4840. Whenever sample static agents contained in some wall or floor finishes increase
holding times must be determined, recommended procedures the effectiveness of disinfection. Floors should never be swept
are described in Practice D 4841. or dry-mopped.
7.3.4 Ventilation SystemLaboratories should be well ven- 7.3.5.7 High standards of cleanliness should be maintained
tilated and free of dust, drafts, and extreme temperature and monitored for contamination in work areas and the
changes. Central air conditioning is recommended because: 1) laboratory. If there is any doubt about the effects of the
incoming air is filtered, reducing the likelihood of airborne surrounding laboratory facility upon the analytical results,
laboratory contamination; 2) uniform temperature is conducive blanks that have been protected against the laboratory environ-
to stable operation of instrumentation and equipment; and 3) ment should be compared periodically against sample blanks
low humidity reduces moisture problems with hygroscopic that have been exposed to the laboratory environment.
chemicals, samples, and corrosion problems with analytical 7.3.5.8 A complete set of material safety data sheets (MS-
balances and other instrumentation. DSs), or equivalent safety information for all chemicals used in
7.3.4.1 In order for the hoods to be effective in removing the laboratory, should be on file in a location accessible to all
fumes and aerosols from the laboratory environment, they must employees. Samples, reagents, and solvents that may contain
be operating at their designed capacity. Proper hood perfor- harmful or interfering fumes shall be used in a properly
mance cannot be assumed. Hoods should be tested periodically operating hood or glove box. Smoking, eating, and drinking
for proper air flow by qualified support staff or a professional should not be allowed in the work area. Soiled hands should be
maintenance contractor. Hoods should not be located in areas washed before handling analytical materials. Sinks shall not be
of countervailing drafts, such as between two open doors. used for sample or reagent disposal. Laboratories shall dispose
Under usual operating conditions, hoods require from 50 to of waste in accordance with applicable environmental and
125 CFM/ft2 (15 to 38 m3/min/m2) of face area. For a more safety regulations and standards. Standard operating proce-
detailed treatment of ventilation consult Industrial dures (SOPs) as described in Guide D 5172 for handling,
VentilationA Manual of Recommended Practice (4). storage, and disposal of hazardous reagents and samples shall
7.3.5 FacilitiesIdeally, the areas provided for cleaning of be defined. Additional information is available in Guide
glassware and portable equipment should be separated from the D 4447, MSDSs, and Refs (5-13), but this information is for
laboratory working area but located close enough for conve- reference purposes only and is not intended to be exhaustive or
nience. to supersede regulations. Short courses on handling hazardous
7.3.5.1 Laboratories conducting trace organic analyses and toxic chemicals are available from chemical companies
which use organic solvents in extraction and clean-up proce- and others.
dures must separate these activities from analytical instrumen- 7.3.5.9 Working AreaAdequate bench space or working
tation rooms to avoid contamination and reduce hazards. areas should be provided for each analyst. As a general
7.3.5.2 Laboratories conducting analyses with a wide range guideline, there should be 150 to 300 ft2(14 to 28 m2) per
of concentrations must take care to avoid cross contamination analyst or 12 to 25 linear ft (3.6 to 7.6 m) of bench space per
among samples in storage or analysis. Relatively clean analyst. The space requirement per analyst will vary with the
samples, highly polluted samples and reagents should be stored instrumentation or equipment in use, the sample load, and the
separately from each other in vented cabinets and hoods to number of operations that are to be performed by a single
avoid cross-contamination. analyst. The laboratory may require specialized facilities such
7.3.5.3 Calibration standards should be stored separately as a perchloric acid hood. The lighting level may vary between
from all samples. 50 and 100 fc (535 and 1070 1x), depending upon the closeness
7.3.5.4 Laboratory DesignLimited facilities and re- of the tasks being performed in the area.
stricted work space may affect the quality and validity of 7.3.5.10 Electric Power SupplyThe reliability of the in-
results. Visitors and incidental traffic should be discouraged in struments is affected by the electrical power supply. Some
work areas. Through traffic can be prevented by good labora- instruments require separate circuits or a regulated power
tory design. supply for stable operation. The line voltage and stability
7.3.5.5 Bench tops should be set at heights of 36 to 38 in. should be monitored periodically and not assumed as based on
(91 to 97 cm) with a depth of 28 to 30 in. (71 to 76 cm). This records. Surge suppressors should be installed for any sensitive
height is comfortable for work in a standing or sitting position. instrumentation or computers. An isolated ground for indi-
Desk tops or sit-down benches should be set at 30 to 31 in. (76 vidual instruments and antistatic pads are helpful in eliminating
to 79 cm) height to accommodate calculations and writing stray currents.
activities. Bench tops should be constructed of stainless steel, 7.3.5.11 Safety ConsiderationsThe laboratory should be
epoxy plastic, or another smooth impervious material that is supplied with fire extinguishers suitable for Class A, B, or C
inert, corrosion-resistant, and has minimal seams. fires; spill control materials for acids, bases, and flammables;
7.3.5.6 Walls should be covered with waterproof paint, eye wash and safety shower facilities; and other safety devices
enamel, tile, or other surface materials that provide a smooth that may be consistent with the particular laboratory operation.

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 D 3856 95 (Reapproval 2000)
The facilities should provide for the safe disposal of reagents measurement system, used in the field, should be traceable to
and samples with written instructions for the utilization of standard weights and measures.
these procedures by all personnel. Wearing of safety glasses, 9.3 All metrology systems should have a record of calibra-
goggles, or face shields should be required for everyone tion and maintenance schedules and should note configuration
entering the laboratory. A senior staff member should be changes that may have occurred in such a system. Records of
assigned the responsibility for monitoring laboratory safety, significant changes in calibration should be noted and reviewed
including periodic inspection of facilities and fire extinguish- periodically.
ers. Staff should be trained and have the training documented
in the following: handling and disposal of potential chemical or 10. Data Recording
biological hazards, or both; use of appropriate safety and
10.1 Any system is acceptable as long as it meets the
personal protection equipment; and general laboratory safety
requirements outlined in 6.5. A commonly used method of
and hygiene.
recording laboratory data is a notebook specifically designed
8. Methodology for this purpose. The pages of the laboratory notebook are
8.1 GeneralThe use of written procedures is an essential generally lined in a grid pattern with provision for information
element in providing useful data. The use of published proce- such as project identification, date, and signatures of the
dures is usually not sufficient to guarantee reliable and repro- analyst and supervisor. The analyst should record information
ducible analytical performance. Each laboratory performing an on the analyte, method of analysis, analytical conditions and
analysis should reduce the methodology to a SOP that clearly results, and remarks. There should be an example of the
and completely delineates the exact steps followed. The use of calculations. Entries shall be in ink with no erasures or
SOPs helps ensure uniform performance among different whiteout. Revisions should be indicated by a single line
analysts using them. through the original entry with the correction alongside or
8.1.1 The quality assurance program should clearly identify referenced. Changes or corrections shall be dated and initialed.
the duties of the following: the laboratory staff for routine 10.2 When data are generated using an automated or semi-
quality control (QC) checks, the senior staff for continuing automated instrumentation, it is generally displayed on a strip
review of the quality control activities, and the laboratory chart recorder or printed tape. Chart paper should contain the
director for periodic quality control reviews. signature of the analyst, the date, the sample identification, and
8.2 For ease of cross-referencing methods and ensuring the operational parameters of the instrument. Chart papers and
completeness of methods, all SOPs should follow the same tapes should be retained as a part of the permanent record.
format. Some laboratories prefer to use microfilm for record retention.
8.3 Strict adherence to the method SOP shall be maintained 10.3 Laboratory sampling, analyses, and data recording are
and checked using a system of method performance audits. increasingly automated and computerized. Projections into the
When deviations are necessary, the SOP should be rewritten to future indicate an even more rapid transition to computerized
reflect the changes. If time does not permit a rewrite, the operations of almost all sampling and analyses in water
necessary deviations from the SOP shall be recorded and chemistry as has begun in clinical chemistry. Universities,
approved in writing by supervision before proceeding with the colleges, and technical schools now require chemists to take
analysis. courses in computer logic, programming, and operation so that
8.4 Whenever a deviation from a written SOP is necessary, graduated chemists and technicians are computer literate and
it should be noted in the final data report along with identifi- able to utilize the advances already available. Instrument
cation of the person who authorized the change. responses to samples, quality control checks, and blanks are
8.5 A file of SOPs should be maintained by the laboratory now directly entered into the computer. Results and limits are
director or manager. Each new SOP or revised SOP should calculated, and data acceptability is indicated immediately.
carry its effective date so that recorded data may be related to Results are reviewed by the analyst on a video screen, and a
the appropriate SOP. Outdated SOPs should be kept on file for hard copy is printed out only as desired. Results, evaluations,
reference purposes. and summaries are archived off-line. Use of hard disks, floppy
disks, and streamer tape back-ups provide the necessary
9. Metrology redundancy to avoid loss from system crashes. A wealth of
9.1 A set of Class S weights or better must be available to versatile software programs for personal computers permits
make periodic checks on balances. A National Institute of statistical evaluations, spread sheets, scheduling, complete
Standards and Technology (NIST) certified thermometer record-keeping for cost monitoring, supply management, qual-
should be used periodically to check temperature measurement ity control monitoring, report writing, and laboratory manage-
devices. A set of color standards may be used to check the ment. For further information and recommendations for ensur-
wavelength calibration and the stray light characteristics of a ing data integrity in automated laboratory operations, consult
spectrophotometer or colorimeter. Systems such as balances the U.S. EPA Good Automated Laboratory Practices (14).
and spectrometers can be maintained and certified under an 10.4 The recording of the data and the analytical results
annual service contract. should be in a format that is agreed to by the laboratory and the
9.2 The laboratory providing analytical services on the data user. The laboratory should have a written protocol
characterization of water may wish to make additional mea- regarding the number of significant figures, detection limits,
surements, such as water flow. The calibration of the flow reporting convention for nondetection, analytical range, etc.

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 D 3856 95 (Reapproval 2000)
11. Data Validation the U.S. EPA Handbook for Analytical Quality Control in
11.1 GeneralThe validation of data will require a variety Water and Wastewater Laboratories (16).
of techniques due to the variety of ways in which data are 11.6 Calibration For each analyte, prepare a calibration
produced. If the data are collected manually, the validation curve which covers the entire working range of the method.
procedures should take into account the sampling, the sample Construct the curve using at least three points, including one
handling, the calibration and performance of the analytical near the upper limit of the concentration range and one near the
system, and the calculations. The sampling, the calibration, and lower limit with a reasonably equitable distribution of the
the instrument performance should be taken into account if the remaining points. The actual minimum number of calibration
data are generated by instrumental means. points depends upon the width of analytical range and the
11.2 SamplingBecause the sampling of water (Practices shape of the calibration curve. For example, a broad range or
D 3370), whether performed manually or by instrumental a curve not known to be linear might require calibration at five
means, involves operations upon a heterogeneous mass under to seven points. The difference (D) between the value observed
uncontrolled conditions, reliable conclusions can seldom be for each calibration standard (XOBS) and the value predicted for
drawn from one or a few samples. The sampling plan must that standard using the fitted calibration curve (XPRED) can be
provide an adequate number and volume of samples to permit evaluated as follows:
statistical evaluation of the data produced. Information on the 11.6.1 After 20 to 25 initial values of D = XOBS XPRED are
number of samples from which a final result is derived should available, calculate the mean ( D) and standard deviation (SD)
be available to the data user. The reasons for obtaining the for each concentration.
information, the methods of obtaining it, and the desired levels
11.6.2 If a subsequent D value is not within the interval D 6
of confidence in the information cannot be addressed within
3 (SD), the system calibration is out of control and the system
this guide for all situations. For further information, see the
shall be recalibrated before continuing routine analyses.
U.S. EPA Handbook for Sampling and Sample Preservation
(15). 11.6.3 If the calibration curve was fitted by minimizing the
11.3 Sample Handling and IdentificationTo ensure that sum-of-squares of the absolute deviations of each calibration
proper procedures are observed, to track sample collection, point from the curve, then the D values should also be in
transportation, storage, and analysis, and to protect against absolute units. However, if percentage deviations were mini-
loss, misidentification, tampering, or other errors that may be mized, then the Ds also should be percentages of the predicted
introduced, the sampler is responsible for providing the fol- value.
lowing information for every sample collected: 11.6.4 If there is no obvious reason to require recalibration,
11.3.1 Collection date, time, and location; instead of following steps in accordance with 11.6, an existing
11.3.2 Weather conditions and other remarks considered calibration curve may be verified at the beginning of the
appropriate; analytical run by measuring two calibration standards, one in
11.3.3 Sample identification number and the name of sam- the lowest quarter of the total range of the existing calibration
pler; curve and one in the highest quarter of the range.
11.3.4 The analytes to be tested and the sample preservation 11.6.5 Evaluate the difference D = X OBS XPRED for each
techniques utilized, if applicable; and calibration standard using the criteria developed in 11.6 and
11.3.5 Appropriate warnings whenever the samples are recalibrate if results are not within the control limits. As in the
time, light, or temperature sensitive, coupled with an indication step described in 11.6, whether the D values are percentages or
of the allowable holding time. If it is necessary to estimate absolute units depends on how the calibration curve was fitted.
appropriate holding times, refer to Practice D 4841. 11.6.6 Record the D values for all acceptable calibration
11.4 Chain of Custody The laboratory should record the analyses and, after 20 to 25 additional results, revise related
available history of every sample received, including its control limits by recalculating D and SD from the new data.
collection, preservation, transportation, transfers, analysis, and 11.6.7 It is important to preserve the sign of all D values.
final disposal. This record will assist the laboratory in the 11.7 Method Blank:
investigation of any problems regarding the sample. If the
sample is to meet regulatory or legal requirements, a formal 11.7.1 A method blank should be run to identify sources of
chain of custody is a must. For details regarding chain of contamination arising from the reagents or handling procedures
custody procedures see Guide D 4840. used in performing the analysis. Determine reagent water,
11.5 Analytical Quality Control (AQC)Items stated in reagents, and solvent blanks for each set of samples analyzed,
11.6 through 11.12 are recommended as the basis for a routine when there is a change in the reagent water system, or
within laboratory analytical quality control program. SOPs for whenever a new source (newly prepared reagent or solvent) is
each method should contain the QC specifications appropriate introduced into the analytical system. Reagents or solvents, or
for that method. The QC program described in 11.6 through both, should also be checked for purity prior to use.
11.12 will be superseded by the QC section that will ultimately 11.7.2 Carry each method blank through the entire proce-
appear in each ASTM Committee D-19 test method. These QC dure.
sections will be prepared in accordance with Practice D 5847. 11.7.3 Response to a significant method blank depends a
If the method will be used to compare results between different great deal on the method, but the associated data shall certainly
laboratories, see Practice D 2777. For further information, see be evaluated, and every effort should be made to resolve or

6
 D 3856 95 (Reapproval 2000)
minimize system contaminants. For each method, establish a UCL 5 3.27 ~ R!
maximum limit for the method blank based on end users
(See Note 2.)
requirements.
11.8 Field Blank: NOTE 2This factor may be found in Table 2, p. 83 of Ref. (2).
11.8.1 Different types of field blanks may be used during 11.9.5 Review the initial data for R values greater than the
sampling to distinguish among potential sources of contami- UCL value for the appropriate concentration range. If such
nation that can affect the sampling process. Transport aliquots values are found, they should be discarded and the related UCL
of analyte-free water or solvent to the field in sealed containers value should be recalculated from the remaining R values
as field blanks for later return to the laboratory with the within that concentration range.
samples. Designate a specific number of field blanks as trip
11.9.6 Within each set of 20 or fewer samples to be
blanks, which are not opened in the field but are used to detect
analyzed together, evaluate system precision by conducting
any contamination arising from handling, transport, or site
duplicate analyses on one of the samples selected at random. If
storage. Designate a specific number of field blanks as equip-
the relative range value ( R) calculated from these duplicates is
ment blanks, which are passed through the sampling equipment
greater than the appropriate UCL value, system precision is
to detect any contamination from the equipment itself or the
judged to be out-of-control and analyses must stop until the
conditions during sampling.
problem has been resolved. Problems with these data may
11.8.2 Analyze appropriate field blanks with each set of
indicate the need for stricter adherence to accepted laboratory
samples from a given source. Carry each field blank through
practices.
the entire procedure.
11.8.3 When interferences occur, it is best to discard the 11.9.7 After obtaining 20 to 25 additional acceptable pairs
associated analytical results, investigate the cause so such of data within each concentration level for a sample type,
losses may be avoided in the future, and resample. In situations periodically update the table of critical relative range values by
where it is impossible to resample, however, it may be repeating the step described in 11.9.4 using the new data.
necessary to report the available results along with a note Review the criteria being maintained and combine any which
explaining the extent of the interference and its affect upon the are very similar for related concentrations or sample types. If
data. the criteria for adjacent concentration ranges are quite differ-
11.9 PrecisionPrecision is the closeness of agreement ent, further subdivision by concentration may be necessary.
between the results of repeated analysis on the same sample. 11.9.8 Table A1.1 gives an example of precision estimates
11.9.1 GeneralDevelop the necessary initial data by ran- from duplicate analyses within specific concentration ranges
domly selecting routine samples to be analyzed twice in order for three analytes.
to provide duplicate analyses. Consider the steps in 11.9.1.1- 11.10 Bias Check Using Standard Solutions:
11.9.8 . 11.10.1 Analyze at least one standard through the complete
11.9.1.1 Develop these data over a reasonable period of time method for every subset of 20 or fewer routine samples to be
to reflect day-to-day operations. analyzed together. This standard of known concentration can
11.9.1.2 Choose the samples that are most representative of be purchased from an external source or prepared in house
the interference potential of the sample type. If the laboratory from materials or solutions of known purity. It should come
handles multiple sample types with different precision charac- from a source of material different from that used for the
teristics, it will be necessary to establish and maintain separate calibration.
background data and evaluation criteria for each sample type. 11.10.2 To provide a complete record of the calibration and
11.9.1.3 Ultimately, samples representing the entire concen- recovery for each analytical run, one of these standard samples
tration range should be included within each sample type if should be the last sample analyzed.
necessary. 11.10.3 Use concentrations that approximate those found in
11.9.2 From each pair of duplicate analytes ( X1 and X2) the related routine samples. Calculate percent recovery ( P) as
calculate their relative range value (R): follows:
? X1 2 X 2? 100 ~observed value!
R5 P5
~X 1 1 X2!/2 ~ true value!

where: 11.10.4 After 20 to 25 standards are analyzed over time,

?X1 2 X2? = means the unsigned difference between X1 and calculate average percent recovery ( P) and standard deviation
X 2. (SP) of the resulting P values.
11.9.3 After 50 to 100 R values are available for an analyte, 11.10.5 If subsequent standards for percent recovery are not
order the R values by their related sample concentration within the interval P 6 3 SP, the analytical system should be
estimates, organize the values into concentration ranges that checked for problems. If problems exist, resolve them before
seem to have a similar underlying R value, and calculate the continuing the analyses. Problems with these data often require
average R value ( R) for each of these concentration ranges. greater care in sample processing prior to actual measurement.
Minimize the number of concentration ranges as much as 11.10.6 Runs of seven or more successive points, all either
practical. above or below P, also indicate the system is out-of-control.
11.9.4 Calculate the upper control limit (UCL) for each Use of a Shewhart X-chart is recommended to facilitate
concentration range as follows: evaluation of percent recovery results. An example of the

7
 D 3856 95 (Reapproval 2000)
calculation of percent recovery and development of a Shewhart 11.12 Summary of the Analytical Quality ControlThe
X-chart is given in Table A1.2 and Fig. A1.1. following recommended analytical quality control program
11.10.7 Record recovery of all acceptable check standards should be the standard practice in any laboratory.
and, after 20 to 25 additional results, revise the related control 11.12.1 Three or more standards are needed to develop a
limits by recalculating P and S P from the new data. As in calibration curve in concentrations covering the working range,
11.9.7, the criteria subdivisions by sample type and concentra- as necessary, or measurement of two calibration standards to
tion range should be periodically reviewed to judge their verify the existing calibration curve.
appropriateness. 11.12.2 One method blank per run.
11.11 Bias Check Using Recovery of Spikes: 11.12.3 One field blank per set of samples.
11.11.1 Do essentially the same thing for recovery as was 11.12.4 One duplicate for precision check (at least one
done in 11.10, except that a concentrate spike is added to a every 20 routine samples).
randomly selected routine environmental sample from the
11.12.5 One standard sample for recovery and calibration
current analytical run rather than to reagent water. Different
check (at least one every 20 routine samples). A standard
types of routine environmental samples may have to be dealt
should be the last sample analyzed in each run.
with separately if the samples exhibit different spike recovery
characteristics. From this point on, this discussion is in terms of 11.12.6 One spiked sample for recovery check in the pres-
a specific identified sample type. P values for the recovery data ence of a sample matrix (at least one every 20 routine samples).
are calculated as follows: 11.12.7 TotalDepending on the end use of the data, seven
to ten analytical quality control analyses may be required for
100 [A~Vs 1 V! 2 ~BV s!#
P5 runs of up to 20 routine samples; 10 to 13 analytical quality
CV
control analyses may be required for runs of 21 to 40 routine
where: samples, etc.
A = measured concentration of the component in the 11.12.8 Minimal Analytical Quality ControlFor very
spiked sample, small operations or small sample loads, the described analyti-
B = measured background concentration of component in cal quality control program may not be practical or necessary
the sample, for all analytes. Whenever analytical quality control must be
C = concentration of component in spiking solution, reduced below the level recommended, the following minimal
Vs = volume of sample before spiking, and analytical quality control program should be maintained.
V = volume of spiking solution used. 11.12.9 Continue calibration or calibration checks as de-
11.11.2 In spiking samples, make sure that: scribed in 11.6.
11.11.2.1 Sufficient spike is added to at least double the
11.12.10 Analyze one field blank per set of samples to
background concentration or to reach a concentration for which
check for contamination. If an out-of-control situation is
the calibration curve has been established. If the background
indicated, a method blank should be run to find out whether the
concentration is higher than the midpoint of the standard curve,
contamination problem is in the laboratory or the field.
the background water should be diluted into the lower half of
the calibration range and reanalyzed before spiking. 11.12.11 Analyze one spiked sample at the end of each
analytical run to check for recovery or precision problems. If
11.11.2.2 The volume of a spike should be kept to a
an out-of-control situation is indicated, analyze a standard to
minimum and not exceed 5 % of the sample volume. In organic
find out whether the problem is basic recovery or calibration,
analyses, the volume of spike should be no greater than 150
or both. Successful recovery of the standard would suggest
mL so that the solubility of the standard in the water will not
either a matrix problem or a precision problem. A precision
be affected.
problem would produce random out-of-control indications,
11.11.3 Resulting P values must fall within P 6 3 SP
probably caused by poor or inconsistent analytical techniques
calculated from previous related spike recovery data. If not, the
or instrumentation.
system may be out-of-control, and the cause must be found and
corrected before continuing the analyses. Problems with these 11.13 Performance ReviewAnalysts should maintain a
data often indicate sample matrix interferences. Related spike permanent record of the quality control checks which are
recovery data are developed from a particular environmental performed. The laboratory supervisor should hold frequent
matrix, that is, groundwater, wastewater, etc. These limits may meetings to review the quality control program with analysts to
differ from the limits calculated in 11.10.3-11.10.5. discuss the quality control checks performed and the resolution
11.11.4 As in 11.10.6, runs of seven or more results on the of any problems which are detected. Deficiencies which are
same side of X indicate the system is out-of-control, and the detected should be documented in the record book indicating
use of a Shewhart X-chart is recommended to facilitate the analytes involved, the problem, the action taken, and the
evaluation of results. date of the action.
11.11.5 By simply calculating P from P values calculated as
specified in either 11.11.1 or 11.10.3, percent recoveries of a 12. Trouble Shooting
spike can be treated as shown in the example given in Table 12.1 Extreme, unexpected or questionable results are nor-
A1.2 and Fig. A1.1. mally detected and reported by the analyst, or are noted by the
11.11.6 Periodically review and update the recovery criteria supervisor in the daily reviews of results. When a deviation is
similarly to 11.10.7. noted, the train of sampling and analytical methods and quality

8
 D 3856 95 (Reapproval 2000)
control shall be investigated. The documented intralaboratory labeled and dated. A mechanism should be established for
quality control checks provide the primary means for the reorder of chemicals within the estimated shelf lives.
investigation. 12.2.3 Reagent blanks should be carried through all sam-
12.1.1 Review the records of the sample collection. Check pling and analytical procedures. In colorimetry, the reagent
the preservation technique used, the chain of custody record, blank should be compared with reagent water to detect an
the time in transit, and comments on the conditions of the unusual reagent blank response.
samples upon arrival at the laboratory, for example, tempera- 12.2.4 When the data are obtained through the use of a
ture upon arrival, etc. standard curve, the points on the curve should be treated
statistically and a regression line should be developed for the
12.1.2 Analytical ProcedureCheck calculations for trans- analytical method.
position of numbers and mathematical error. Any significant 12.2.5 Use of reference materials of known quality from
positive blank result indicates field or laboratory contamination sources such as NIST, or others, should be used to confirm the
of sample, sampling device, sample container, reagents, re- adequacy of the technique and the analyst.
agent water, etc. Check monitoring data on reagent water. 12.3 Senior analysts must maintain a permanent log of
Check reagents for changes in bottle and lot and expiration quality control checks performed. The laboratory supervisor
dates. Analyze or reanalyze samples to confirm source and shall hold frequent quality assurance review meetings with
resolution of problem. Confirm recoveries with analyses of senior analysts to discuss the quality control checks performed
known reference samples. and the resolution of problems detected. Deficiencies and
12.2 The investigation may indicate good field and labo- corrective actions must be recorded in a log indicating the
ratory practices were not followed, such as the following: analytes involved, the problem, the action taken, and the date
12.2.1 The field sampling team should keep a bound field of the action. Only when the deficiencies have been discovered,
logbook for recording field measurements, time, temperature, corrected, and confirmed as corrected is the real benefit of a
sampling location, weather conditions, and other pertinent quality assurance plan realized, that is, improved data quality.
information. 13. Keywords
12.2.2 The analyst should keep records on incoming chemi- 13.1 analytical practices; analytical resources; good labora-
cals and reagents, and the preparation of reagents, with tory practice; quality assurance; quality control; trouble
estimated shelf lives. Reagent containers should be properly shooting

ANNEX

(Mandatory Information)

A1. QUALITY CONTROL EXAMPLES

A1.1 Table A1.1 presents the results of carrying out the 1 n

2105.27
steps described in 11.9.2 through 11.9.4 for three different P 5 n (
i51
Pi 5 21 5 100.25 (A1.2)
analytes to illustrate use of the UCL values. If duplicate
chromium results of 31.2 and 33.7 were obtained, the system
precision would be checked as follows: Sp 5 (~Pi 2 P! 2
n21 5
719.839
20 5 5.999 (A1.3)
? 31.2 2 33.7 ? ? 22.5? 2.5
R 5 5 5 5 0.0770 (A1.1) P 63 Sp 5 100.25 6 18.00 5 82.25 to 118.25 (A1.4)
~31.2 1 33.7!/2 64.9/2 32.45

A1.3 Therefore, as specified in 11.11.3, percent recovery

Since the appropriate UCL from Table A1.1 is 0.109 and the
values for total PO 4-P standards roughly within the concen-
current R values are not greater, precision of the analytical
tration range from 0.34 to 4.9, that occurred below 82.2 % or
system is judged to be within control.
above 118 %, would indicate that the accuracy of the analytical
A1.2 The following calculations result from carrying out system is under control. The related Shewhart X-Chart is
the step described in 11.11.3 using the data in Table A1.2: illustrated in Fig. A1.1.

9
 D 3856 95 (Reapproval 2000)
TABLE A1.1 Precision Estimates from Duplicate Analyses Within Specific Concentration Ranges for Three Analytes
No. R
of Average Average for
Sets Concentration Relative Combined Final
Concentration of of Range Concentration UCL
Analytes Range Duplicates Data (R) Ranges Results
BOD, 1 21 5.85 0.1776
5-Day to
(mg/L) <10
L
10 30 17.6 0.1104 0.1381 0.452
to
<25

25 27 36.1 0.0924
to
<50
50 29 102.0 0.0638
to
<150
150 17 197.0 0.0564 0.0652 0.213
to
<300
300 12 520.0 0.0232
to
<1,000
1,000 3 3341.0 0.0528
up

Chromium 5 32 6.15 0.0612 0.0612 0.200

(g/L) to<
L 10

10 15 16.7 0.0340
to
<25
25 16 36.2 0.0310
to
<50
50 15 85.1 0.0446 0.0334 0.109
to
<150
150 8 240.0 0.0218
to
<500
500 5 3170.0 0.0240
up

Copper 5 16 11.1 0.1234

(g/L) to
L <15
15 23 19.1 0.0736 0.0940 0.307
to
<25

25 21 35.4 0.0338
to<
50
50 26 65.9 0.0354
to<
100
100 10 134.0 0.0210 0.0313 0.102
to<
200
200 3 351.0 0.0130
up

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 D 3856 95 (Reapproval 2000)
TABLE A1.2 Analysis A of Total Phosphate-Phosphorus
Standards, in mg/L Total PO4-P
%
Point Known Obtained (Pi P) 2
Recovery = Pi
1 0.34 0.33 97.06 10.176
2 0.34 0.34 100.00 0.062
3 0.40 0.40 100.00 0.062
4 0.49 0.49 100.00 0.062
5 0.49 0.49 100.00 0.062
6 0.50 0.47 94.00 39.063
7 0.50 0.53 106.00 33.062
8 0.50 0.56 112.00 138.063
9 0.52 0.59 113.46 174.504
10 0.66 0.70 106.06 33.756
11 0.66 0.60 90.91 87.236
12 0.67 0.65 97.01 10.498
13 0.68 0.65 95.59 21.716
14 0.83 0.80 96.39 14.900
15 1.30 1.20 92.31 63.044
16 1.30 1.30 100.00 0.062
17 1.60 1.70 106.25 36.000
18 2.30 2.30 100.00 0.062
19 2.30 2.40 104.35 16.810
20 3.30 3.30 100.00 0.062
21 4.90 4.60 93.88 40.577
SUMS: 2105.27 719.839
A
Using a colorimetric method with persulfate digestion.

FIG. A1.1 Shewart Control Chart for Percent Recovery Data

REFERENCES

(1) ANSI/ASQC Q90-1987 through Q94-1987, ISO 9000 Series of (8) Prudent Practices Laboratory Series, National Research Council,
Quality Management and Quality Assurance Standards, the ISO/IEC National Academy Press, Washington, DC: Prudent Practices for
Guide 25-1990, General Requirements for the Competence of Cali- Handling Hazardous Chemicals in Laboratories, 1981; Prudent Prac-
bration and Testing Laboratories, American National Standards Insti- tices for Disposal of Chemicals from Laboratories, 1983; and Bio-
tute, New York, NY. safety in the Laboratory, 1989.
(2) ASTM Manual on Presentation of Data and Control Chart Analysis, (9) NIOSH Pocket Guide to Chemical Hazards, NIOSH Publication No.
ASTM MNL 7 , 6th Edition, ASTM, Philadelphia, PA, 1990. 85-114, Superintendent of Documents, U.S. Government Printing
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Lewis, H. F., ed., Reinhold Publishing Corp., New York, NY, 1962. (10) The Merck Index: An Encyclopedia of Chemicals and Drugs ,
(4) Industrial VentilationA Manual of Recommended Practice, Ameri- Merck and Company, Inc., Rahway, NJ.
can Conference of Governmental Industrial Hygienists, Cincinnati, (11) Sax, N. I., and Lewis, R. J., Sr., Dangerous Properties of Industrial
OH. Materials, 8th Edition, Van Nostrand Reinhold Co., New York, NY,
(5) The Firefighters Handbook of Hazardous Materials, Baker, C. J., ed., 1992.
Indianapolis, IN. (12) Registry of Toxic Effects of Chemical Substances, NIOSH Publica-
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Title 29, Code of Federal Regulations, Part 1910, Section 1910.1450 Printing Office, Washington, DC.
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Printing Office, Washington, DC, 20402. Agents in the Work Environment and Biological Exposure Indices
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NFPA 45, National Fire Protection Association, Batterymarch Park, trial Hygienists (ACGIH), Cincinnati, OH.
Quincy, MA, 1986. (14) Good Automated Laboratory Practices, Office of Information

11
 D 3856 95 (Reapproval 2000)
Resources Management, U.S. Environmental Protection Agency, (16) Handbook for Analytical Quality Control in Water and Wastewater
Research Triangle Park, NC, 1992. Laboratories , Document No. EPA-600/4-79-019, U.S. Environmen-
(15) Handbook for Sampling and Sample Preservation of Water and tal Protection Agency, Environmental Monitoring and Support Labo-
Wastewater, Document No. EPA-600/4-82-029, National Tech-nical ratory, Cincinnati, OH.
Information Service, Springfield, VA.

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12