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METHOD 8015B

NONHALOGENATED ORGANICS USING GC/FID

1.0 SCOPE AND APPLICATION

1.1 Method 8015 is used to determine the concentration of various nonhalogenated volatile

organic compounds and semivolatile organic compounds by gas chromatography. The following

compounds can be determined quantitatively by this method:

 Appropriate Technique 

Compound Name Purge-and- Direct Solvent

 CAS No. Trap Injection Extraction a

Acetone 67-64-1 pp b,d I

Acetonitrile 75-05-8 pp b,d I

Acrolein 107-02-8 pp b,d I

Acrylonitrile 107-13-1 pp b,d I

Allyl alcohol 107-18-6 ht b,d I

1-Butanol (n-Butyl alcohol) 71-36-3 ht b,d I

t-Butyl alcohol 75-65-0 pp b,d I

2-Chloroacrylonitrile (I.S.) 920-37-6 NA d NA

Crotonaldehyde 123-73-9 pp b,d I

Diethyl ether 60-29-7 b b I

1,4-Dioxane 123-91-1 pp b,d I

Ethanol 64-17-5 I b,d I

Ethyl acetate 141-78-6 I b,d I

Ethylene glycol 107-21-1 I b I

Ethylene oxide 75-21-8 I b,d I

Hexafluoro-2-propanol (I.S.) 920-66-1 NA d NA

Hexafluoro-2-methyl2-propanol (I.S.) 515-14-6 NA d NA

Isobutyl alcohol 78-83-1 pp b,d I

Isopropyl alcohol 67-63-0 pp b,d I

Methanol 67-56-1 I b,d I

Methyl ethyl ketone (MEK) 78-93-3 pp b,d I

Methyl isobutyl ketone (MIBK) 108-10-1 pp b,d I

N-Nitroso-di-n-butylamine 924-16-3 pp b,d b

Paraldehyde 123-63-7 pp b,d I

2-Pentanone 107-87-9 pp b,d I

2-Picoline 109-06-8 pp b,d I

1-Propanol 71-23-8 pp b,d I

Propionitrile 107-12-0 ht d I
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 Appropriate Technique 

Compound Name Purge-and- Direct Solvent

 CAS No. Trap Injection Extraction a

Pyridine 110-86-1 I b,d b

o-Toluidine 95-53-4 I b,d b

 Chemical Abstract Services Registry Number. a

 b Adequate response using this technique

 d Amenable to concentration by azeotropic distillation (Method 5031)

 ht Method analyte only when purged at 80EC

 I Inappropriate technique for this analyte

 pp Poor purging efficiency, resulting in high EQLs

 NA Not available

I.S. Internal standard appropriate for Method 5031

1.2 This method may also be applicable to the analysis of petroleum hydrocarbons, including

gasoline range organics (GROs) and diesel range organics (DROs). GROs correspond to the range

of alkanes from C6 to C 10 and covering a boiling point range of approximately 60EC - 170EC

(Reference 6). DROs correspond to the range of alkanes from C to C and covering a boiling point 10 28

range of approximately 170EC - 430EC (Reference 6). 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 GROs and

DROs, since these hydrocarbons are not regulated under RCRA. Consult State and local regulatory

authorities for specific requirements.

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

in the use of gas chromatographs and skilled in the interpretation of gas chromatograms. In addition,

if this method is used for the analysis of petroleum hydrocarbons, it is limited to analysts experienced

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

acceptable results with this method.

1.4 The method can also be used as a screening tool (for both volatile and semivolatile

organics) to obtain semiquantitative data for the prevention of sample overload during quantitative

analysis on a GC/MS system. This may be accomplished using an automated (Method 5021)

headspace method or by direct injection if a solvent extraction method has been utilized for sample

preparation. Single point calibration would be acceptable in this situation. Performance data are

not provided for screening.

2.0 SUMMARY OF METHOD

2.1 Method 8015 provides gas chromatographic conditions for the detection of certain

nonhalogenated volatile and semivolatile organic compounds.

2.1.1 Samples may be introduced into the GC:

@ following solvent extraction (Methods 3510, 3520, 3540, 3541, 3545, 3550, or

3560)
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@ by direct injection (aqueous samples) including the concentration of analytes by

azeotropic distillation (Method 5031)

@ by purge-and-trap (Methods 5030 or 5035), or

@ by vacuum distillation (Method 5032)

2.1.2 Ground or surface water samples must generally be analyzed in conjunction with

Methods 5030, 5031, 5032, 3510, 3520, or other appropriate preparatory methods to obtain

the necessary quantitation limits. Method 3535 (solid-phase extraction) may also be applicable

to the target analytes, but has not yet been validated by EPA in conjunction with Method 8015.

2.1.3 Diesel range organics (DROs) may be prepared by an appropriate solvent

extraction method.

2.1.4 Gasoline range organics (GROs) may be introduced into the GC/FID by purgeand-trap, automated headspace, vacuum distillation, or other appropriate technique.

2.2 An appropriate column and temperature program is used in the gas chromatograph to

separate the organic compounds. Detection is achieved by a flame ionization detector (FID).

2.3 The method allows the use of packed or capillary columns for the analysis and

confirmation of the non-halogenated individual analytes. Columns and conditions listed have been

demonstrated to provide separation of those target analytes. Analysts may change these conditions

as long as they demonstrate adequate performance.

2.4 Fused silica capillary columns are necessary for the analysis of petroleum hydrocarbons.

3.0 INTERFERENCES

3.1 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 must serve as a check on such

contamination.

3.2 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 must 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.

3.2.1 Clean purging vessels with a detergent solution, rinse with distilled water, and

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

surfaces that contact samples using appropriate solvents.

3.2.2 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 in an oven at 130EC for several hours or rinse with methanol and drain.

Store dry glassware in a clean environment.
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3.3 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.

4.0 APPARATUS AND MATERIALS

4.1 Gas chromatograph

4.1.1 Gas Chromatograph - Analytical system complete with gas chromatograph

suitable for solvent injections or purge-and-trap sample introduction and all required

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

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

4.1.2 Recommended GC Columns

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

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

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

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

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

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

4.1.2.4 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.

4.1.2.4.1 Capillary columns are needed for petroleum hydrocarbon

analyses. Laboratories may use other capillary columns (e.g. 0.25-0.32 mm ID

capillary columns) if they document method performance data (e.g.

chromatographic resolution and MDLs) if appropriate for the intended use of the

data.

4.1.2.4.2 Wide-bore columns should be installed in 1/4-inch

injectors, with deactivated liners designed specifically for use with these columns.

4.1.3 Detector - Flame ionization (FID)

4.2 Sample introduction and preparation apparatus 

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

apparatus.

4.2.2 Samples may also be introduced into the GC via injection of solvent extracts or

direct injection of aqueous samples.

4.3 Syringes

4.3.1 A 5-mL Luer-Lok glass hypodermic and a 5-mL gas-tight syringe with shutoff

valve for volatile analytes.
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4.3.2 Microsyringes - 10- and 25-μL with a 0.006 in. ID needle (Hamilton 702N or

equivalent) and 100-μL.

4.4 Volumetric flasks, Class A - Appropriate sizes with ground glass stoppers.

4.5 Analytical balance - 0 - 160 g capacity, capable of measuring differences of 0.0001 g.

5.0 REAGENTS

5.1 Reagent grade chemicals shall be used whenever possible. Unless otherwise indicated,

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

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

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

use without lessening the accuracy of the determination.

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

reagent water, as defined in Chapter One.

5.3 Methanol, CH OH. Pesticide quality or equivalent. Store away from other solvents. 3

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

components in fuel evaporate quickly. If available, obtain fuel from the leaking tank on site.

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

establishing retention times (e.g., C -C for diesel). 10 32

5.6 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.

5.7 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. 5.8 will bracket the working range of the analytical system. Secondary

dilution standards should be stored with minimal headspace for volatiles and should be checked

frequently for signs of degradation or evaporation, especially just prior to preparing calibration

standards from them.

5.8 Calibration standards - Calibration standards at a minimum of five different concentrations

are prepared in water (purge-and-trap or direct injection) or in methylene chloride (solvent injection)

from the secondary dilution of the stock standards. One of the standards should be at or below the

concentration equivalent to the appropriate quantitation limit for the project. The 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 for detection

by this method (e.g., some or all of the compounds listed in Sec. 1.1 may be included). Volatile

organic standards are prepared in organic-free reagent water. In order to prepare accurate aqueous

standard solutions, the following precautions must be observed:

5.8.1 Do not inject more than 20 μL of methanolic standards into 100 mL of water.
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5.8.2 Use a 25-μL Hamilton 702N microsyringe or equivalent (variations in needle

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

standards into water).

5.8.3 Rapidly inject the primary standard into the filled volumetric flask. Remove the

needle as fast as possible after injection.

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

5.8.5 Fill the sample syringe from the standard solution contained in the expanded area

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

5.8.6 Never use pipets to dilute or transfer samples or aqueous standards when diluting

volatile organic standards.

5.8.7 Aqueous standards used for purge-and-trap analyses (Method 5030) are not

stable and should be discarded after 1 hour, unless held in sealed vials with zero headspace.

If so stored, they may be held for up to 24 hours. 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 4EC, and protected from light.

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

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

compounds of interest. The analyst must further demonstrate that the measurement of the internal

standard is not affected by method or matrix interferences. Because of these limitations, no internal

standard can be suggested that is applicable to all samples. The following internal standards are

recommended when preparing samples by azeotropic distillation: 2-chloroacrylonitrile,

hexafluoro-2-propanol and hexafluoro-2-methyl-2-propanol.

5.10 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

sample matrix by spiking each sample, standard, and blank with one or two surrogate compounds

which are not affected by method interferences.

6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

See the introductory material to this chapter, Organic Analytes, Sec. 4.1.

7.0 PROCEDURE

7.1 Introduction/preparation methods

Various alternate methods are provided for sample introduction. All internal standards,

surrogates, and matrix spikes (when applicable) must be added to samples before introduction into

the GC/FID system. Follow the introduction method on when to add standards.
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7.1.1 Direct injection - This involves direct syringe injection into the GC injection port.

7.1.1.1 Volatile organics (includes gasoline range organics [GROs])

This may involve injection of an aqueous sample containing a very high

concentration of analytes; injection of aqueous concentrates from Method 5031

(azeotropic distillation for nonpurgeable volatile organics); and injection of an organic

solvent waste. Direct injection of aqueous samples (non-concentrated) has very limited

applications. It is only permitted 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 the test for ignitability in aqueous samples (along with

Methods 1010 and 1020) to determine if alcohol is present at > 24%.

7.1.1.2 Semivolatile organics (includes diesel range organics [DROs])

This may involve syringe injection of extracts of aqueous samples prepared by

Methods 3510 or 3520 or extracts of soil/solids prepared by Methods 3540, 3541, 3545,

3550 or 3560.

WARNING: Ultrasonic extraction (Method 3550) is not as rigorous a method as

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

critical that the method be followed explicitly to achieve extraction

efficiency which approaches that of Soxhlet extraction. Consult

Method 3550 for information on the critical aspects of this extraction

procedure.

7.1.2 Purge and trap - this includes purge and trap for aqueous samples (Method 5030)

and purge and trap 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 40EC purge to improve extraction efficiency. Occasionally, there may be a need to

perform a heated purge for aqueous samples to lower detection limits; however, a 25-mL

sample should provide the sensitivity needed in most situations.

7.1.3 Vacuum distillation - this is a device for the introduction of volatile organics from

aqueous, solid or tissue samples (Method 5032) into the GC/FID system.

7.1.4 Automated static headspace - this is a device for the introduction of volatile

organics from solid samples (Method 5021) into the GC/FID system.

7.2 Chromatographic conditions (recommended)

7.2.1 Column 1

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

Temperature program:

Initial temperature: 45EC, hold for 3 minutes

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

Final temperature: 220EC, hold for 15 minutes.
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7.2.2 Column 2

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

Temperature program:

Initial temperature: 50EC, hold for 3 minutes

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

Final temperature: 170EC, hold for 4 minutes.

7.2.3 Column 3

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

Temperature program:

Initial temperature: 45EC, hold for 4 minutes

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

Final temperature: 220EC, hold for 3 minutes.

7.2.4 Column 4 (DROs)

Carrier gas (Helium) flow rate: 5-7 mL/minute

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

Injector temperature: 200EC

Detector temperature: 340EC

Temperature program:

Initial temperature: 45EC, hold 3 minute

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

Final temperature: 275EC, hold 12 min

7.2.5 Column 4 (GROs)

Carrier gas (Helium) flow rate: 5-7 mL/minute

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

Injector temperature: 200EC

Detector temperature: 340EC

Temperature program:

Initial temperature: 45EC, hold 1 minute

Program: 45EC to 100EC at 5EC/min

Final temperature: 100EC to 275EC, at 8EC/min

Final hold: 5 min

7.3 Initial calibration

7.3.1 Set up the sample introduction system as outlined in the method of choice (see

Sec. 7.1). A different calibration curve is necessary for each sample introduction mode

because of the differences in conditions and equipment. Establish chromatographic operating

parameters that provide instrument performance equivalent to that documented in this method.

Prepare calibration standards using the procedures described above (Sec. 5.8). The external

standard technique is described below. Analysts wishing to use the internal standard

technique are referred to Method 8000. Recommended internal standards for the

non-purgeable volatiles include hexafluoro-2-propanol, hexafluoro-2-methyl-2-propanol, and

2-chloroacrylonitrile.
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7.3.2 External standard calibration procedure for single component analytes

7.3.2.1 For each analyte and surrogate of interest, 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. One

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

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

preparation method, with no dilutions). The other concentrations should correspond to

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

range of the detector.

7.3.2.2 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.

7.3.3 External standard calibration procedure for DROs and GROs

The calibration of DROs and GROs is markedly different from that for single component

analytes. In particular, the response used for calibration must represent the entire area of the

chromatogram within the retention time range for the fuel type (DROs or GROs), including the

unresolved complex mixture that lies below the individual peaks. See Sec. 7.7.2 for

information on calculating this area.

7.3.3.1 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. One of the external

standards should be at a concentration at or below the quantitation limit necessary for

the project (based on the concentration in the final volume specified in the preparation

method, with no dilutions). The other concentrations 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 commerciallyavailable fuel. A qualitative screening injection and GC run may be

performed to identify unknown fuels.

7.3.3.2 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. 7.7.2. Calculate the calibration factor (CF) for each fuel

type as shown below:

Calibration Factor = Total Area within Retention Time Range

Mass injected (in nanograms)

7.3.4 Calibration linearity

The linearity of the calibration must be assessed. This applies to both the single

component analytes and the fuel types. 
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7.3.4.1 If the percent relative standard deviation (%RSD) of the calibration

factor is less than 20% over the working range, linearity through the origin can be

assumed, and the average calibration factor can be used in place of a calibration curve.

7.3.4.2 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.

7.4 Retention time windows

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

time windows. GROs and DROs are distinguished on the basis of the ranges of retention

times for characteristic components in each type of fuel.

7.4.1 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 Sec. 7.0

of Method 8000.

7.4.2 The retention time range for GROs 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 Sec. 7.0 of 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.

7.4.3 The retention time range for DROs 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 Sec. 7.0 of 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.

7.5 Calibration verification

7.5.1 The working calibration curve, and retention times must be verified at the

beginning of each 12-hour work shift as a minimum requirement. Verification is accomplished

by the measurement of one or more calibration standards (normally mid-concentration) that

contain all of the target analytes and surrogates when individual target analytes are being

analyzed. Verification is accomplished by the measurement of the fuel standard and the

hydrocarbon retention time standard when petroleum hydrocarbons are being analyzed.

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

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

Sec. 7.0 "calibration verification" of Method 8000 for more detailed information.

7.5.2 Calculate the % difference as detailed in Sec. 7.0 of Method 8000. If the

response for any analyte is within ±15% of the response obtained during the initial calibration,

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

CF or RF values from the initial calibration to quantitate sample results. For analyses

employing azeotropic distillation as the sample introduction technique, the % difference may

be up to ±20%. If the response for any analyte varies from the predicted response by more
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than ±15% (±20% for azeotropic distillation), corrective action must be taken to restore the

system or a new calibration curve must be prepared for that compound.

7.5.3 All target analytes and surrogates or n-alkanes in the calibration verification

analyses must fall within previously established retention time windows. If the retention time

of any analyte does not fall within the ± 3F window, corrective action must be taken to restore

the system or a new calibration curve must be prepared for that compound.

7.5.4 Solvent blanks and any method blanks should be run with calibration verification

analyses to confirm that laboratory contamination does not cause false positives.

7.6 Gas chromatographic analysis

7.6.1 Samples are analyzed in a set referred to as an analysis sequence. The

sequence begins with calibration verification followed by sample extract analyses. Additional

analyses of the verification standard(s) throughout a 12-hour 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. 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 must

be bracketed with acceptable data quality analyses (e.g., calibration and retention time criteria).

Therefore, all samples must be reanalyzed that fall within the standard that exceeded criteria

and the last standard that was acceptable.

7.6.2 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 samples for purge-and-trap analysis. The second sample can be stored for 24

hours to ensure that an uncompromised sample is available for analysis or dilution, if the

analysis of the first sample is unsuccessful or if results exceed the calibration range of the

instrument. Distillates from Method 5031 may be split into two portions and held at 4EC prior

to analysis. It is recommended that the distillate be analyzed within 24 hours of distillation.

Distillates must be analyzed within 7 days of distillation.

7.6.3 Sample concentrations are calculated by comparing sample response data with

the initial calibration of the system (Sec. 7.3). Therefore, if sample response exceeds the limits

of the initial calibration range, a dilution of the sample must be analyzed. For volatile organic

aqueous samples, the dilution must be performed on a second aliquot of the sample which has

been properly sealed and stored prior to use and reanalysis. 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 all peaks are on scale over

a 100-fold range, are 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.

7.6.4 Tentative identification of a single component analyte occurs when a peak from

a sample extract falls within the daily retention time window. Confirmation is required on a

second column or by GC/MS. Since the flame ionization detector is non-specific, it is highly
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recommended that GC/MS confirmation be performed on single component analytes unless

historical data are available to support the identification(s). 

7.6.5 Second column confirmation is generally not necessary for petroleum

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

second GC column is required. Also, the analyst must ensure that the sample hydrocarbons

fall within the retention time range established during the initial calibration.

NOTE: 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 sampled 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 least likely to be

present in an environmental sample or present in only very low concentration

in relation to the remainder of a gasoline chromatogram.

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

hours, using data gathered from analyses of blanks, standards, and replicate samples.

Significant peak tailing must 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. 7.9 for GC/FID system maintenance. Follow manufacturer's instructions for maintenance

of the introduction device.

7.7 Calculations

7.7.1 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

calibration curve or the mean CF or RF from the initial curve.

7.7.2 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.

7.7.2.1 For the analysis of DROs, 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 C and C . 10 28

7.7.2.2 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, a methylene chloride blank should be analyzed

during each 12-hour analytical shift during which samples are analyzed for DROs. The

area of this chromatogram is measured in the same fashion as is used for samples (see

Sec. 7.7.2.1), by projecting a horizontal baseline across the retention time range for

DROs. This area is then subtracted from the area measured for the sample and the

difference in areas is used to calculate the DRO concentration, using the equations in

Method 8000.
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7.7.2.3 For the analysis of GROs, sum the area of all peaks eluting between 2-

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

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

generally required for GRO analysis.

7.7.3 Refer to Method 8000, Sec. 7.0 for calculation formulae. The formulae cover

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

non-linear calibration curves. 

7.8 Screening

7.8.1 Method 8015 with single-point calibration can also be used for GC/FID screening

in order to reduce instrument down-time when highly contaminated samples are analyzed using

GC/MS (e.g., Methods 8260 and 8270).

7.8.2 The same configuration of introduction device interfaced to the GC/MS may be

utilized for the GC/FID or alternative configurations are acceptable.

7.8.3 Establish that the system response and chromatographic retention times are

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

7.8.4 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. However, the FID is much

less sensitive to halogenated compounds than the GC/MS system, therefore, the above

comparison is not an absolute certainty.

7.8.5 It is recommended that the high-point standard should be run at least every 12

hours to confirm the stability of instrument response and chromatographic retention times.

However, there is no QC requirement for screening.

7.9 Instrument Maintenance

7.9.1 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 effects 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 required.

7.9.2 Suggested chromatograph maintenance

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

see Sec. 7.0 in Method 8000 for additional guidance on corrective action for capillary columns

and the injection port.

7.9.2.1 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
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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.

7.9.2.2 Column rinsing - The column should be rinsed 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 satisfactory final rinse and in

some cases may be the only solvent required. 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.

8.0 QUALITY CONTROL

8.1 Refer to Chapter One and Method 8000 for specific quality control (QC) procedures.

Quality control procedures to ensure the proper operation of the various sample preparation and/or

sample introduction techniques can be found in Methods 3500 and 5000. Each laboratory should

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

document the quality of the data generated.

8.2 Quality control procedures necessary to evaluate the GC system operation are found in

Method 8000, Sec. 7.0 and include evaluation of retention time windows, calibration verification and

chromatographic analysis of samples.

8.3 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. The laboratory must also

repeat the following operations whenever new staff are trained or significant changes in

instrumentation are made. See Method 8000, Sec. 8.0 for information on how to accomplish this

demonstration.

8.4 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,

and detection limit). At a minimum, this includes 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.

8.4.1 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.

8.4.2 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 the results of the matrix spike analysis indicate a
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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.

8.4.3 See Method 8000, Sec. 8.0 for the details on carrying out sample quality control

procedures for preparation and analysis.

8.5 Surrogate recoveries - The laboratory must evaluate surrogate recovery data from

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

8000, Sec. 8.0 for information on evaluating surrogate data and developing and updating surrogate

limits.

8.6 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.

9.0 METHOD PERFORMANCE

9.1 Specific method performance information for non-purgeable volatiles prepared using the

azeotropic microdistillation technique from Method 5031 is included in Tables 1, 3 and 4 for aqueous

matrices and in Tables 2 and 5 for solid matrices.

9.2 Specific method performance information is provided for diesel fuel spiked into soil in

Tables 6 and 7.

10.0 REFERENCES

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

by Gas Chromatography", J. Amer. Water Works Assoc., 66(12), pp. 739-744 (1974).

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

and Industrial Waters for 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. Bruce, M.L., 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. Tsang, S.F., 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.
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TABLE 1

METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS

IN AQUEOUS MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

 MDL (μg/L)a

Analyte Reagent Water Ground Water TCLP Leachate

Acetone 48 16 63 b

Acetonitrile 15 6 14

Acrolein 13 15 7

Acrylonitrile 8 9 14

1-Butanol 14 8 7

t-Butyl alcohol 8 7 17

1,4-Dioxane 12 15 16

Ethanol 18 12 13

Ethyl acetate 9 8 16

Ethylene oxide 8 9 10

Isobutyl alcohol 11 8 4

Isopropyl alcohol 18 17 7

Methanol 21 21 22

Methyl ethyl ketone 4 5 9

Methyl isobutyl ketone 4 2 8

2-Pentanone 2 2 7

1-Propanol -- 7 --

Propionitrile 10 6 13

Pyridine 11 9 21

 Produced by analysis of 7 aliquots of water spiked at 25 μg/L, using internal standard

a

calibration.

 Problematic due to transient laboratory contamination. b
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TABLE 2

METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS

IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

MDL (mg/kg)

Analyte Incinerator Ash Kaolin

Acrylonitrile 0.42 0.09

1-Butanol 0.23 0.09

t-Butyl alcohol 0.34 0.13

1,4-Dioxane 0.31 0.16

Ethanol 0.47 0.19

Ethyl acetate 0.18 0.07

Isopropyl alcohol 0.40 0.19

Methanol 0.46 0.31

Methyl ethyl ketone 0.27 0.12

Methyl isobutyl ketone 0.12 0.05

2-Pentanone 0.16 0.07

Pyridine 0.20 0.08

The MDLs calculated for this table were produced by the analysis of 7 replicates spiked at 0.50

mg/kg, using internal standard calibration.
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TABLE 3

METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN GROUND

WATER BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Low Conc. Medium Conc. High Conc. a b c

 Average Average Average d d d

Compound %Rec %RSD %Rec %RSD %Rec %RSD

Acetone 126 17 N/A -- N/A --

e

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 --

 25 μg/L spikes, using internal calibration. a

 100 μg/L spikes, using internal calibration. b

 750 μg/L spikes, using internal calibration. c

 Average of 7 replicates d

 Problematic due to transient laboratory contamination. e

 N/A Data not available
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TABLE 4

METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN TCLP

LEACHATE BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Low Conc. Medium Conc. High Conc. a b c

 Average Average Average d d d

Compound %Rec %RSD %Rec %RSD %Rec %RSD

Acetone 99 91 N/A -- N/A --

e

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 --

 25 μg/L spikes, using internal calibration. a

 100 μg/L spikes, using internal calibration. b

 750 μg/L spikes, using internal calibration. c

 Average of 7 replicates d

 Problematic due to transient laboratory contamination. e

 N/A Data not available
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TABLE 5

METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILE COMPOUNDS

IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

 Incinerator Ash Kaolin 

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

 Average Average Average Average c c c c

%Rec %RSD %Rec %RSD %Rec %RSD %Rec %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

 0.5 mg/kg spikes, using internal calibration. a

 25 mg/kg spikes, using internal calibration. b

 Average of 7 replicates c
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TABLE 6

RESULTS FROM ANALYSIS OF LOW AROMATIC DIESEL BY GC/FID a b

(5 replicates/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

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

a

amounts of low aromatic diesel. Extractions were accomplished using methylene

chloride as a solvent (Method 3550, high concentration option).

 Low aromatic diesel is sold in California (Section 2256, CCR). For this study it was b

purchased at a gas station in San Diego, California. 

TABLE 7

RESULTS FROM ANALYSIS OF LOW AROMATIC DIESEL BY GC/FID a b

(5 replicates/test)

Spike Concentration Analysis Results

25 ppm 51.2 ± 6.4 ppm

75 ppm 75.9 ± 7.8 ppm

125 ppm 98.9 ± 5.2 ppm

150 ppm 162 ± 10.4 ppm

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

a

amounts of regular #2 diesel purchased at a gas station in Northern Virginia.

Extractions were accomplished using methylene chloride as a solvent (Method 3550).
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FIGURE 1

CHROMATOGRAM OF A 300 PPM GASOLINE STANDARD
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FIGURE 2

CHROMATOGRAM OF A 30 PPM DIESEL STANDARD
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FIGURE 3

CHROMATOGRAM OF A 30 PPM DIESEL STANDARD WITH THE 

BASELINE PROJECTED BETWEEN C10 AND C18
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FIGURE 4

CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN

SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)
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FIGURE 5

CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN

SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)
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METHOD 8015B

NONHALOGENATED ORGANICS USING GC/FID
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METHOD 8015B

(continued)