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:

Compound Name CAS No.a

Appropriate Technique Purge-andDirect Solvent Trap Injection Extraction

Acetone Acetonitrile Acrolein Acrylonitrile Allyl alcohol 1-Butanol (n-Butyl alcohol) t-Butyl alcohol 2-Chloroacrylonitrile (I.S.) Crotonaldehyde Diethyl ether 1,4-Dioxane Ethanol Ethyl acetate Ethylene glycol Ethylene oxide Hexafluoro-2-propanol (I.S.) Hexafluoro-2-methyl2-propanol (I.S.) Isobutyl alcohol Isopropyl alcohol Methanol Methyl ethyl ketone (MEK) Methyl isobutyl ketone (MIBK) N-Nitroso-di-n-butylamine Paraldehyde 2-Pentanone 2-Picoline 1-Propanol Propionitrile

67-64-1 75-05-8 107-02-8 107-13-1 107-18-6 71-36-3 75-65-0 920-37-6 123-73-9 60-29-7 123-91-1 64-17-5 141-78-6 107-21-1 75-21-8 920-66-1 515-14-6 78-83-1 67-63-0 67-56-1 78-93-3 108-10-1 924-16-3 123-63-7 107-87-9 109-06-8 71-23-8 107-12-0

pp pp pp pp ht ht pp NA pp b pp I I I I NA NA pp pp I pp pp pp pp pp pp pp ht

b,d b,d b,d b,d b,d b,d b,d d b,d b b,d b,d b,d b b,d d d b,d b,d b,d b,d b,d b,d b,d b,d b,d b,d d

I I I I I I I NA I I I I I I I NA NA I I I I I b I I I I I

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Compound Name CAS No.a

Appropriate Technique Purge-andDirect Solvent Trap Injection Extraction

Pyridine o-Toluidine

110-86-1 95-53-4

I I

b,d b,d

b b

b d ht I pp NA I.S.

Chemical Abstract Services Registry Number. Adequate response using this technique Amenable to concentration by azeotropic distillation (Method 5031) Method analyte only when purged at 80EC Inappropriate technique for this analyte Poor purging efficiency, resulting in high EQLs Not available 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 C10 to C28 and covering a boiling point 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) 8015B - 2 Revision 2 December 1996

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

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. CD-ROM 8015B - 3 Revision 2 December 1996

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-m 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-m 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 4.2 Detector - Flame ionization (FID)

Sample introduction and preparation apparatus Refer to the 5000 series sample preparation methods for the appropriate

4.2.1 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-L with a 0.006 in. ID needle (Hamilton 702N or equivalent) and 100-L. 4.4 4.5 5.0 Volumetric flasks, Class A - Appropriate sizes with ground glass stoppers. Analytical balance - 0 - 160 g capacity, capable of measuring differences of 0.0001 g.

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, CH3OH. Pesticide quality or equivalent. Store away from other solvents.

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., C10-C32 for diesel). 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 L of methanolic standards into 100 mL of water.

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5.8.2 Use a 25-L 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 g/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 40 mL/min 45EC, hold for 3 minutes 45EC to 220EC at 8EC/min 220EC, hold for 15 minutes.

Carrier gas (Helium) flow rate: Temperature program: Initial temperature: Program: Final temperature:

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7.2.2

Column 2 40 mL/min 50EC, hold for 3 minutes 50EC to 170EC at 6EC/min 170EC, hold for 4 minutes.

Carrier gas (Helium) flow rate: Temperature program: Initial temperature: Program: Final temperature: 7.2.3 Column 3

Carrier gas (Helium) flow rate: Temperature program: Initial temperature: Program: Final temperature: 7.2.4 Column 4 (DROs)

15 mL/min 45EC, hold for 4 minutes 45EC to 220EC at 12EC/min 220EC, hold for 3 minutes.

Carrier gas (Helium) flow rate: Makeup gas (Helium) flow rate: Injector temperature: Detector temperature: Temperature program: Initial temperature: Program: Final temperature: 7.2.5 Column 4 (GROs)

5-7 mL/minute 30 mL/min 200EC 340EC 45EC, hold 3 minute 45EC to 275EC at 12EC/min 275EC, hold 12 min

Carrier gas (Helium) flow rate: Makeup gas (Helium) flow rate: Injector temperature: Detector temperature: Temperature program: Initial temperature: Program: Final temperature: Final hold: 7.3 Initial calibration

5-7 mL/minute 30 mL/min 200EC 340EC 45EC, hold 1 minute 45EC to 100EC at 5EC/min 100EC to 275EC, at 8EC/min 5 min

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 = 7.3.4 Calibration linearity Total Area within Retention Time Range Mass injected (in nanograms)

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 1,2,4trimethylbenzene. 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 CD-ROM 8015B - 10 Revision 2 December 1996

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 CD-ROM 8015B - 11 Revision 2 December 1996

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 C10 and C28. 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 2methylpentane 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 CD-ROM 8015B - 13 Revision 2 December 1996

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 CD-ROM 8015B - 14 Revision 2 December 1996

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. 2. 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). 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. 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. 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. 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. "Interlaboratory Study of Three Methods for Analyzing Petroleum Hydrocarbons in Soils," API Publication Number 4599, American Petroleum Institute, March 1994.

3.

4.

5. 6.

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TABLE 1 METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS IN AQUEOUS MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Analyte Acetoneb Acetonitrile Acrolein Acrylonitrile 1-Butanol t-Butyl alcohol 1,4-Dioxane Ethanol Ethyl acetate Ethylene oxide Isobutyl alcohol Isopropyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone 2-Pentanone 1-Propanol Propionitrile Pyridine

Reagent Water

MDL (g/L)a Ground Water

TCLP Leachate

48 15 13 8 14 8 12 18 9 8 11 18 21 4 4 2 -10 11

16 6 15 9 8 7 15 12 8 9 8 17 21 5 2 2 7 6 9

63 14 7 14 7 17 16 13 16 10 4 7 22 9 8 7 -13 21

Produced by analysis of 7 aliquots of water spiked at 25 g/L, using internal standard calibration. Problematic due to transient laboratory contamination.

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TABLE 2 METHOD DETECTION LIMITS FOR NON-PURGEABLE VOLATILE COMPOUNDS IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Analyte

MDL (mg/kg) Incinerator Ash

Kaolin

Acrylonitrile 1-Butanol t-Butyl alcohol 1,4-Dioxane Ethanol Ethyl acetate Isopropyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone 2-Pentanone Pyridine

0.42 0.23 0.34 0.31 0.47 0.18 0.40 0.46 0.27 0.12 0.16 0.20

0.09 0.09 0.13 0.16 0.19 0.07 0.19 0.31 0.12 0.05 0.07 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)

Compound Acetonee Acetonitrile Acrolein Acrylonitrile 1-Butanol t-Butyl alcohol 1,4-Dioxane Ethanol Ethyl Acetate Ethylene oxide Isobutyl alcohol Isopropyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone 2-Pentanone 1-Propanol Propionitrile Pyridine

Low Conc.a Averaged %Rec %RSD

Medium Conc.b Averaged %Rec %RSD

High Conc.c Averaged %Rec %RSD

126 147 146 179 127 122 124 152 142 114 122 167 166 105 66 94 N/A 135 92

17 5 13 7 8 7 16 10 7 10 8 13 14 6 4 3 -5 12

N/A 105 120 143 86 N/A 96 N/A 135 N/A 87 N/A 94 N/A N/A N/A 91 102 N/A

-8 27 28 8 -10 -33 -13 -9 ---7 14 --

N/A 92 80 94 90 N/A 99 N/A 92 N/A 89 N/A 95 N/A N/A N/A 91 90 N/A

-9 20 21 9 -8 -25 -13 -7 ---7 14 --

a b c d e

25 g/L spikes, using internal calibration. 100 g/L spikes, using internal calibration. 750 g/L spikes, using internal calibration. Average of 7 replicates Problematic due to transient laboratory contamination. Data not available

N/A

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TABLE 4 METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILES IN TCLP LEACHATE BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Compound Acetonee Acetonitrile Acrolein Acrylonitrile 1-Butanol t-Butyl alcohol 1,4-Dioxane Ethanol Ethyl Acetate Ethylene oxide Isobutyl alcohol Isopropyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone 2-Pentanone 1-Propanol Propionitrile Pyridine

Low Conc.a Averaged %Rec %RSD

Medium Conc.b Averaged %Rec %RSD

High Conc.c Averaged %Rec %RSD

99 107 88 133 119 70 103 122 164 111 115 114 107 87 78 101 N/A 100 46

91 17 10 13 7 31 20 13 12 12 4 8 10 13 13 8 -16 59

N/A 111 109 123 89 N/A 103 N/A 119 N/A 86 N/A 102 N/A N/A N/A 98 100 N/A

-10 29 29 12 -16 -29 -13 -6 ---10 11 --

N/A 95 87 103 86 N/A 102 N/A 107 N/A 82 N/A N/A N/A N/A N/A 89 90 N/A

-11 41 38 8 -7 -41 -13 -----7 17 --

a b c d e

25 g/L spikes, using internal calibration. 100 g/L spikes, using internal calibration. 750 g/L spikes, using internal calibration. Average of 7 replicates Problematic due to transient laboratory contamination. Data not available

N/A

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TABLE 5 METHOD PERFORMANCE DATA FOR NON-PURGEABLE VOLATILE COMPOUNDS IN SOLID MATRICES BY AZEOTROPIC MICRODISTILLATION (METHOD 5031)

Incinerator Ash Low Conc.a High Conc.b c Average Averagec %Rec %RSD %Rec %RSD

Kaolin Low Conc.a High Conc.b c Average Averagec %Rec %RSD %Rec %RSD

Acrylonitrile 1-Butanol t-Butyl alcohol 1,4-Dioxane Ethanol Ethyl acetate Isopropyl alcohol Methanol Methyl ethyl ketone Methyl isobutyl ketone 2-Pentanone Pyridine
a b c

50 105 101 106 117 62 119 55 81 68 79 52

53 14 21 19 25 19 21 53 21 11 13 24

10 61 60 48 52 39 61 33 40 57 54 44

31 12 13 18 20 12 15 28 12 14 10 20

102 108 97 105 108 90 108 117 91 71 91 50

6 5 9 10 11 5 11 17 8 5 5 10

12 58 59 48 48 41 58 37 42 55 54 49

52 25 23 25 24 25 24 22 20 23 19 31

0.5 mg/kg spikes, using internal calibration. 25 mg/kg spikes, using internal calibration. Average of 7 replicates

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TABLE 6 RESULTS FROM ANALYSISa OF LOW AROMATIC DIESELb BY GC/FID (5 replicates/test) Spike Concentration 12.5 ppm 75 ppm 105 ppm 150 ppm 1000 ppm
a

Analysis Results ND 54 7 ppm 90 15 ppm 125 12 ppm 960 105 ppm

Samples were prepared using 2 g aliquots of sandy loam soil spiked with known 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 purchased at a gas station in San Diego, California.

TABLE 7 RESULTS FROM ANALYSISa OF LOW AROMATIC DIESELb BY GC/FID (5 replicates/test) Spike Concentration 25 ppm 75 ppm 125 ppm 150 ppm
a

Analysis Results 51.2 6.4 ppm 75.9 7.8 ppm 98.9 5.2 ppm 162 10.4 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).

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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)

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