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METHOD 8015C

NONHALOGENATED ORGANICS BY GAS CHROMATOGRAPHY

SW-846 is not intended to be an analytical training manual. Therefore, method

procedures are written based on the assumption that they will be performed by analysts who are

formally trained in at least the basic principles of chemical analysis and in the use of the subject

technology.

In addition, SW-846 methods, with the exception of required method use for the analysis

of method-defined parameters, are intended to be guidance methods which contain general

information on how to perform an analytical procedure or technique which a laboratory can use

as a basic starting point for generating its own detailed Standard Operating Procedure (SOP),

either for its own general use or for a specific project application. The performance data

included in this method are for guidance purposes only, and are not intended to be and must

not be used as absolute QC acceptance criteria for purposes of laboratory accreditation.

1.0 SCOPE AND APPLICATION

1.1 This method may be used to determine the concentrations of various

nonhalogenated volatile organic compounds and semivolatile organic compounds by gas

chromatography. The following RCRA compounds were quantitatively determined by this

method, using the preparative techniques indicated.

Appropriate Technique

Compound CAS No.a PurgeandTrapb

HeadspaceeDirect

Aqueous

Injection

Azeo.

Dist.c

Vacuum

Dist.d

Acetone 67-64-1 pp / ht x x x x

Acetonitrile 75-05-8 pp ne x x ne

Acrolein 107-02-8 pp ne x xx

Acrylonitrile 107-13-1 pp ne x xx

Allyl alcohol 107-18-6 ht ne x x ne

t-Amyl alcohol (TAA) 75-85-4 ht x ne ne x

t-Amyl ethyl ether (TAEE) 919-94-8 x/ ht x ne ne x

t-Amyl methyl ether (TAME) 994-05-8 x/ ht x ne ne x

Benzene 71-43-2 x x ne ne x

t-Butyl alcohol (TBA) 75-65-0 ht x x xx

Crotonaldehyde 123-73-9 pp ne x x ne

Diethyl ether 60-29-7 x ne x ne ne

Diisopropyl ether (DIPE) 108-20-3 x/ ht x ne ne x

Ethanol 64-17-5 I x x x x

Ethyl acetate 141-78-6 I x x x ne

Ethyl benzene 100-41-4 x x ne ne x

Ethylene oxide 75-21-8 I ne x x ne

Ethyl tert-butyl ether (ETBE) 637-92-3 x/ ht x ne ne x

Isopropyl alcohol (2-Propanol) 67-63-0 pp x x x ne
Appropriate Technique

Compound CAS No.a PurgeandTrapb

HeadspaceeDirect

Aqueous

Injection

Azeo.

Dist.c

Vacuum

Dist.d

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Methanol 67-56-1 I x x x ne

Methyl ethyl ketone (MEK, 

 2-Butanone)

78-93-3 pp x x x x

Methyl tert-butyl ether (MTBE) 1634-04-4 x/ ht x x ne x

N-Nitroso-di-n-butylamine 924-16-3 pp ne x x ne

Paraldehyde 123-63-7 pp ne x x ne

2-Pentanone 107-87-9 pp x x x ne

2-Picoline 109-06-8 pp ne x x ne

1-Propanol (n-Propyl alcohol) 71-23-8 pp x x x ne

Propionitrile (Ethyl cyanide) 107-12-0 ht ne x x ne

Pyridine 110-86-1 I ne x x ne

Toluene 108-88-3 x x ne ne x

o-Toluidine 95-53-4 I ne x x ne

o-Xylene 95-47-6 x x ne ne x

m-Xylene 108-38-3 x x ne ne x

p-Xylene 106-42-3 x x ne ne x

a Chemical Abstract Service Registry Number

b Purge-and-Trap (Methods 5030 or 5035)

c Azeotropic distillation (Method 5031)

d Vacuum distillation (Method 5032)

e Headspace (Method 5021)

x Adequate response using this technique

ht Method analyte only when purged at 80 EC (high temperature purge)

I Inappropriate technique for this analyte

ne Not evaluated

pp Poor purging efficiency, resulting in higher limits of quantitation. Use of an alternative sample

preparative method is strongly recommended. May be amenable to purging at elevated

temperature.

1.2 This method may be applicable to the analysis of other analytes, including

triethylamine and petroleum hydrocarbons. The petroleum hydrocarbons include gasoline

range organics (GRO) and diesel range organics (DRO). The sample preparation techniques

are shown in the table below.

Appropriate Technique

Compound CAS No.a Purgeand-Trap

Headspace

Direct

Aqueous

Injection

Solvent

Extraction

Triethylamine 121-44-8 I ne x I

Gasoline range organics (GRO) -- x x x I

Diesel range organics (DRO) -- I x I x

a Chemical Abstract Service Registry Number

x: Adequate response using this technique; I: Inappropriate technique for this analyte; 

ne: Not evaluated
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1.2.1 This method was applied to the analysis of triethylamine in water samples

by direct aqueous injection onto a different GC column than is used for any other analytes. 

Descriptions of the GC column, temperature program, and performance data for

triethylamine are provided in this method (see Secs. 6.2.5 and 11.2.6, and Table 6).

1.2.2 GRO corresponds to the range of alkanes from C6 to C10 and a boiling

point range of approximately 60 EC - 170 EC (Reference 6). DRO corresponds to the

range of alkanes from C10 to C28 and a boiling point range of approximately 170 EC - 430

EC (Reference 6). The quantitative analyses of these fuel types are based on the

procedures described in Sec. 11.11. The identification of specific fuel types may be

complicated by environmental processes such as evaporation, biodegradation, or when

more than one fuel type is present. Methods from other sources may be more appropriate

for GRO and DRO, since these hydrocarbons are not regulated under RCRA. Consult

State and local regulatory authorities for any specific regulatory requirements.

1.2.3 This method may be applicable to classes of analytes and to fuel types

and petroleum hydrocarbons other than those listed in Secs. 1.1 and 1.2. However, in

order to be used for additional analytes, fuel types, or petroleum hydrocarbons, the analyst

must demonstrate that the gas chromatographic conditions, including the GC column, are

appropriate for the analytes of interest. The analyst must also perform the initial

demonstration of proficiency described in Sec. 9.4 and Method 8000. Expansion of this

method to other fuel types or petroleum hydrocarbons will also necessitate careful defining

of the boiling point range or carbon number range of the material and modification of the

quantitation approach to match such ranges. Analysts are advised to consult authoritative

sources, such as the American Petroleum Institute (API), for relevant definitions of other

fuel types or petroleum fractions.

NOTE: Mention of the analyses of other fuel types and petroleum fractions does not

imply a regulatory requirement for such analyses, using this or any other

method.

1.3 This method can also be used as a screening tool (for both volatile and

semivolatile organics) to obtain semiquantitative data to prevent overloading the GC/MS system

during quantitative analysis. This may be accomplished using a purge-and-trap method (e.g.,

Method 5030), an automated headspace method (e.g., Method 5021), direct aqueous injection,

or by direct injection, if a solvent extraction method has been utilized for sample preparation. 

Single-point calibration is acceptable in this situation. Performance data are not provided for

screening.

1.4 Prior to employing this method, analysts are advised to consult the base method

for each type of procedure that may be employed in the overall analysis (e.g., Methods 3500,

3600, 5000, and 8000) for additional information on quality control procedures, development of

QC acceptance criteria, calculations, and general guidance. Analysts also should consult the

disclaimer statement at the front of the manual and the information in Chapter Two for guidance

on the intended flexibility in the choice of methods, apparatus, materials, reagents, and

supplies, and on the responsibilities of the analyst for demonstrating that the techniques

employed are appropriate for the analytes of interest, in the matrix of interest, and at the levels

of concern. 

In addition, analysts and data users are advised that, except where explicitly specified in a

regulation, the use of SW-846 methods is not mandatory in response to Federal testing
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requirements. The information contained in this method is provided by EPA as guidance to be

used by the analyst and the regulated community in making judgments necessary to generate

results that meet the data quality objectives for the intended application.

1.5 This method is restricted for use by, or under the supervision of, analysts

appropriately experienced and trained in the use of a gas chromatograph and skilled in the

interpretation of gas chromatograms. In addition, if this method is to be used for the analysis of

petroleum hydrocarbons, its use then should be limited to analysts experienced in the

interpretation of hydrocarbon data. Each analyst must demonstrate the ability to generate

acceptable results with this method.

2.0 SUMMARY OF METHOD

2.1 This method provides gas chromatographic conditions for the detection of certain

nonhalogenated volatile and semivolatile organic compounds.

2.2 Depending on the analytes of interest, samples may be introduced into the GC by

a variety of techniques, including:

• Purge-and-trap (Methods 5030 or 5035)

• Equilibrium headspace (Method 5021)

• Direct injection of aqueous samples

• Injection of the concentrate from azeotropic distillation (Method 5031)

• Vacuum distillation (Method 5032)

• Following solvent extraction (Methods 3510, 3520, 3535, 3540, 3541, 3545,

3546, 3550, 3560, or other appropriate technique)

2.3 Groundwater or surface water samples generally need to be analyzed in

conjunction with Methods 5021, 5030, 5031, 5032, 3510, 3520, or other appropriate preparatory

methods to obtain the necessary lower limits of quantitation. Method 3535 (solid-phase

extraction) may also be applicable to some of the target analytes, however, this method has not

been validated by EPA in conjunction with this determinative method.

2.4 Samples to be analyzed for diesel range organics may be prepared by an

appropriate solvent extraction method.

2.5 Gasoline range organics may be introduced into the GC/FID by purge-and-trap

(Methods 5030 and 5035), automated headspace (Method 5021), vacuum distillation (Method

5032), or other appropriate technique.

2.6 Triethylamine may be analyzed by direct injection of aqueous samples. This

compound has not been found to be amenable to purge-and-trap techniques.
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2.7 An appropriate column and temperature program are used in the gas

chromatograph to separate the organic compounds. Detection is achieved by a flame ionization

detector (FID).

2.8 This method allows the use of capillary or packed columns for the analysis and

confirmation of the non-halogenated individual analytes. The GC columns and conditions listed

have been demonstrated to provide separation of those target analytes. Other columns and

conditions may be employed, provided that the analyst demonstrates adequate performance for

the intended application.

2.9 The quantitative analyses of GRO and DRO are based on the definitions provided

in Sec. 1.2.2 and the procedures described in Sec. 11.11. 

2.10 Given the large number of components to be separated, fused-silica capillary

columns are necessary for the analysis of petroleum hydrocarbons, including GRO and DRO,

and are recommended for all other analytes. A capillary column is also necessary for the

analysis of triethylamine.

3.0 DEFINITIONS

Refer to Chapter One and the manufacturer's instructions for definitions that may be

relevant to this procedure.

4.0 INTERFERENCES

4.1 Solvents, reagents, glassware, and other sample processing hardware may yield

artifacts and/or interferences to sample analysis. All of these materials must be demonstrated

to be free from interferences under the conditions of the analysis by analyzing method blanks. 

Specific selection of reagents and purification of solvents by distillation in all-glass systems may

be necessary. Refer to each method to be used for specific guidance on quality control

procedures and to Chapter Four for general guidance on the cleaning of glassware.

4.2 When analyzing for volatile organics, samples can be contaminated by diffusion of

volatile organics (particularly chlorofluorocarbons and methylene chloride) through the sample

container septum during shipment and storage. A trip blank prepared from organic-free reagent

water and carried through sampling and subsequent storage and handling will serve as a check

on such contamination.

4.3 Contamination by carryover can occur whenever high-concentration and

low-concentration samples are analyzed in sequence. To reduce the potential for carryover, the

sample syringe or purging device needs to be rinsed out between samples with an appropriate

solvent. Whenever an unusually concentrated sample is encountered, it should be followed by

injection of a solvent blank to check for cross contamination.

4.3.1 Clean purging vessels with a detergent solution, rinse with distilled water,

and then dry in a 105 EC oven between analyses. Clean syringes or autosamplers by

flushing all surfaces that contact samples using appropriate solvents.
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4.3.2 All glassware must be scrupulously cleaned. Clean all glassware as soon

as possible after use by rinsing with the last solvent used. This should be followed by

detergent washing with hot water, and rinses with tap water and organic-free reagent

water. Drain the glassware and dry it in an oven at 130 EC for several hours or rinse it

with methanol and drain. Store dry glassware in a clean environment.

4.4 The flame ionization detector (FID) is a non-selective detector. There is a potential

for many non-target compounds present in samples to interfere with this analysis. There is also

the potential for analytes to be resolved poorly, especially in samples that contain many

analytes. The data user should consider this and may wish to alter the target analyte list

accordingly. 

5.0 SAFETY

This method does not address all safety issues associated with its use. The laboratory is

responsible for maintaining a safe work environment and a current awareness file of OSHA

regulations regarding the safe handling of the chemicals listed in this method. A reference file

of material safety data sheets (MSDSs) should be available to all personnel involved in these

analyses. 

6.0 EQUIPMENT AND SUPPLIES

The mention of trade names or commercial products in this manual is for illustrative

purposes only, and does not constitute an EPA endorsement or exclusive recommendation for

use. The products and instrument settings cited in SW-846 methods represent those products

and settings used during method development or subsequently evaluated by the Agency. 

Glassware, reagents, supplies, equipment, and settings other than those listed in this manual

may be employed provided that method performance appropriate for the intended application

has been demonstrated and documented. 

This section does not list common laboratory glassware (e.g., beakers and flasks).

6.1 Gas chromatograph -- Analytical system equipped with gas chromatograph

suitable for solvent injections, direct aqueous injection, headspace, vacuum distillation sample

introduction, or purge-and-trap sample introduction, and equipped with all necessary

accessories, including detectors, column supplies, recorder, gases, and syringes. A data

system for measuring peak heights and/or peak areas is recommended.

6.2 Recommended GC columns

The choice of GC column will depend on the analytes of interest, the expected

concentrations, and the intended use of the results. The packed columns listed below are

generally used for screening analyses. The capillary columns are necessary for petroleum

hydrocarbon analyses and for triethylamine analyses and are recommended for all other

analyses. 

The columns listed in this section were the columns used to develop the method. The

listing of these columns in this method is not intended to exclude the use of other columns that

are available or that may be developed. The laboratory may use either the columns listed in this
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method or other columns and columns of other dimensions, provided that the laboratory

documents method performance data (e.g., chromatographic resolution, analyte breakdown,

and sensitivity) that are appropriate for the intended application.

6.2.1 Column 1 -- 8-ft x 0.1-in. ID stainless steel or glass column, packed with

1% SP-1000 on Carbopak-B 60/80 mesh or equivalent.

6.2.2 Column 2 -- 6-ft x 0.1-in. ID stainless steel or glass column, packed with

n-octane on Porasil-C 100/120 mesh (Durapak) or equivalent.

6.2.3 Column 3 -- 30-m x 0.53-mm ID fused-silica capillary column bonded with

DB-Wax (or equivalent), 1-μm film thickness.

6.2.4 Column 4 -- 30-m x 0.53-mm ID fused-silica capillary column chemically

bonded with 5% methyl silicone (DB-5, SPB-5, RTx, or equivalent), 1.5-μm film thickness.

6.2.5 Column 5 -- 30-m x 0.53-mm ID fused-silica capillary column bonded with

HP Basic Wax (or equivalent), 1-μm film thickness. This column is used for triethylamine.

6.2.6 Wide-bore columns should be installed in 1/4-inch injectors, equipped

with deactivated liners designed specifically for use with these columns.

6.3 Detector -- Flame ionization (FID)

6.4 Sample introduction and preparation apparatus 

6.4.1 Refer to the 5000 series sample preparation methods for the appropriate

apparatus for purge-and-trap, headspace, azeotropic distillation, and vacuum distillation 

analyses.

6.4.2 Samples may also be introduced into the GC via injection of solvent

extracts or direct injection of aqueous samples.

6.5 Syringes

6.5.1 5-mL Luer-Lok glass hypodermic and 5-mL gas-tight syringe equipped

with a shutoff valve, for volatile analytes.

6.5.2 Microsyringes -- 10- and 25-μL equipped with a 0.006-in. ID needle

(Hamilton 702N or equivalent) and 100-μL.

6.6 Volumetric flasks, Class A -- Appropriate sizes equipped with ground-glass

stoppers.

6.7 Analytical balance -- 160-g capacity, capable of measuring to 0.0001 g.
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7.0 REAGENTS AND STANDARDS

7.1 Reagent-grade chemicals must be used in all tests. Unless otherwise indicated, it

is intended that all reagents conform to the specifications of the Committee on Analytical

Reagents of the American Chemical Society, where such specifications are available. Other

grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity

to permit its use without lessening the accuracy of the determination. Reagents should be

stored in glass to prevent the leaching of contaminants from plastic containers.

7.2 Organic-free reagent water -- All references to water in this method refer to

organic-free reagent water, as defined in Chapter One.

7.3 Methanol, CH3OH, pesticide quality or equivalent -- Store away from other

solvents.

7.4 Fuels, e.g., gasoline or diesel -- Purchase from a commercial source. Low-boiling

components in fuel evaporate quickly. As applicable and available, obtain the fuel from the

leaking tank on site.

7.5 Alkane standard -- A standard containing a homologous series of n-alkanes for

establishing retention times (e.g., C10-C28 for diesel). 

7.6 Standard solutions

The following sections describe the preparation of stock, intermediate, and working

standards for the compounds of interest. This discussion is provided as an example, and other

approaches and concentrations of the target compounds may be used, as appropriate for the

intended application. See Method 8000 for additional information on the preparation of

calibration standards.

7.7 Stock standards -- Stock solutions may be prepared from pure standard materials

or purchased as certified solutions. When methanol is a target analyte or when using

azeotropic distillation for sample preparation, standards should not be prepared in methanol. 

Standards must be replaced after 6 months or sooner, if comparison with check standards

indicates a problem.

7.8 Secondary dilution standards -- Using stock standard solutions, prepare secondary

dilution standards, as needed, that contain the compounds of interest, either singly or mixed

together. The secondary dilution standards should be prepared at concentrations such that the

aqueous calibration standards prepared in Sec. 7.9 will bracket the working range of the

analytical system. Secondary dilution standards should be stored with minimal headspace for

volatiles and should be checked frequently for signs of degradation or evaporation, especially

just prior to preparing calibration standards from them.

7.9 Calibration standards -- Prepare calibration standards at a minimum of five

different concentrations in organic-free reagent water (for purge-and-trap, direct aqueous

injection, azeotropic distillation, or vacuum distillation) or in methylene chloride (for solvent

injection) from the secondary dilution of the stock standards. For headspace, prepare the

standards as directed in Method 5021. One of the standards should be at or below the

concentration equivalent to the appropriate lower limit of quantitation for the project. The
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remaining concentrations should correspond to the expected range of concentrations found in

real samples or should define the working range of the GC. Each standard should contain each

analyte to be determined by this method (e.g., some or all of the compounds listed in Sec. 1.1

may be included). In order to prepare accurate aqueous standard solutions, the following

precautions need to be observed:

7.9.1 Do not inject more than 20 μL of methanolic standards into 100 mL of

water.

7.9.2 Use a 25-μL Hamilton 702N microsyringe or equivalent (variations in

needle geometry will adversely affect the ability to deliver reproducible volumes of

methanolic standards into water).

7.9.3 Rapidly inject the primary standard into the filled volumetric flask. 

Remove the needle as fast as possible after injection.

7.9.4 Mix diluted standards by inverting the flask three times only.

7.9.5 Fill the sample syringe from the standard solution contained in the

expanded area of the flask (do not use any solution contained in the neck of the flask).

7.9.6 The negative pressure generated by pipettes makes them inappropriate

for routine use in the transfer of spiked solutions. As such, use of pipettes to dilute or

transfer aqueous standards should be avoided. When sample transfer is absolutely

necessary, (such as in the performance of headspace sample preparation for water

samples) only high quality, automatic pipettes should be used, and then with extreme

care.

7.9.7 Aqueous standards used for purge-and-trap analyses (Method 5030) are

not stable and should be discarded after 1 hr, unless held in sealed vials with zero

headspace. If so stored, they may be held for up to 24 hrs. Aqueous standards used for

azeotropic distillation (Method 5031) may be stored for up to a month in

polytetrafluoroethylene (PTFE)-sealed screw-cap bottles with minimal headspace, at #6

EC, and protected from light.

7.9.8 Standards for direct aqueous injection of triethylamine are prepared by

dissolving an appropriate weight of neat triethylamine in organic-free reagent water and

diluting to volume in a volumetric flask.

7.10 Internal standards (if internal standard calibration is used) -- To use this approach,

the analyst needs to select one or more internal standards that are similar in analytical behavior

to the compounds of interest. The analyst needs to further demonstrate that the measurement

of the internal standard is not affected by method or matrix interferences. Because of these

limitations, no internal standard can be suggested that is applicable to all samples. The

following internal standards are recommended when preparing samples by azeotropic

distillation (Method 5031): 2-chloroacrylonitrile, hexafluoro-2-propanol, and

hexafluoro-2-methyl-2-propanol.

7.11 Surrogate standards -- Whenever possible, the analyst should monitor both the

performance of the analytical system and the effectiveness of the method in dealing with each
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sample matrix, by spiking each sample, standard, and blank with one or two surrogate

compounds which are not affected by method interferences.

8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE

8.1 See the introductory material to Chapter Four, "Organic Analytes," and Method

5035.

8.2 If the headspace technique is used, also see Method 5021.

9.0 QUALITY CONTROL

9.1 Refer to Chapter One for guidance on quality assurance (QA) and quality control

(QC) protocols. When inconsistencies exist between QC guidelines, method-specific QC

criteria take precedence over both technique-specific criteria and those criteria given in Chapter

One, and technique-specific QC criteria take precedence over the criteria in Chapter One. Any

effort involving the collection of analytical data should include development of a structured and

systematic planning document, such as a Quality Assurance Project Plan (QAPP) or a Sampling

and Analysis Plan (SAP), which translates project objectives and specifications into directions

for those that will implement the project and assess the results. Each laboratory should

maintain a formal quality assurance program. The laboratory should also maintain records to

document the quality of the data generated. All data sheets and quality control data should be

maintained for reference or inspection.

9.2 Refer to Method 8000 for specific determinative method QC procedures. Refer to

Methods 3500 and 5000 for QC procedures to ensure the proper operation of the various

sample preparation and/or sample introduction techniques. If an extract cleanup procedure is

performed, refer to Method 3600 for the appropriate QC procedures. Any more specific QC

procedures provided in this method will supersede those noted in Methods 8000, 3500, 5000, or

3600.

9.3 Quality control procedures necessary to evaluate the GC system operation are

found in Method 8000 and include evaluation of retention time windows, calibration verification

and chromatographic analysis of samples.

9.4 Initial demonstration of proficiency

Each laboratory must demonstrate initial proficiency with each sample preparation and

determinative method combination it utilizes, by generating data of acceptable accuracy and

precision for target analytes in a clean matrix. If an autosampler is used to perform sample

dilutions, before using the autosampler to dilute samples, the laboratory should satisfy itself that

those dilutions are of equivalent or better accuracy than is achieved by an experienced analyst

performing manual dilutions. The laboratory must also repeat the demonstration of proficiency

whenever new staff members are trained or significant changes in instrumentation are made. 

See Methods 5000 and 8000 for information on how to accomplish a demonstration of

proficiency.
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9.5 Initially, before processing any samples, the analyst should demonstrate that all

parts of the equipment in contact with the sample and reagents are interference-free. This is

accomplished through the analysis of a method blank. As a continuing check, each time

samples are extracted, cleaned up, and analyzed, and when there is a change in reagents, a

method blank should be prepared and analyzed for the compounds of interest as a safeguard

against chronic laboratory contamination. If a peak is observed within the retention time window

of any analyte that would prevent the determination of that analyte, determine the source and

eliminate it, if possible, before processing the samples. The blanks should be carried through

all stages of sample preparation and analysis. When new reagents or chemicals are received,

the laboratory should monitor the preparation and/or analysis blanks associated with samples

for any signs of contamination. It is not necessary to test every new batch of reagents or

chemicals prior to sample preparation if the source shows no prior problems. However, if

reagents are changed during a preparation batch, separate blanks need to be prepared for each

set of reagents.

9.6 Sample quality control for preparation and analysis

The laboratory must also have procedures for documenting the effect of the matrix on

method performance (precision, accuracy, method sensitivity). At a minimum, this should

include the analysis of QC samples including a method blank, a matrix spike, a duplicate, and a

laboratory control sample (LCS) in each analytical batch and the addition of surrogates to each

field sample and QC sample when surrogates are used. Any method blanks, matrix spike

samples, and replicate samples should be subjected to the same analytical procedures (Sec.

11.0) as those used on actual samples. 

9.6.1 Documenting the effect of the matrix should include the analysis of at

least one matrix spike and one duplicate unspiked sample or one matrix spike/matrix spike

duplicate pair. The decision on whether to prepare and analyze duplicate samples or a

matrix spike/matrix spike duplicate must be based on a knowledge of the samples in the

sample batch. If samples are expected to contain target analytes, then laboratories may

use one matrix spike and a duplicate analysis of an unspiked field sample. If samples are

not expected to contain target analytes, laboratories should use a matrix spike and matrix

spike duplicate pair. Consult Method 8000 for information on developing acceptance

criteria for the MS/MSD.

9.6.2 A laboratory control sample (LCS) should be included with each analytical

batch. The LCS consists of an aliquot of a clean (control) matrix similar to the sample

matrix and of the same weight or volume. The LCS is spiked with the same analytes at

the same concentrations as the matrix spike, when appropriate. When the results of the

matrix spike analysis indicate a potential problem due to the sample matrix itself, the LCS

results are used to verify that the laboratory can perform the analysis in a clean matrix. 

Consult Method 8000 for information on developing acceptance criteria for the LCS.

9.6.3 Also see Method 8000 for details on carrying out sample quality control

procedures for preparation and analysis. In-house method performance criteria for

evaluating method performance should be developed using the guidance found in Method

8000.
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9.7 Surrogate recoveries 

If surrogates are used, the laboratory should evaluate surrogate recovery data from

individual samples versus the surrogate control limits developed by the laboratory. See Method

8000 for information on evaluating surrogate data and developing and updating surrogate limits. 

Procedures for evaluating the recoveries of multiple surrogates and the associated corrective

actions should be defined in an approved project plan.

9.8. It is recommended that the laboratory adopt additional quality assurance practices

for use with this method. The specific practices that are most productive depend upon the

needs of the laboratory and the nature of the samples. Whenever possible, the laboratory

should analyze standard reference materials and participate in relevant performance evaluation

studies.

10.0 CALIBRATION AND STANDARDIZATION

See Secs. 11.3 through 11.5 for information on calibration and standardization.

11.0 PROCEDURE

11.1 Introduction/preparation methods

Various techniques are available for sample introduction. All internal standards,

surrogates, and matrix spikes (when applicable) need to be added to samples before

introduction into the GC/FID system. Consult the applicable sample introduction method

regarding when to add standards.

Other sample introduction techniques may be appropriate for specific applications and the

techniques described here also may be appropriate for other matrices and analytes. Whatever

technique is employed, including those specifically listed below, the analyst must demonstrate

adequate performance for the analytes of interest. At a minimum, such a demonstration will

encompass the initial demonstration of proficiency described in Sec. 9.6, using a clean

reference matrix. Method 8000 describes procedures that may be used to develop performance

criteria for such demonstrations as well as for matrix spike and laboratory control sample

results.

11.1.1 Direct aqueous injection - This technique involves direct syringe injection

of an aliquot of an aqueous sample into the GC injection port. This technique is applicable

to the following groups of analytes in this method.

11.1.1.1 Volatile organics (includes GRO)

This technique may involve injection of an aqueous sample containing a

very high concentration of analytes. Direct injection of aqueous samples has very

limited application in the analysis of volatile organics. It is only appropriate for the

determination of volatiles at the toxicity characteristic (TC) regulatory limits or at

concentrations in excess of 10,000 μg/L. It may also be used in conjunction with
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the test for ignitability in aqueous samples (along with Methods 1010 and 1020) to

determine if alcohol is present at > 24%.

11.1.1.2 Triethylamine in aqueous samples

Triethylamine may be determined by injecting a portion of an aqueous

sample directly into the GC injection port. This technique has been demonstrated

to be appropriate for samples containing low μg/L (ppb) concentrations of

triethylamine. 

11.1.2 Purge-and-trap of volatile organics (includes GRO)

This includes purge-and-trap for aqueous samples (Method 5030) and purge-andtrap for solid samples (Method 5035). Method 5035 also provides techniques for

extraction of solid and oily waste samples by methanol (and other water-miscible solvents)

with subsequent purge-and-trap from an aqueous matrix using Method 5030. Normally,

purge-and-trap for aqueous samples is performed at ambient temperatures, while

soil/solid samples utilize a 40 EC purge to improve extraction efficiency. Heated purge

may also be used to improve the purging of compounds with high solubilities in water,

particularly alcohols associated with fuel oxygenates such as TBA and TAA. 

Occasionally, there may be a need to perform a heated purge for aqueous samples to

lower detection limits; however, using a 25-mL sample will often provide the sensitivity

needed in most situations.

11.1.3 Azeotropic distillation

This technique exploits the ability of selected water-soluble organic compounds to

form binary azeotropes with water during distillation. The organic compounds are

removed from the bulk water sample and concentrated in a distillate, as described in

Method 5031. An aliquot of the distillate is then injected into the GC/FID.

11.1.4 Vacuum distillation of volatile organics

This technique employs a vacuum distillation apparatus to introduce volatile

organics from aqueous, solid, or tissue samples into the GC/FID system, as described in

Method 5032.

11.1.5 Automated static headspace

This technique employs a device that collects the volatile organics from the

headspace over a sample contained in a sealed vial and introduces them into the GC/FID

system, as described in Method 5021. 

11.1.6 Solvent injection

This technique involves the syringe injection of solvent extracts of aqueous

samples prepared by Methods 3510, 3520, 3535, or other appropriate technique, or

extracts of soil/solids prepared by Methods 3540, 3541, 3545, 3546, 3550, 3560, or other

appropriate technique. It is applicable to many semivolatile organics, including DRO.
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CAUTION: Ultrasonic extraction (Method 3550) may not be as rigorous a method as the

other extraction methods for soil/solids. This means that it is critical that the

method be followed explicitly to achieve an extraction efficiency which

approaches that of Soxhlet extraction. Consult Method 3550 for information

on the critical aspects of this extraction procedure.

11.2 Suggested chromatographic conditions

Establish the GC operating conditions appropriate for the GC column being utilized and

the target analytes specified in the project plan. Optimize the instrumental conditions for

resolution of the target analytes and sensitivity. Suggested operating conditions are given

below for the columns recommended in Sec. 6.2. The laboratory may use either the columns

listed in this method or other columns and columns of other dimensions, provided that the

laboratory documents method performance data (e.g., chromatographic resolution, analyte

breakdown, and sensitivity) that are appropriate for the intended application.

11.2.1 Column 1

Carrier gas (helium) flow rate: 40 mL/min

Temperature program:

 Initial temperature: 45 EC, hold for 3 min

 Program: 45 EC to 220 EC, at 8 EC/min

 Final temperature: 220 EC, hold for 15 min.

11.2.2 Column 2

Carrier gas (helium) flow rate: 40 mL/min

Temperature program:

 Initial temperature: 50 EC, hold for 3 min

 Program: 50 EC to 170 EC, at 6 EC/min

 Final temperature: 170 EC, hold for 4 min.

11.2.3 Column 3

Carrier gas (helium) flow rate: 15 mL/min

Temperature program:

 Initial temperature: 45 EC, hold for 4 min

 Program: 45 EC to 220 EC, at 12 EC/min

 Final temperature: 220 EC, hold for 3 min.

11.2.4 Column 4 (DRO)

Carrier gas (helium) flow rate: 5-7 mL/min

Makeup gas (helium) flow rate: 30 mL/min 

Injector temperature: 200 EC

Detector temperature: 340 EC

Temperature program:

 Initial temperature: 45 EC, hold for 3 min
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February 2007

 Program: 45 EC to 275 EC, at 12 EC/min

 Final temperature: 275 EC, hold for 12 min.

11.2.5 Column 4 (GRO)

Carrier gas (helium) flow rate: 5-7 mL/min

Makeup gas (helium) flow rate: 30 mL/min 

Injector temperature: 200 EC

Detector temperature: 340 EC

Temperature program:

 Initial temperature: 45 EC, hold for 1 min

 1st Ramp: 45 EC to 100 EC at 5 EC/min

 2nd Ramp: 100 EC to 275 EC, at 8 EC/min

 Final temperature: 275 EC, hold for 5 min.

11.2.6 Column 5 (triethylamine only)

Carrier gas (helium) flow rate: 5 mL/min

Makeup gas (helium) flow rate: 30 mL/min 

Injector temperature: 200 EC

Detector temperature: 250 EC

Temperature program:

 Initial temperature: 110 EC

 Program: 110 EC to 175 EC, at 10 EC/min

 Final temperature: 175 EC, hold for 3 min.

11.3 Initial calibration

11.3.1 Set up the sample introduction system as outlined in the method of choice

(see Sec. 11.1). A separate calibration is necessary for each sample introduction mode

because of the differences in conditions and equipment. Establish chromatographic

operating parameters that provide instrument performance appropriate for the intended

application. Prepare calibration standards using the procedures described above (see

Sec. 7.9). The external standard technique is described below. Analysts wishing to use

the internal standard technique should refer to Sec. 7.10 and Method 8000.

11.3.2 External standard calibration procedure for single-component analytes

11.3.2.1 For each analyte and surrogate of interest, prepare calibration

standards at a minimum of five different concentrations. For headspace analysis,

the standards should be prepared in methanol or organic-free reagent water and

then spiked into the organic-free water in the headspace vial. The spiking

solutions should be at concentrations which will dilute to the desired standard

concentrations when added into the organic-free water in the headspace vials. 

Otherwise, standards should be made by adding volumes of one or more stock

standards to a volumetric flask and diluting to volume with an appropriate solvent. 

One of the standards should be at a concentration at or below the lower limit of

quantitation necessary for the project (based on the concentration in the final

volume described in the preparation method, with no dilutions). The
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Calibration Factor ' Total Area within Retention Time Range

Mass injected (nanograms)

concentrations of the other standards should correspond to the expected range of

concentrations found in real samples or should define the working range of the

detector.

11.3.2.2 Introduce each calibration standard using the technique that

will be used to introduce the actual samples into the gas chromatograph. Tabulate

peak height or area responses against the mass injected. Calculate the calibration

factor (CF) for each single-component analyte as described in Method 8000.

11.3.3 External standard calibration procedure for DRO and GRO

The calibration of DRO and GRO is markedly different from that for

single-component analytes. In particular, the response used for calibration needs

to represent the entire area of the chromatogram within the retention time range for

the fuel type (DRO or GRO), including the unresolved complex mixture that lies

below the individual peaks. See Sec. 11.11 for information on calculating this

area.

11.3.3.1 For each fuel type, prepare calibration standards at a minimum

of five different concentrations by adding volumes of one or more stock standards

to a volumetric flask and diluting to volume with an appropriate solvent (for

headspace analysis, follow the instructions in Sec. 11.3.2.1, above). One of the

standards should be at a concentration at or below the lower limit of quantitation

necessary for the project (based on the concentration in the final volume described

in the preparation method, with no dilutions). The concentrations of the other

standards should correspond to the expected range of concentrations found in real

samples or should define the working range of the detector.

NOTE: Whenever possible, the calibration should be performed using the specific

fuel that is contaminating the site (e.g., a sample of the fuel remaining in

the tank suspected of leaking). Where such samples are not available or

not known, use recently purchased commercially-available fuel. A

qualitative screening injection and GC run may be performed to identify

unknown fuels.

11.3.3.2 Introduce each calibration standard using the technique that

will be used to introduce the actual samples into the gas chromatograph. 

Determine the area of the response as described in Sec. 11.10. Calculate the

calibration factor (CF) for each fuel type as shown below:

11.3.4 Calibration linearity

The linearity of the calibration must be assessed. This applies to both the singlecomponent analytes and the fuel types.
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11.3.4.1 If the percent relative standard deviation (%RSD) of the

calibration factors is less than 20% over the working range, then linearity through

the origin can be assumed, and the average calibration factor can be used in place

of a calibration curve.

11.3.4.2 If the RSD is more than 20% over the working range, linearity

through the origin cannot be assumed. See Method 8000 for other calibration

options that may be employed, which may include a linear calibration not through

the origin or a non-linear calibration model (e.g., a polynomial equation).

11.4 Retention time windows

Single-component target analytes (see Sec. 1.1) are identified on the basis of

retention time windows. GRO and DRO are distinguished on the basis of the ranges of

retention times for characteristic components in each type of fuel.

11.4.1 Before establishing retention time windows, make sure that the

chromatographic system is functioning reliably and that the operating parameters have

been optimized for the target analytes and surrogates in the sample matrix to be analyzed. 

Establish the retention time windows for single component target analytes using the

procedure described in Method 8000.

11.4.2 The retention time range for GRO is defined during initial calibration. Two

specific gasoline components are used to establish the range, 2-methylpentane and 1,2,4-

trimethylbenzene. Use the procedure described in Method 8000 to establish the retention

time windows for these two components. The retention time range is then calculated

based on the lower limit of the RT window for the first eluting component and the upper

limit of the RT window for the last eluting component.

11.4.3 The retention time range for DRO is defined during initial calibration. The

range is established from the retention times of the C10 and C 28 alkanes. Use the

procedure described in Method 8000 to establish the retention time windows for these two

components. The retention time range is then calculated based on the lower limit of the

RT window for the first eluting component and the upper limit of the RT window for the last

eluting component.

11.4.4 If this method is expanded to address other fuel types or petroleum

fractions, then the analyst needs to establish appropriate retention time ranges for the

boiling point range or carbon number range used to define each additional fuel type or

petroleum fraction. Use the procedure described in Method 8000 to establish the retention

time windows.

11.5 Calibration verification

11.5.1 The initial calibration and retention times need to be verified at the

beginning of each 12-hr work shift, at a minimum. When individual target analytes are

being analyzed, verification is accomplished by the analysis of one or more calibration

standards (normally mid-concentration, but a concentration at or near the action level may

be more appropriate) that contain all of the target analytes and surrogates. When

petroleum hydrocarbons are being analyzed, verification is accomplished by the

measurement of the fuel standard and the hydrocarbon retention time standard. 

Additional analyses of the verification standard(s) throughout a 12-hr shift are strongly
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recommended, especially for samples that contain visible concentrations of oily material. 

See Method 8000 for more detailed information on calibration verification.

11.5.2 Calculate the % difference as detailed in Method 8000. If the response

for any analyte is within ±20% of the response obtained during the initial calibration, then

the initial calibration is considered still valid, and the analyst may continue to use the mean

CF or RF values from the initial calibration to quantitate sample results. If the response

for any analyte varies from the predicted response by more than ±20%, corrective action

must be taken to restore the system or a new calibration curve must be prepared for that

compound.

11.5.3 All target analytes, surrogates, and/or n-alkanes in the calibration

verification analyses need to fall within previously established retention time windows. If

the retention time of any analyte does not fall within the established window, then

corrective action must be taken to restore the system or a new calibration curve must be

prepared for that compound.

11.5.4 Solvent blanks and any method blanks should be run with calibration

verification analyses to confirm that laboratory contamination does not cause false positive

results.

11.6 Gas chromatographic analysis

11.6.1 Samples are analyzed in a set referred to as an analytical sequence. The

sequence begins with calibration verification followed by sample extract analyses. 

Additional analyses of the verification standard(s) throughout a 12-hr shift are strongly

recommended, especially for samples that contain visible concentrations of oily material. 

A verification standard is also necessary at the end of a set (unless internal standard

calibration is used). The sequence ends when the set of samples has been injected or

when retention time and/or % difference QC criteria are exceeded.

If the criteria are exceeded, inspect the gas chromatographic system to determine

the cause and perform whatever maintenance is necessary before recalibrating and

proceeding with sample analysis. All sample analyses performed using external standard

calibration need to be bracketed with acceptable data quality analyses (e.g., calibration

and retention time criteria). Therefore, all samples that fall between the standard that

failed to meet the acceptance criteria and the preceding standard that met the acceptance

criteria need to be reanalyzed. Samples analyzed using internal standard calibration need

not be bracketed (see Method 8000).

11.6.2 Samples are analyzed with the same instrument configuration as is used

during calibration. When using Method 5030 for sample introduction, analysts are

cautioned that opening a sample vial or drawing an aliquot from a sealed vial (thus

creating headspace) will compromise samples analyzed for volatiles. Therefore, it is

recommended that analysts prepare two aliquots for purge-and-trap analysis. The second

aliquot can be stored for 24 hrs to ensure that an uncompromised sample is available for

analysis or dilution, if the analysis of the first aliquot is unsuccessful or if results exceed

the calibration range of the instrument. Distillates from Method 5031 may be split into two

aliquots and held at 4 EC prior to analysis. It is recommended that the distillate be

analyzed within 24 hrs of distillation. Distillates should be analyzed within 7 days of

distillation.
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11.6.3 Sample concentrations are calculated by comparing the sample response

with the response from the initial calibration of the system (see Sec. 11.3). Therefore, if

the sample response exceeds the limits of the initial calibration range, a dilution of the

sample or sample extract needs to be analyzed. For volatile organic analyses of aqueous

samples, the dilution needs to be performed on a second aliquot of the sample which has

been properly sealed and stored prior to use and reanalysis. Samples and/or sample

extracts should be diluted so that all peaks are on scale, as overlapping peaks are not

always evident when peaks are off scale. Computer reproduction of chromatograms,

manipulated to ensure that all peaks are on scale over a 100-fold range, is acceptable as

long as calibration limits are not exceeded. Peak height measurements are recommended

over peak area integration when overlapping peaks cause errors in area integration.

11.6.4 Tentative identification of a single-component analyte occurs when a

peak from a sample extract falls within the daily retention time window. Confirmation may

be necessary on a second column or by GC/MS. Since the flame ionization detector is

non-specific, it is highly recommended that GC/MS confirmation be performed on singlecomponent analytes unless historical data are available to support the identification(s). 

See Method 8000 for additional information on confirmation.

11.6.5 Second-column confirmation is generally not necessary for petroleum

hydrocarbon analysis. However, if analytical interferences are indicated, analysis using

the second GC column may be necessary. Also, the analyst needs to ensure that the

sample hydrocarbons fall within the retention time range established during the initial

calibration.

NOTE: The identification of fuels, especially gasoline, is complicated by their inherent

volatility. The early eluting compounds in fuels are obviously the most volatile

and the most likely to have weathered unless the samples were taken

immediately following a spill. The most highly volatile fraction of gasoline

constitutes 50% of the total peak area of a gasoline chromatogram. This fraction

is the least likely to be present in an environmental sample or may be present at

only very low concentration in relation to the remainder of a gasoline

chromatogram.

11.6.6 The performance of the entire analytical system should be checked every 12 

hrs, using data gathered from analyses of blanks, standards, and samples. Significant

peak tailing needs to be corrected. Tailing problems are generally traceable to active sites

on the column, cold spots in a GC, the detector operation, or leaks in the system. See

Sec. 11.8 for GC/FID system maintenance. Follow manufacturer's instructions for

maintenance of the introduction device.

11.7 Screening

11.7.1 This method can be used with a single-point calibration for screening

samples prior to GC/MS analyses (e.g., Methods 8260 and 8270). Such screening can

reduce GC/MS down-time when highly-contaminated samples are analyzed.

11.7.2 When this method is used for screening, it is recommended that the same

sample introduction device (e.g., purge-and-trap versus direct injection) that is used for the

subsequent GC/MS analyses also be used for the screening analysis. This will improve

the correlation between the results and make the screening results more useful in

predicting those samples that may overload the GC/MS system. However, other sample

introduction techniques may be employed as well.
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11.7.3 Establish that the system response and chromatographic retention times are

stable. Analyze the high-point GC/MS calibration standard. 

11.7.4 Analyze samples or sample extracts. Compare peak heights in the sample

chromatograms with the high-point standard to establish that no compound with the same

retention time as a target analyte exceeds the calibration range of the GC/MS system. 

CAUTION: The FID is much less sensitive to halogenated compounds than the MS

detector. As a result, a simple peak height comparison for such compounds

in the GC/MS standard may underestimate the actual concentration of

halogenated compounds. When using this method as a screening tool, such

an underestimate could lead to GC/MS results over the calibration range or

result in contamination of the GC/MS system. Therefore, the analyst should

exercise caution when screening samples that also contain halogenated

compounds.

11.7.5 There are no formal QC requirements applied to screening analyses

using this method. However, it is recommended that the high-point standard be run at

least once every 12 hrs to confirm the stability of the instrument response and

chromatographic retention times. The analyst should consider the costs associated with

making the wrong decision from the screening results (e.g., GC/MS instrument down-time

and maintenance) and use appropriate judgment.

11.8 Instrument maintenance

11.8.1 Injection of sample extracts from waste sites often leaves a high boiling

residue in the injection port area, splitters (when used), and the injection port end of the

chromatographic column. This residue affects chromatography in many ways (i.e., peak

tailing, retention time shifts, analyte degradation, etc.) and, therefore, instrument

maintenance is very important. Residue buildup in a splitter may limit flow through one leg

and therefore change the split ratios. If this occurs during an analytical run, the

quantitative data may be incorrect. Proper cleanup techniques will minimize the problem

and instrument QC will indicate when instrument maintenance is necessary.

11.8.2 Recommended chromatograph maintenance

Corrective measures may need any one or more of the following remedial actions. 

Also see Method 8000 for additional guidance on corrective action for capillary columns

and the injection port.

11.8.2.1 Splitter connections -- For dual columns which are connected

using a press-fit Y-shaped glass splitter or a Y-shaped fused-silica connector,

clean and deactivate the splitter or replace with a cleaned and deactivated splitter. 

Break off the first few inches (up to one foot) of the injection port side of the

column. Remove the columns and solvent backflush according to the

manufacturer's instructions. If these procedures fail to eliminate the degradation

problem, it may be necessary to deactivate the metal injector body and/or replace

the columns.

11.8.2.2 Column rinsing -- Rinse the column with several column

volumes of an appropriate solvent. Both polar and nonpolar solvents are

recommended. Depending on the nature of the sample residues expected, the first

rinse might be water, followed by methanol and acetone; methylene chloride is a
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satisfactory final rinse and in some cases may be the only solvent necessary. The

column should then be filled with methylene chloride and allowed to remain flooded

overnight to allow materials within the stationary phase to migrate into the solvent. 

The column is then flushed with fresh methylene chloride, drained, and dried at

room temperature with a stream of ultrapure nitrogen passing through the column.

11.9 Calculations and data handling

Results need to be reported in units commensurate with their intended use and all

dilutions need to be taken into account when computing final results.

11.10 The concentration of each analyte in the sample may be determined by calculating

the amount of standard purged or injected, from the peak response, using the mean CF or RF

from the initial calibration, or another appropriate calibration model (see Method 8000).

11.11 While both diesel fuel and gasoline contain a large number of compounds that will

produce well-resolved peaks in a GC/FID chromatogram, both fuels contain many other

components that are not chromatographically resolved. This unresolved complex mixture

results in the "hump" in the chromatogram that is characteristic of these fuels. In addition,

although the resolved peaks are important for the identification of the specific fuel type, the area

of the unresolved complex mixture contributes a significant portion of the area of the total

response.

11.11.1 For the analysis of DRO, sum the area of all peaks eluting between C10

and C28. This area is generated by projecting a horizontal baseline between the retention

times of C10 and C28. 

11.11.2 Because the chromatographic conditions employed for DRO analysis can

result in significant column bleed and a resulting rise in the baseline, it is appropriate to

perform a subtraction of the column bleed from the area of the DRO chromatogram. In

order to accomplish this subtraction, analyze a methylene chloride blank during each 12-hr

analytical shift during which samples are analyzed for DRO. Measure the area of this

chromatogram in the same fashion as is used for samples (see Sec. 11.11.1), by

projecting a horizontal baseline across the retention time range for DRO. Then subtract

this area from the area measured for the sample and use the difference in areas to

calculate the DRO concentration, using the equations in Method 8000.

11.11.3 For the analysis of GRO, sum the areas of all peaks eluting between 2-

methylpentane and 1,2,4-trimethylbenzene. This area is used to calculate the GRO

concentration, using the equations in Method 8000. Column bleed subtraction is not

generally necessary for GRO analysis.

11.12 Refer to Method 8000 for the calculation formulae. The formulae cover external

and internal standard calibration, aqueous and non-aqueous samples, and linear and non-linear

calibrations. 

12.0 DATA ANALYSIS AND CALCULATIONS

See Sec. 11.9 for information on data analysis and calculation.
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13.0 METHOD PERFORMANCE

13.1 Performance data and related information are provided in SW-846 methods only as

examples and guidance. The data do not represent required performance criteria for users of

the methods. Instead, performance criteria should be developed on a project-specific basis,

and the laboratory should establish in-house QC performance criteria for the application of this

method. These performance data are not intended to be and must not be used as absolute QC

acceptance criteria for purposes of laboratory accreditation.

13.2 Example method performance data for non-purgeable volatiles prepared using the

azeotropic microdistillation technique from Method 5031 are included in Table 1 and 2 for

aqueous matrices and in Table 3 for solid matrices. Typical chromatograms are included in

Figs. 4 and 5. These data are for guidance purposes only.

13.3 Example method performance information are provided in Tables 4 and 5 for diesel

fuel spiked into soil as are chromatograms of GRO and DRO standards in Figures 1 to 3. 

These data are for guidance purposes only.

13.4 Table 6 contains example precision and bias data for the analysis of triethylamine. 

Reagent water was spiked with triethylamine at 1.0 μg/L and analyzed by direct aqueous

injection in a GC/FID equipped with an HP Basic Wax column (30-m x 0.53-mm ID). These

data are for guidance purposes only.

13.5 Table 7 contains example single-laboratory data on the pressurized fluid extraction

of diesel range organics (DRO) from three types of soil (sand, loam, and clay). The soils were

spiked at two levels of DRO, approximately 5 mg/kg each and approximately 2000 mg/kg. 

Seven replicates of each level and soil type were extracted using pressurized fluid extraction

(Method 3545), using a mixture of methylene chloride and acetone (1:1). The data are taken

from Reference 8 and are for guidance purposes only. This extraction technique may be

applicable to other analyte classes, fuel types, or petroleum fractions (see Sec. 1.2.3).

13.6 This method was the determinative technique used by one of the three laboratories

participating in the study of headspace analysis of oxygenated gasoline contaminated

groundwater samples. Refer to the new version of Method 5021, which can be found at

http://www.epa.gov/epaoswer/hazwaste/test/pdfs/5021a_r1.pdf, for a discussion and the results

of that study. These data are provided for guidance purposes only.

13.7 This method was used in combination with Method 5021 to analyze a standard with

several gasoline components, including MTBE and 2-methylpentane. As can be seen from the

chromatogram in Figure 6, the two analytes were resolved quite well (column: Restek 502.2

105m x 0.53 um, 3 df). See http://www.epa.gov/epaoswer/hazwaste/test/pdfs/5021a_r1.pdf for

more information. These data are provided for guidance purposes only. 

14.0 POLLUTION PREVENTION

14.1 Pollution prevention encompasses any technique that reduces or eliminates the

quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution

prevention exist in laboratory operations. The EPA has established a preferred hierarchy of

environmental management techniques that places pollution prevention as the management

option of first choice. Whenever feasible, laboratory personnel should use pollution prevention
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techniques to address their waste generation. When wastes cannot be feasibly reduced at the

source, the Agency recommends recycling as the next best option.

14.2 For information about pollution prevention that may be applicable to laboratories

and research institutions consult Less is Better: Laboratory Chemical Management for Waste

Reduction available from the American Chemical Society's Department of Government

Relations and Science Policy, 1155 16th St., N.W. Washington, D.C. 20036, http://www.acs.org.

15.0 WASTE MANAGEMENT

The Environmental Protection Agency requires that laboratory waste management

practices be conducted consistent with all applicable rules and regulations. The Agency urges

laboratories to protect the air, water, and land by minimizing and controlling all releases from

hoods and bench operations, complying with the letter and spirit of any sewer discharge permits

and regulations, and by complying with all solid and hazardous waste regulations, particularly

the hazardous waste identification rules and land disposal restrictions. For further information

on waste management, consult The Waste Management Manual for Laboratory Personnel

available from the American Chemical Society at the address listed in Sec. 14.2.

16.0 REFERENCES

1. T. A. Bellar, and J. J. Lichtenberg, "Determining Volatile Organics at Microgram-per-Liter

Levels by Gas Chromatography," J. Amer. Water Works Assoc., 66(12), pp. 739-744

(1974).

2. T. A. Bellar, and J. J. Lichtenberg, "Semi-Automated Headspace Analysis of Drinking

Waters and Industrial Waters for Purgeable Volatile Organic Compounds," in Van Hall,

ed., Measurement of Organic Pollutants in Water and Wastewater, ASTM STP 686, pp.

108-129, 1979.

3. "Development and Application of Test Procedures for Specific Organic Toxic Substances

in Wastewaters: Category 11 - Purgeables and Category 12 - Acrolein, Acrylonitrile, and

Dichlorodifluoromethane," Report for EPA Contract 68-03-2635.

4. M. L. Bruce, R. P. Lee, and M. W. Stevens, "Concentration of Water Soluble Volatile

Organic Compounds from Aqueous Samples by Azeotropic Microdistillation," Environ. Sci.

Technol. 1992, 26, 160-163.

5. S. F. Tsang, N. Chau, P. J. Marsden, and K. R. Carter, "Evaluation of the EnSys PETRO

RISc kit for TPH," Report for Ensys, Inc., Research Triangle Park, NC, 27709, 1992.

6. "Interlaboratory Study of Three Methods for Analyzing Petroleum Hydrocarbons in Soils,"

API Publication Number 4599, American Petroleum Institute, March 1994.

7. Science Applications International Corporation, "Carbamates Method Evaluation Report,"

Report for EPA Contract No. 68-W6-0068, August 1998.

8. B. E. Richter, "Single Laboratory Method Validation Report. Extraction of Diesel Range

Organics (DRO), Waste Oil Organics (WOO), and Total Petroleum Hydrocarbons (TPH)

using Accelerated Solvent Extraction (ASE) with Analytical Validation by GC," Document

118357, Dionex Corporation, June 21, 1999.
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9. R. J. Pirkle, and P. W. McLoughlin, "The Analysis of Selected Components of

Reformulated Gasoline in Environmental Samples" from MTBE Handbook, ed. Kostecki,

P. and Moyer, E. Amherst Scientific Publishers, 2002.

10. USEPA OUST, Environmental Fact Sheet: Analytical Methods for Fuel Oxygenates, EPA

510-F-03-001, April 2003, http://www.epa.gov/oust/mtbe/omethods.pdf

11. H. White, B. Lesnik, and J. T. Wilson, "Analytical Methods for Fuel Oxygenates,"

LUSTLine (Bulletin #42), October, 2002, http://www.epa.gov/oust/mtbe/LL42Analytical.pdf

17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA

The following pages contain the tables and figures referenced by this method.
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TABLE 1

EXAMPLE METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN

GROUND WATER BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Low

Concentrationa

Med.

Concentrationb

High

Concentrationc

Analyte Mean

Recd

%RSD Mean

Recd

%RSD Mean

Recd

%RSD

Acetonee 126 17 N/A -- N/A --

Acetonitrile 147 5 105 8 92 9

Acrolein 146 13 120 27 80 20

Acrylonitrile 179 7 143 28 94 21

1-Butanol 127 8 86 8 90 9

t-Butyl alcohol 122 7 N/A -- N/A --

1,4-Dioxane 124 16 96 10 99 8

Ethanol 152 10 N/A -- N/A --

Ethyl acetate 142 7 135 33 92 25

Ethylene oxide 114 10 N/A -- N/A --

Isobutyl alcohol 122 8 87 13 89 13

Isopropyl alcohol 167 13 N/A -- N/A --

Methanol 166 14 94 9 95 7

Methyl ethyl ketone 105 6 N/A -- N/A --

Methyl isobutyl ketone 66 4 N/A -- N/A --

2-Pentanone 94 3 N/A -- N/A --

1-Propanol N/A -- 91 7 91 7

Propionitrile 135 5 102 14 90 14

Pyridine 92 12 N/A -- N/A --

a 25 μg/L spikes, using internal standard calibration.

b 100 μg/L spikes, using internal standard calibration. c 750 μg/L spikes, using internal standard calibration.

d Mean of 7 replicates. e Problematic, due to transient laboratory contamination.

N/A = Data not available

These data are provided for guidance purposes only.
8015C - 26 Revision 3

February 2007

TABLE 2

EXAMPLE METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES

IN TCLP LEACHATE BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Low

Concentrationa

Med.

Concentrationb

High

Concentrationc

Analyte Mean

Recd

%RSD Mean

Recd

%RSD Mean

Recd

%RSD

Acetonee 99 91 N/A -- N/A --

Acetonitrile 107 17 111 10 95 11

Acrolein 88 10 109 29 87 41

Acrylonitrile 133 13 123 29 103 38

1-Butanol 119 7 89 12 86 8

t-Butyl alcohol 70 31 N/A -- N/A --

1,4-Dioxane 103 20 103 16 102 7

Ethanol 122 13 N/A -- N/A --

Ethyl Acetate 164 12 119 29 107 41

Ethylene oxide 111 12 N/A -- N/A --

Isobutyl alcohol 115 4 86 13 82 13

Isopropyl alcohol 114 8 N/A -- N/A --

Methanol 107 10 102 6 N/A --

Methyl ethyl ketone 87 13 N/A -- N/A --

Methyl isobutyl ketone 78 13 N/A -- N/A --

2-Pentanone 101 8 N/A -- N/A --

1-Propanol N/A -- 98 10 89 7

Propionitrile 100 16 100 11 90 17

Pyridine 46 59 N/A -- N/A --

a 25 μg/L spikes, using internal standard calibration.

b 100 μg/L spikes, using internal standard calibration. c 750 μg/L spikes, using internal standard calibration.

d Mean of 7 replicates. e Problematic, due to transient laboratory contamination.

N/A = Data not available

These data are provided for guidance purposes only.
8015C - 27 Revision 3

February 2007

TABLE 3

EXAMPLE METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILE

COMPOUNDS IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION

(METHOD 5031)

Incinerator Ash Kaolin

Low Conc.a High Conc.b Low Conc.a High Conc.b

Mean

Recc

%RSD Mean

Recc

%RSD Mean

Recc

%RSD Mean

Recc

%RSD

Acrylonitrile 50 53 10 31 102 6 12 52

1-Butanol 105 14 61 12 108 5 58 25

t-Butyl alcohol 101 21 60 13 97 9 59 23

1,4-Dioxane 106 19 48 18 105 10 48 25

Ethanol 117 25 52 20 108 11 48 24

Ethyl acetate 62 19 39 12 90 5 41 25

Isopropyl alcohol 119 21 61 15 108 11 58 24

Methanol 55 53 33 28 117 17 37 22

Methyl ethyl ketone 81 21 40 12 91 8 42 20

Methyl isobutyl

ketone

68 11 57 14 71 5 55 23

2-Pentanone 79 13 54 10 91 5 54 19

Pyridine 52 24 44 20 50 10 49 31

a 0.5 mg/kg spikes, using internal standard calibration.

b 25 mg/kg spikes, using internal standard calibration. c Mean of seven replicates.

These data are provided for guidance purposes only.
8015C - 28 Revision 3

February 2007

TABLE 4

EXAMPLE RESULTS FROM ANALYSIS OF LOW AROMATIC DIESEL BY GC/FID

(5 replicates per test)

Spike Concentration Analysis Results

12.5 ppm ND

75 ppm 54 ± 7 ppm

105 ppm 90 ± 15 ppm

150 ppm 125 ± 12 ppm

1000 ppm 960 ± 105 ppm

ND = Not detected

Samples were prepared using 2-g aliquots of sandy loam soil spiked with

known amounts of low aromatic diesel. Low aromatic diesel is sold in

California. It was purchased for this study at a gas station in San Diego,

California. Extractions were accomplished using methylene chloride as

a solvent (Method 3550, high concentration option).

These data are provided for guidance purposes only.

TABLE 5

EXAMPLE RESULTS FROM ANALYSIS OF DIESEL BY GC/FID

(5 replicates per test)

Spike Concentration Analysis Results

25 ppm 51 ± 6 ppm

75 ppm 76 ± 8 ppm

125 ppm 99 ± 5 ppm

150 ppm 160 ± 10 ppm

Samples were prepared using 10-g aliquots of sandy loam soil spiked

with known amounts of regular #2 diesel purchased at a gas station in

Northern Virginia. Extractions were accomplished using methylene

chloride as a solvent (Method 3550).

These data are provided for guidance purposes only.
8015C - 29 Revision 3

February 2007

TABLE 6

EXAMPLE TRIETHYLAMINE PERFORMANCE DATA FOR SPIKED REAGENT WATER

(Analyses by Direct Aqueous Injection)

Triethylamine Concentration (μg/L)

Spike Conc. Rep. 1 Rep. 2 Rep. 3 Rep. 4 Rep. 5 Rep. 6 Rep. 7 Mean

1.00 1.12 1.17 1.14 1.20 1.19 1.18 1.18 1.169

Mean Recovery 117% S.D. 0.0288 μg/L 

The estimated lower limit of quantitation was derived from the analyses of seven aliquots of

water spiked at 1.00 μg/L, using external standard calibration, on a 30-m, 0.53-mm ID, HP Basic

Wax GC column. A 1-μL injection volume was used. Lower limits of quantitation provided

in SW-846 are for illustrative purposes and may not always be achievable. Laboratories

should establish their own in-house lower limits of quantitation, if necessary to document

method performance.

Data are taken from Reference 7.

These data are provided for guidance purposes only.
8015C - 30 

TABLE 7

EXAMPLE SINGLE-LABORATORY DATA FOR PRESSURIZED FLUID EXTRACTION (METHOD 

OF DIESEL RANGE ORGANICS FROM THREE SOIL MATRICES

DRO Concentration in mg/kg

Matrix and SpikingLevel

Rep. 1 Rep. 2 Rep. 3 Rep. 4 Rep. 5 Rep. 6 Rep. 7 Mean 

Reco

Low Sand 3.2 8.2 5.9 6.3 7.0 7.7 6.4 6.4 

Low Loam 6.5 6.0 7.9 5.1 6.9 9.5 6.4 6.9 

Low Clay 4.3 5.8 5.7 8.6 5.4 7.5 7.6 6.4 

High Sand 1850 1970 2030 2390 2210 2400 2430 2183 

High Loam 1790 1870 1860 1970 1790 1990 1990 1894 

High Clay 1910 1890 1990 2860 2880 2150 2040 2246 

Low level samples were spiked with approximately 5 mg/kg of DRO. High level samples were spiked with approximately 2000 mg/kg of DRO.Seven replicates of each sample were extracted and analyzed by GC/FID.Data are taken from Reference 8.These data are provided for guidance purposes only.
8015C - 31 

FIGURE 1

EXAMPLE CHROMATOGRAM OF A 300 PPM GASOLINE STANDARD
8015C - 32 Revision 3

February 2007

FIGURE 2

EXAMPLE CHROMATOGRAM OF A 30 PPM DIESEL STANDARD
8015C - 33 Revision 3

February 2007

FIGURE 3

EXAMPLE CHROMATOGRAM OF A 30 PPM DIESEL STANDARD WITH THE 

BASELINE PROJECTED BETWEEN C10 AND C28
8015C - 34 Revision 3

February 2007

FIGURE 4

EXAMPLE CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN

SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Mix 1: Analytes distilled at 0.25 mg/L, internal standards at 2.5 mg/L

GC Column: J&W DB-Wax column with 0.53-mm ID

Temperature program: 30 EC for 2 min.

3 EC/min. to 100 EC and held for 0 min.

25 EC/min. to 200 EC and held for 4 min.
8015C - 35 Revision 3

February 2007

FIGURE 5

EXAMPLE CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN

SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Mix 2: Analytes distilled at 0.25 mg/L, internal standards at 2.5 mg/L

GC Column: J&W DB-Wax column with 0.53-mm ID

Temperature program: 30 EC for 2 min.

3 EC/min. to 100 EC and held for 0 min.

25 EC/min. to 200 EC and held for 4 min.
8015C - 36 Revision 3

February 2007

FIGURE 6

EXAMPLE CHROMATOGRAM OF MULTI-COMPONENT MIXTURE