AK103

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Method AK 103
For Determination of Residual Range Organics
Version 04/08/02

1. Scope and Application

1.1 Objectives

1.1.1 This method is designed to measure the concentration of Residual Range Organics
(RRO) in soil. This corresponds to an n-alkane range from the beginning of C25 to the end
of C36, and compounds with boiling points from approximately 400° C to 500° C. (See
Figure 1 of this method.)

1.1.2 The method is primarily designed to measure lubricating or motor oils or other
heavy petroleum products. Components greater than C36 present in products such as
asphalts, and mid-range boiling point products such as diesel and bunker C, are also
detectable under the conditions of the method.

1.1.3 This method can be an extension of the Method for Determination of Diesel
Range Organics as specified in AK 102. All quality control requirements of both methods
(Section 10 of this method) must be met. Reasonable modification to accommodate the
concurrent analysis of DRO and RRO is within the scope of this method.

1.2 Quantitation Limits: The practical quantitation limit (PQL) for this method of analysis of
RROs is based on studies done by laboratories other than the State of Alaska, Department
of Environmental Conservation, State Chemistry Laboratory and is approximately 100
mg/kg for soils using motor oil as a standard.

1.3 Dynamic Range: Dilutions should be performed as necessary to put the chromatographic
envelope within the linear range of the method. Linear range is dependent in part upon
column type, detector sensitivity, and injection volume. Typically, the approximate range
is 10 mg/L to 200 mg/L in extracts.

1.4 Experience: This method is based on a solvent extraction, gas chromatography (GC)
procedure. This method should be used by, or under the supervision of, analysts
experienced in the use of solvent extractions and gas chromatographs and skilled in
interpreting gas chromatograms and their use as a quantitative tool.
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2. Method Summary

2.1 This method provides gas chromatographic conditions for the detection of high molecular
weight with similar characteristics and boiling points, may also be detected with this
method. The sample is spiked with a surrogate compound and extracted with methylene
chloride. The extract is dried and concentrated to a known volume. A portion of the dried,
concentrated extract is injected into a capillary column gas chromatograph equipped with
a flame ionization detector (FID), which has been temperature programmed to facilitate
separation of organic compounds. Quantitation must be performed by comparing the total
chromatographic area between the peak start of C25 and the peak end of C36, both resolved
and unresolved components, based on FID response, and using forced baseline-baseline
integration, compared to a blended commercial standard called the Residuals Calibration
Standard (see Section 3.2 of this method).

2.2 This version of the method was developed by Mary Jane Pilgrim, Ph.D. and is based in
part on US EPA Methods 8000 and 8100, SW-846, Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods, adopted by reference in 18 AAC 78.090(i) [1],
Method OA-2 [2], the API consensus method "Method for the Determination of
Petroleum Hydrocarbons", Original version, 2/3/92 [3] and work by the EPA Total
Petroleum Hydrocarbons Method Committee [41, the State of Oregon, "Total Petroleum
Hydrocarbon Methods" QAR 340-122-3 50 dated December 11, 1990, and the State of
Washington, "Hydrocarbon Identification Method" WTPH-HCID from Guidance for
Remediation of Releases from Underground Storage Tanks, Document 91-30 dated July
1991, and data from Alaska's State Chemistry Laboratory, with support from the Storage
Tank Program.

3. Definitions

3.1 Residual Range Organics (RRO): All chromatographic peaks, both resolved and
unresolved, eluting between the peak start of n-pentacosane (C25) and the peak end of
n-hextriacontane (C36). Quantitation is based on direct comparison of the area within this
range to the total area of the motor oil standard within the same (C25 - C36) range as
determined from FID response using baseline-baseline integration. Surrogate peak areas
shall be determined by valley to valley integration.

3.2 Residuals Calibration Standard (RCS): A blend of equal weights of 30 weight and 40
weight motor oils (1:1) and diluted to appropriate concentrations in methylene chloride.
This standard serves as a calibration standard for RRO. It is recommended that the RCS
components be combined with the DCS components if DRO (AK102) is to be done
simultaneously. If the source of the spill is known, it is suggested that the known source
be used as the calibration standard.
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3.3 Surrogate: n-Triacontane d62 or equivalent. A demonstration of suitability must be

performed. Any variance from this surrogate must be approved by the ADEC Approval
Authority.

3.4 Calibration Verification Standard (CVS): A commercial motor oil blend, prepared as in
Section 3.2 of this method but with products from a source other than those used to
prepare the RCS. It is used by the laboratory to verify the accuracy of the calibration. If
the source of the spill is known, it can be used to verify the curve if the calibration
standards are prepared from a second source. Greater than 95% of the hydrocarbons must
elute between the retention time markers.

3.5 Laboratory Fortified Blank (LFB): A method blank sample spiked with diluted RCS
(Section 3.2 of this methods) . The spike recovery is used to evaluate method control (see
Table 1 of this method).

3.6 Retention Time Window Standard: A mixture of the normal alkanes n-pentacosane (C25)
and n-hexatriacontane (C36) which is analyzed once every 24 hour "day" or with each batch
of samples, whichever is less frequent, not to exceed 20 samples per batch. This standard
serves to define the retention time window for RRO.

3.7 Internal Standard: No internal standard has been used in development of this method. Any
internal standard which mimics the chemical characteristics of heavy petroleum products
may be used, with prior ADEC approval.

3.8 Standard Soil: Ottawa sand or other standard soil with characteristics that match the field
samples as closely as possible, used in quality control standards.

3.9 Continuing Calibration Standard (CCS): A mid-range working standard diluted from the
RCS (Section 3.2 of this method), used to verify that the analytical system is operating in a
manner comparable to that at the time of calibration.

3.10 Method Detection Limit (MDL): The minimum concentration of a compound that can be
measured and reported with 99 percent confidence that the value is greater than zero,
determined from analysis of a sample in a given matrix containing the analyte. (See 40
C.F.R. 136, Appendix B, for method of determining method detection limit.) Each
laboratory must demonstrate and periodically update method detection limits for each
analyte of interest.
3.11 Practical Quantification Limit (PQL): is defined as 5 times the MDL.

3.12 Method Blank – also known as a procedural blank demonstrates that apparatus and
reagents used to perform the method are free from contamination

3.13 Instrument Blank – demonstrates that the instrument is free from contamination.
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3.14 Solvent Blank – demonstrates that the solvent (in this case methylene chloride) used in the
method is free from contamination. It should not go through the procedure. It may also
serve as an instrument blank.

3.15 Other terms are as defined in SW-846 [1].

4. Interferences

4.1 Other organic compounds including, but not limited to, animal and vegetable oil and
grease, chlorinated hydrocarbons, phenols, phthalate esters, and biogenic terpenes are
measurable under the conditions of this method. Some lighter petroleum products such as
bunker C and diesels, as well as crude oils, may produce a response within the retention
time range for RRO. As defined in the method, the RRO results include these
compounds.

4.2 Method interferences are reduced by washing all glassware with hot soapy water and then
rinsing it with tap water, methanol, and methylene chloride. Heating the glassware to
reduce contaminants should not be necessary if this cleaning method is followed. At least
one blank must be analyzed with each extraction batch to demonstrate that the samples
are free from method interferences.

4.3 High purity reagents must be used to minimize interference problems.

4.4 Contamination by carryover can occur whenever high-level and low-level samples are
sequentially analyzed. When an unusually concentrated sample is encountered, it should
be followed by a solvent blank to check for instrument contamination.

5. Safety Issues

5.1 The toxicity or carcinogenicity of each reagent 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 Occupational Safety and Health Administration (OSHA) regulations
regarding the safe handling of the chemicals specified in this method. A reference file of
Material Safety Date Sheets (MSDS) should also be made available to all personnel
involved in the chemical analysis. Additional references to laboratory safety should be
available and should be identified for use by the analyst.

5.2 A hearing protection device should be used when performing sonication.

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6. Apparatus and Materials

(Unless otherwise indicated, all apparatus and materials are recommended, not required.)

6.1 Glassware

6. 1.1 4-oz. amber glass wide mouth jars with Teflon-lined screw caps

6.1.2 250-mL glass centrifuge tubes (if using sonication extraction).

6.1.3 2-mL glass vials with Teflon-lined cap (autosampler vials).

6.1.4 Disposable pipettes: Pasteur.

6.1.5 Graduated cylinders: 250-mL.

6.1.6 Glass or Teflon funnels.

6.2 Boiling chips - Approximately 10/40 mesh. Heat to 400°C for 30 minutes or Soxhlet
extract with methylene chloride.

6.3 Micro syringes: 1-µL, 5-µl, 10-µL, 25-µL, and 100-µL or as needed.

6.4 An analytical balance capable of accurately weighing 0.0001 g should be used for
preparing standards. A top-loading balance capable of weighing to the nearest 0.01 g
should be used for sample preparation.

6.5 Stainless steel spatula.

6.6 Gas Chromatography

6.6.1 Gas Chromatograph: Analytical system including appropriate gas supply and all
required accessories, including a Flame Ionization Detector (FID), column
supplies, gases, and syringes. A data system capable of determining peak areas
using a forced baseline - baseline projection is required. A data system capable of
storing and reintegrating chromatographic data is recommended.

6.6.2 Columns

6.6.2.1 Column 1: J&W DB-1 30m x 0.32 mm, 0.25 film

6.6.2.2 Alternate columns: DB-5 30m x 0.32 mm, 0.25 micron film thickness.

6.6.2.3 Other Columns may be used - capillary columns may be required to

achieve the necessary resolution. The column must resolve C24 from C25 in a
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midrange RCS and C36 must be clearly identified. See Section 9.2.2 of this
method for additional column performance criteria.

6.7 Sonication

6.7.1 Ultrasonic cell disrupter: A horn-type sonicator equipped with a titanium tip
should be used. A Heat Systems-Ultrasonics, Inc. Model W-385 (475 watt) sonicator or
equivalent (power wattage must be a minimum of 375 with pulsing capability and No.
200 ½ inch Tapped Disrupter Horn) plus No. 207 ¾ inch Tapped Disrupter Horn, and
No. 419 1/8 inch Standard tapered Microtip probe.

6.7.2 A Sonabox or equivalent is recommended with the above disrupter for decreasing
sound (Heat Systems-Ultrasonics, Inc., Model 432 13 or equivalent).

6.8 Soxhlet extraction apparatus as described in SW-846 Method 3540 [1].

6.9 Nitrogen evaporator with high purity (grade 4.5 or equivalent) nitrogen gas source.

7. Reagents and Standards

7.1 Reagent Water: Water that has been shown to be free from target analytes and interfering
substances.

7.2 Methylene Chloride, Acetone - pesticide grade or equivalent. At a minimum, the solvents
must be shown to be free from RRO.

7.3 Sodium Sulfate - (American Chemical Society (ACS) grade) granular, anhydrous. Purify
by heating at 400°C for 4 hours in a shallow tray, or by extracting three times with
methylene chloride and drying at 100 ±5° C. Incomplete cleaning of sodium sulfate can
result in contamination.

7.4 Stock Standard Solutions - Prepare the following stock standards. Unless noted, all are
prepared in the methylene chloride listed in Section 7.2 above. Standards preparation
should follow guidelines in SW-846 [1 ]. All standards prepared by the laboratory should
be stored at -10 to -20° C and protected from light. Marking of the meniscus is helpful in
maintaining stock standard integrity. Standards should be checked no more than six
months prior to use to assure their integrity.

7.4.1 Recommended Surrogate: 5000 µg/mL n-Triacontane-d62 (dTC). A working

solution is made at 500 µg/mL (recommended concentration) in acetone.

7.4.2 Residuals Calibration Standard (RCS): A blend of equal weights of motor oil,
mixed together to form a composite motor oil (1:1, 30 weight: 40 weight) is used
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to prepare stock calibration standards in methylene chloride. No fewer than 3

concentrations of this Residuals Calibration Standard are used for instrument
calibration. A five point calibration curve is recommended. Other than one
standard concentration near the practical quantitation limit, the expected range of
concentrations found in project samples should define the working range of the
calibration.

7.4.3 Retention Time Window Standard: A stock solution of C25 and C36 n-alkanes with
each component at a level of at least 10,000 µg/mL (recommended). This blend of
alkanes serves as a retention time window defining mix for RRO.

7.4.4 Stock CVS: From a blend of commercial motor oils other than those used to
prepare the RCS, make an equal weight mixture as described above (see Section
7.4.2). Prepare a stock solution of 25,000 µg/mL in methylene chloride. A
working solution is made at a recommended concentration of 5,000 µg/mL in
acetone.

8. Sample Collection, Preservation, Containers, and Holding Times

8.1 Soils are collected in a core tube or 4- or 8-oz amber glass jar with Teflon lined lid. The
samples are stored at 4 ± 2° C from the time of collection until extraction. Extraction must
be performed on soils within 14 days.[ 1]. All analyses of extracts must take place within
40 days.

8.2 Soil samples to be analyzed for volatiles, DRO, and RRO may be collected in the same,
methanol preserved container and stored as for GRO (AK101). If this option is selected, the
mechanics of the collection, preservation, and container should be discussed with the client
before sampling kit preparation. RRO extraction and analysis must still meet the
requirements of 8.1, above.

9. Procedure

9.1 Sample Preparation: The preferred procedure for extraction is Method 3540 (Soxhlet
Extraction). However, any sample extraction technique which meets the quality assurance
requirements specified in Section 10 and Table 1 of this method may be used, and the
extraction solvent must be methylene chloride.

9. 1.1 Soil Preparation - Soxhlet Extraction

9. 1. 1.1 Decant any water layered on the sample. Refer to method AK 102,
Section 9.1.2 if DRO is to be done simultaneously. Mix the sample well and note
any foreign objects or anomalies (variable particle size, presence of oil sheen,
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multiple phases, etc.).

9.1.1.2 Weigh 10 g to 30 g of the original sample into an extraction thimble. Add

an equal weight of anhydrous sodium sulfate and stir the mixture well with
stainless steel or Teflon spatula, taking care to not rupture the thimble. The
sample should have a grainy texture - if the sample clumps, add more sodium
sulfate until a grainy texture is achieved and note the addition.

9.1.1.3 Place loaded thimbles in extractors and add surrogate to all samples, both
field and quality control.

9.1.1.4 Prepare an LFB from the RCS and 10 g of methylene chloride rinsed
standard soil. In addition, prepare a method blank.

9.1.1.5 Add 300 mL of methylene chloride to the 500-mL extraction flask. More
or less extraction solvent may be used if the quality control criteria specified in
Section 10 and Table 1 are met. Also add a few methylene chloride washed
boiling chips to the flask. Connect the extractor to the flask and the condenser to
the extractor. Allow samples to extract for 18-24 hours, or as long as necessary to
achieve optimum surrogate recovery. Be sure that coolant is flowing around the
condensers.

9.1.1.6 Dry the extract with anhydrous sodium sulfate (This assures that the
extract is water-free before concentration.)

9.1.1.7 Concentrate extract to 1 mL at a temperature not to exceed 55 ° C or that

recommended by the manufacturer of concentration apparatus being used.
Transfer extracts to GC vials for analysis. Extracts should be stored in a freezer
<-10° C. Record the information for extraction and concentration steps.

Note: The extraction and concentration steps must be performed under a hood. Methylene
chloride is a potential health hazard (See MSDS.)

9.1.2 Moisture Determination for Solids

9.1.2.1 Moisture determinations must accompany all soils data (reported in

mg/dry kg) so the client can, at will, determine the results in the original soil
condition. Because of the potential for high petroleum compound concentrations
in the soil, all drying should be done under a functioning hood.

9.1.2.2 To determine percentage of moisture, pre-weigh an aluminum weighing

boat. Weigh 5-10 g of the sample into the boat and record both weights to the
nearest 0.001 g. Dry the sample overnight in a warm (105°C) oven.
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9.1.2.3 Remove the sample from the oven and cool in a desiccator until the
sample reaches room temperature, and weigh to the nearest 0.01g. Record the
weight.

9.1.3 Dilution Technique

9.1.3.1 This is used for product or waste samples for which extraction is not
appropriate and which are soluble in methylene chloride.

9.1.3.2 Weigh 1 g of sample into a 10-mL volumetric flask. Dilute to 10 mL with

methylene chloride. Transfer to a 12-mL vial with a Teflon-lined lid. Mark
meniscus and store at <4° C.

9.2 Gas Chromatography

9.2.1 Conditions (Recommended): Set helium column pressure to 20#. Set column
temperature to 40° C for 2 minutes, then ramp at a rate of 120° C/min to 380° C and hold
for 15 min. (run time = 49 minutes). Set FID Detector to 380° C and injector to 280° C.

9.2.2 Performance Criteria: GC run conditions and columns must be chosen to meet the
following criteria:

9.2.2.1 Resolution of the methylene chloride solvent front from C10, if DRO (AK
102) is to be done simultaneously.

9.2.2.2 The separation number, TZ, should be greater than 15 for C24 and C25 if
DRO is to be analyzed concomitantly.

TZ = [(retention time C25 - retention time C24 )/ (W ½ of C25 + W ½ of C24)] -1

Where "W ½ " = peak width at half-height

9.2.2.3 The column must be capable of separating typical motor oil components
from surrogate and internal standards.

9.3 Calibration

9.3.1 Calibrate the GC, set up as in Section 9.2 of this method, with a minimum of three
concentrations of RCS (five concentrations are recommended).
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9.3.2 Choose Residual Calibration Standard concentrations to cover the RRO range
expected in the samples, or the linear range of the instrument, whichever is less.
Linearity of the calibration curve at the PQL must be documented.

9.3.3 Curve fit must be linear regression with a R2 of 0.995 or better, quadratic fit with
a R2 of 0.995 or better, or if using response factors the average percent relative
standard deviation (%RSD) is less than 25% over the working range.

9.3.4 The calibration curve must be confirmed using the CVS (see Section 7.4.4 of this
method). This standard verifies the accuracy of the calibration. The concentration
of the CVS should be within the expected concentration range of the samples to
be analyzed.

9.3.5 The working response factor or calibration curve must be verified on each
working day (24 hours) by the injection of a CCS (see Section 7.4.2 of this
method) at a concentration mid-point on the calibration curve. The CCS is a
diluted aliquot of the same standard used to initially calibrate the instrument.

9.4 Retention Time Window Definition

9.4.1 Before establishing windows, be certain that the GC system is within optimum
operating conditions (see Section 9.2 of this method). Make three injections of the
Retention Time Window Standard (see Section 7.4.3 of this method) and
surrogate 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.

9.4.2 Calculate the standard deviation of the three absolute retention times for C25, C36,
and the surrogate.

9.4.2.1 The retention time (RT) window for individual peaks is defined as the
average RT plus or minus three times the standard deviation of the absolute
retention times for each component.

9.4.2.2 In those cases where the standard deviation for a particular analyte is zero,
the laboratory should use ± 0.05 min. instead of the standard deviation.

9.4.3 The laboratory must calculate retention time windows for each standard on each
GC column and whenever a new GC column is installed or instrument conditions
changed. The data must be retained by the laboratory.

9.4.4 Retention time windows must be verified regularly and updated no less frequently
than once a year.

9.5 Gas Chromatograph Analysis

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9.5.1 Samples are analyzed by GC/FID. Optimum injection volumes (2 µL using the
conditions established in Section 9.2 of this method) must be established for
specific instrument conditions.

9.5.2 For internal standard calibration, the internal standard is spiked into each sample
and standard at a specified concentration. Note: High RRO values may lead to
measurement bias due to coelution with the internal standard.

9.5.3 If initial calibration (Section 9.3 of this method) has been performed, verify the
calibration by analysis of a mid-point CCS (see Section 9.3.5 of this method).
With each day's run, open a 24 hour analysis window. This is done by running the
Retention Time Window Standard (Section 7.4.3 of this method).

9.5.4 Calculate the percent recovery of the CCS concentration. This is done for RRO as
a group from the CCS. If the response factor has a percent difference greater than
25%, corrective action must be taken.

9.5.5 A solvent blank may be analyzed each day to determine the area generated on
normal baseline noise under the conditions prevailing in the 24 hour period. This
area is generated by projecting a horizontal baseline between the retention times
observed for the peak start of C25 and the peak end of C36. This blank is integrated
over the RRO area in the same manner as for the field samples and is reported as
the solvent blank (refer to Section 4 of this method). Do not baseline subtract.
This information is for data interpretation purposes only.

9.5.6 Blanks should also be run after samples suspected of being highly concentrated, to
prevent carryover. If the blank analysis shows contamination above the practical
quantitation limit, the column must be baked out and subsequent blanks analyzed
until the system is shown to retain contaminants at concentrations less than the
PQL.

9.5.7 If the RRO concentration exceeds the linear range of the method (as defined by
the range of the calibration curve) in the final extract, corrective action must be
taken. The response of the major peaks should be kept in the upper half of the
linear range of the calibration curve. Due to potential measurement bias, internal
standard calibration should not be used when RRO exceeds 5000 µg/mL in the
final extract. The sample should be diluted or external standard calibration should
be used.

9.6 Calculations:

9.6.1 Percent Moisture Calculation

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% Moisture = [(A-C)/(A-B)] x 100

Where: A = weight of boat + wet sample

B = weight of boat
C = weight of boat + dry sample

The % moisture calculation must be included in the data package.

Note: Make sure drying oven is placed under a hood. Heavily contaminated soils will
produce strong organic vapors.

9.6.2 Internal Standard Calibration: The concentration of RROs in the sample must be
determined by calculating the absolute weight of analyte chromatographed from a
summation of peak response for all chromatographic peaks eluting between the
peak start of n-pentacosane and the peak start of n-pentetracontane, using the
calibration curve or the response factor determined in Section 9.3 of this method.
Also refer to Section 9.4 of this method (Retention Time Window Definition).

The concentration of RRO is calculated as follows:

Soil samples:

Cs = (Ax)(Cis)(D)(Vt)
(Ais)(RF)(Vs)

Where: Cs = Concentration of RROs (mg/kg).

Ax = Response for the RROs in the sample, units in area.
RF = Response Factor from CCS (see Section 9.3. 1).
Ais = Response for the internal standard, units same as for Ax.
Cis = Internal standard concentration (mg/mL).
Vt = Volume of final extract in mL.
D = Dilution factor, if dilution was performed on the sample prior to analysis
if no dilution was made, D = 1, dimensionless.
Vs = Amount of sample extracted in kg.

To calculate mg/dry kg for soil samples,

mg/dry kg RRO = ________CS______

1-(% moisture/100)

The % moisture calculation must be included in the data package (see

Section 9.1.2 of this method).

9.6.3 External Standard Calibration:

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Soil samples:

Cs = (Ax)(A)(Vt)(D)
(As)(Vs)

Where: Cs = Concentration of RROs (mg/kg).

Ax = Response for the RROs in the sample, units in area.
As = Response for the external standard, units same as for Ax.
A = External standard concentration (mg/mL).
Vt = Volume of Final extract in mL.
D = Dilution factor, if dilution was performed on the sample prior to analysis. If
no dilution was made, D = 1, dimensionless.
Vs = Amount of sample extracted in kg.

9.6.4 Some software programs are capable of performing moisture calculations with
minimal analyst intervention.

10. Quality Control

10.1 Curve Verification Standard (CVS)

10.1.1 The CVS is not extracted.
10.1.2 The CVS is analyzed once with calibration standards to verify the calibration
curve.
10.1.3 The CVS recovery requirement is 75-125% of true value.

10.2 Continuing Calibration Samples (CCS)

10.2.1 The CCS is not extracted.
10.2.2 The CCS is analyzed at the start and end of an analytical batch and for every 20
samples in that batch.
10.2.3 The CCS recovery requirement is 75-125% of true value.

10.3 Blanks
10.3.1 Instrument Blank may be analyzed with each analytical batch to demonstrate that
the system is free from contamination.
10.3.2 Method Blank must be analyzed with each extraction batch.
10.3.3 BLANK SUBTRACTION IS NOT ALLOWED. Blanks are reported by value.
This information is for data quality assessment purposes only.
10.3.4 Other blanks may be analyzed as necessary following the recommendations of
Chapter 2, Section 9 of the UST Procedures Manual.

10.4 Lab Fortified Blanks (LFB)

10.4.1 LFB is extracted using the method procedure.
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10.4.2 One LFB is analyzed with each analytical batch

10.4.3 The LFB recovery requirement is 60-120% of true value.
10.4.4 If any LFB recovery fails to meet method criteria, appropriate corrective action
must be taken. See Section 10.7 of this method, “Corrective Actions”.

10.5 Matrix Spike (MS) and Matrix Spike Duplicates (MSD)

10.5.1 MS & MSD are samples that are spiked with RCS to produce a known
concentration greater than the sample background concentration. Both are processed as
samples.
10.5.2 MS & MSD are analyzed only when requested.
10.5.3 There are no RPD or recovery requirements for MS and MSD.
10.5.4 The recovery and relative percent difference (RPD) for the MS and MSD are for
informational purposes only.

10.6 Surrogate
10.6.1 Surrogate recoveries must be 60-120% for laboratory control samples (CCS, CVS,
method blank, LFB) and 50-150 % for field samples(all other samples).
10.6.2 If any surrogate recovery fails to meet method criteria, corrective action must be
taken. See Section 10.7 of this method, “Corrective Actions”.
10.6.3 If field samples show poor surrogate recovery which is not attributable to
laboratory error, RRO results must be flagged. Re-sampling, matrix spikes, or other
remedial action is at the discretion of the client and is not the responsibility of the
laboratory.

10.7 Corrective Action

10.7.1 The actions listed below are recommended and may not apply to a particular
failure.
10.7.2 Check for matrix interference or carry-over.
10.7.3 Check for errors in calculation and that concentrations of surrogates and internal
standards are correct.
10.7.4 Check that instrument performance meets method criteria.
10.7.5 Re-process the data.
10.7.6 Re-analyze the extracts.
10.7.7 Extract additional aliquots of the failing sample(s) and re-analyze.
10.7.8 Collect replacement samples.

11. Method Performance

11.1 Specific method performance data for Revision 3.0 of AK 103, Residual Range
Organics, is not available at this time. Information on method performance for the
C25 - C44 range (Revision 2.1) follows.

11.1.1 The method performance data presented, other than the performance
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evaluation samples, is based on single lab work (State of Alaska,

Department of Environmental Conservation, State Chemistry Laboratory).
Performance data for the RROs method in Ottawa sand and other soil
types is presented below.

11.1.2 Results for motor oil spikes (methylene chloride extraction direct
injection, soils) are from duplicate analyses of matrix spikes on field
projects. Biases due to naturally occurring materials and existence of
mixed products in the samples may exist.

RCS Spike Amount Percent

Matrix mg/kg Recovery
Performance Samples 2001 1231 104 ± 14

1993 Composite 250 77 ± 13

(S.E. Alaska Soils) 500 107 ±15

1994 Composite 250 103 ± 10

(S.E. Alaska Soils) 500 103 ± 9

1995 Single Project 500 116 ± 9

(S. E. Alaska Soils)

11.1.3 The method detection limit for soil calculated according to 40 C.F.R. 136,
Appendix B (1994) was 51 mg/kg (external standard calibration).
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12.References

1. USEPA, Test Methods for Evaluating Solid Waste, 3d Edition; Methods 8000, 8100, 3510, 3520, 3540,
3611 and 3550.

2. "Method OA-2: Extractable Petroleum in Products", Revision January 10, 1990, University Hygienic
Laboratory, Iowa City, Iowa.

3. "Method for Determination of Extractable Petroleum Hydrocarbons (EPH) in Soil and Water,
Draft-February 28, 1990, prepared for Total Petroleum Hydrocarbons Method Committee by Midwest
Research Institute.

4. Zilis, K., M. McDevitt, and J. Parr, "A Reliable Technique for Measuring Petroleum Hydrocarbons in
the Environment", presented at the conference on Petroleum Hydrocarbons and Organic Chemicals in
Groundwater, NWWA, Houston, Texas, November 1988.

5. American Petroleum Institute "Method for the Determination of Diesel Range Organics", Draft
Revision 2-February 5, 1992, prepared for Total Petroleum Hydrocarbons Method Committee.

6. "Leaking Underground Fuel Tank (LUFT) Field Manual", State Water Resources Control Board, State
of California, Sacramento, CA, May 1988.

7. Fitzgerald, John, "Onsite Analytical Screening of Gasoline Contaminated Media Using a Jar Headspace
Procedure" in Petroleum Contaminated Soils, Vol. 2, 1989.

8. Senn, R.B., and M.S. Johnson, "Interpretation of Gas Chromatographic Data in Subsurface
Hydrocarbon Investigations" Ground Water Monitoring Review , 1987.

9. Hughes, B.M., and D.E. McKenzie, C.K. Trang, L.S.R. Minor, "Examples of the Use of an Advanced
Mass Spectrometric Data Processing Environment for the Determination of Sources of Wastes"
presented at 5th Annual Waste Testing and Quality Assurance Symposium, July 1989.

10. American Petroleum Institute, "Method for Determination of Petroleum Hydrocarbons", Draft
Revision, Original, 3 February 1992, prepared for the Total Petroleum Hydrocarbons Methods
Committee.

11. State of Washington, Department of Ecology, “Total Petroleum Hydrocarbons Analytical Method
WTPH-HCID.”

12. Research done by the State of Alaska, Department of Environmental Conservation, Division of
Environmental Quality, State Chemistry Laboratory.

13. Carrell, Robert, “Method for the Determination of Extractable Petroleum Hydrocarbons”, Laboratory
Advisory Board Project Oversight Group, Duwamish Brownfields/TPI-I Project, September 1, 1997.

14. USEPA “Guidelines for Establishing Test Procedures for the Analysis of Pollutants Under the Clean
Water Act” (40 C.F.R. 136, Part VIII, July 1994).
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Figure 1. Residual Range Organics at 25 mg/mL, or 25,000,000 ug/L

Chromatogram is based on 25mg/mL of RRO standard made from 1:1 mixture of Valvoline 30 wt and Valvoline 40
wt motor oil.100 ug/mL of n-Triacontane-d62 surrogate. GC conditions: HP 5890 series II GC/FID, HP-5 column
30m x 0.32mm x 0.25um, H2 carrier gas, Merlin high pressure microseal septum, Injector temperature - 320°C,
Detector temperature - 330°C Oven temperature program - 45°C for 3 minutes, 8°C/minute to 320°C hold for 2.63
minutes for total run time of 40 minutes.
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Method AK 103, Table 1

ACCEPTANCE CRITERIA FOR QUALITY CONTROL

ANALYTE SPIKE CONCENTRATION CONTROL LIMITS

Relative
Soil (mg/kg) % Recovery % Difference
Lab Fortified Blank
Residual Range Organics 500 mg/kg 60-120 20

CVS/CCS
Residual Range Organics 2000 mg/L 75-125

Surrogate Control Samples

n-Triacontane-d62 50 mg/kg 60-120

Surrogate Recovery (field samples)

n-Triacontane-d62 50 mg/kg 50-150
 APPENDIX E

Alaska Series Laboratory Methods for the Analysis of Aliphatic and Aromatic Gasoline
Range Organics (AK101AA), Aliphatic and Aromatic Diesel Range Organics (AK102AA),
and Aliphatic and Aromatic Residual Range Organics (AK103AA)

Forward for AK Methods 101AA, 102AA, 103AA

The Alaska Department of Environmental Conservation (ADEC) has published these laboratory
methods to provide ADEC-approved laboratory test methods and related information for
laboratory analysts, data users, and other interested parties.
In order to obtain approval for the AK Series “AA” Methods, AK101AA,AK102AA, AK
103AA, laboratories must pass a performance evaluation audit for each method as outlined in the
Underground Storage Tank Regulations, 18 AAC 78.800-815. Guidelines for the performance
evaluation sampling for these methods are outlined below.
1) One sample for each hydrocarbon range (GRO, DRO, RRO) and above the reporting limit for
both aromatic and aliphatic compounds and below 500X the reporting limit shall be analyzed
for each reporting matrix within the ADEC defined time period. The aromatics should be
fortified in the mixtures such that they are no less than 40% of the total hydrocarbon to
ensure the ability to detect them in low concentration samples.
2) All volatiles samples can be mixed using methanol.
3) Soil semivolatile standards should be relatively simple. The sample concentrates can be
made up in hexane or methylene chloride. ADEC suggests hexane for the semivolatile
samples as it will be easier to quantitatively transfer without losses due to evaporation.
4) Semivolatile water standards require a concentrate that can be mixed with water and will not
adversely affect the SiO2 or Al2O3 partitioning. ADEC experience has shown small amounts
of methanol or acetone cause significant breakthrough on the columns. To attempt to
alleviate the concern of using a non-miscible solvent, we suggest the following possibilities.
Of these options the first two are the most desirable.
a) Create concentrates in water. Make up 50 or 100mL water concentrates and require the
labs to quantitatively measure 40 or 80mL of water standard into a liter of “clean” water.
This has been relatively easy for the lower concentrations, but the higher pose a slight
problem.
b) Send full 1L samples to each lab. It is the same as the labs are used to seeing from their
clients. Preservatives may be necessary.
c) Create concentrates in hexane. Hexane rather than methylene chloride will be better since
it does not drop to the bottom of a continuous extractor. It would have to be extracted
both from the top of the water and in the water allowing some equilibrium to be
established. Either way, if a shakeout is used, an equilibrium is established during the
process of shaking the sample.
5) Results required for these Performance Evaluation samples include:
a) standard deviation;
b) two and three sigma limits;
c) true values; and
d) percent recoveries.