CD-ROM 8015B - 1 Revision 2 December 1996 METHOD 8015B NONHALOGENATED ORGANICS USING GC/FID
1.0 SCOPE AND APPLICATION 1.1 Method 8015 is used t o determine the concentration of various nonhalogenated volatile organic c ompounds and semivolatile organic compounds by gas chromatography. The followin g 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 NAHexafluoro-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 ICD-ROM 8015B - 2 Revision 2 December 1996 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 80 E C 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 orga nics (DROs). GROs correspond to the range of alkanes from C to C and covering a boiling point range of approximately 60 E C - 170 E C 6 10 (Reference 6). DROs correspond to the range of alkanes from C to C and covering a boiling point 10 28 range of app roximately 170 E C - 430 E C (Reference 6). The identification of specific fuel types may be complicated by environmental processes such as evaporation, biodegradation, or when mor e than one fuel type is present. Methods from other sources may be more appropriate for GROs and DROs , since these hydrocarbons are not regulated und er 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 ch romatograms. In addition, if this method is used for the analysis of petroleum hydrocarbons, it i s limited to analysts experienced in the interpretation of hydrocarbon data. Each analyst must demonstrate the ability to generat e acceptable results with this method. 1.4 The method can also be used as a screening tool (for both volatile and semivolatil e 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 i njection 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 certai n nonhalogenated volatile and semivolatile organic compounds.

2.1.1 Samples may be introduced into the GC:

@ fol lowing solvent extraction (Methods 3510, 3520, 3540, 3541, 3545, 3550, o r 3560)CD-ROM 8015B - 3 Revision 2 December 1996 @ by direct inje ction (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 gen erally 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 ext raction) may also be applicable to the target analytes, but has not yet been valid ated by EPA in conjunction with Method 8015. 2.1.3 Diesel range organics (DROs) may be prepared by an appropriate solven t 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 an d confirmation of the n on-halogenated individual analytes. Columns and conditions listed have been demonstrated to provide separation of those target anal ytes. 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 diffu sion of volatile org anics (particularly chlorofluorocarbons and methylene chloride) through the sample containe r septum during shipment and storage. A trip blank prepared from organic-free reagent water an d ca rried through sampling and subsequent storage and handling must serve as a check on suc h contamination. 3.2 Con tamination by carryover can occur whenever high-concentration an d low -concentration samples are analyzed in sequence. To reduce the potential for carryover, th e sample syringe or purging device m ust be rinsed out between samples with an appropriate solvent. Wheneveran unusually concentrated sample is encountered, it should be followed by injection of a solvent blank to check for cross contamination.

3.2.1 Clean p urging vessels with a detergent solution, rinse with distilled water, an d then dry in a 105 E C oven between analyses. Clean syringes or autosamplers by flushing all surfaces that contact samples using appropriate solvents. 3.2.2 All glasswa re must be scrupulously cleaned. Clean all glassware as soon a s possible after use by

rinsing with the last solvent used. This should be followed by detergent washi ng with hot water, and rinses with tap water and organic-free reagent water. Drain the glassware and dry in an oven at 130 E C for several hours or rinse with methanol and drain

. Store dry glassware in a clean environment.CD-ROM 8015B - 4 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 chromatograp h su itable for solvent injections or purge-and-trap sample introduction and all require d access ories, including detectors, column supplies, recorder, gases, and syringes. A dat a 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 b onded 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 col umns are needed for petroleum hydrocarbon anal yses. 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 resolu tion 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-inc h injectors, with deactivated liners designed specifically fo r 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 appropriat e apparatus. 4.2.2 Sample s 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 shutof f valve for volatile analytes.CD-ROM 8015B - 5 Revision 2 December 1996 4.3.2 Microsy ringes - 10- and 25-μL with a 0.006 in. ID needle (Hamilton 702N o r 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 u sed whenever possible. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytica l Reagents of the American Chemical Soci ety, where such specifications are available. Other grades may be used, provided it is first ascertaine d that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. 5.2 Organic-free rea gent 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 boilin g 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 fo r establishing retention times (e.g., C -C for diesel). 10 32 5.6 Stock s tandards - Stock solutions may be prepared from pure standard materials o r purchased as certified solutions. When methanol is a target analyte or when using azeotropi c distillation for sampl e 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 cont ain the compounds of interest, either singly or mixed together. The secondary dilution standards should be prepared at concentrationssuch that the aqueous calibration standards prepa red in Sec. 5.8 will bracket the working range of the analytical system. Secondary dil ution standards should be stored with minimal headspace for volatiles and should be checke d frequentl y

for signs of degradation or evaporation, especially just prior to preparing calibratio n standards from them. 5.8 Calibration standards - Calibration standards at a minimum of five differentconcentrations 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 concentrati on equivalent to the appropriate quantitation limit for the project. The remainin g concentrations should correspond to t he 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 t his method (e.g., some or all of the compounds listed in Sec. 1.1 may be included). Volatil e organic standards are prepared in organic-free reagent wate r. 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.CD-ROM 8015B - 6 Revision 2 December 1996 5.8.2 Use a 25- μL Hamilton 702N microsyringe or equivalent (variations in needl e geometry will adversely affect the ability to deliver reproducible volumes of methanoli c standards into water). 5.8.3 Rapidlyinject 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 contain ed 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 Aq ueous standards used for purge-and-trap analyses (Method 5030) are no t stable and should be discard ed 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 azeotropi c distillatio n (Method 5031) may be stored for up to a month in polytetrafluoroethylene (PTFE)- sealed screw-cap bottles with minimal headspace, at 4 E C, and protected from light. 5.9 Inte rnal standards (if internal standard calibration is used) - To use this approach, th e an alyst must select one or more internal standards that are similar in analytical behavior to th e compounds of interest. The analy st must further demonstrate that the measurement of the internal standard is not affected by method or matrix interfe rences. Because of these limitations, no internal standard can be suggested that is applicable to all samples. The following internal standards are recom mended when preparing samples by azeotropic distillation: 2-chloroacrylonitrile , hexafluoro-2-propanol and hexafluoro-2-methyl-2-propanol. 5.10 Surroga te standards - Whenever possible, the analyst should monitor both th e performance of the analytical system and the effectiveness of the method in dealing with eac h 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 a lternate 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.CD-ROM 8015B - 7 Revision 2 December 1996 7.1.1 Direct inje ction - 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 hig h conce ntration of analytes; injection of aqueous concentrates from Method 503 1 (azeotro pic distillation for nonpurgeable volatile organics); and injection of an organi c solvent waste. Direct injection of aqueous samples (non-concentrated) has very limited app lications. It is only permitted for the determination of volatiles at the toxicit y characteristic (TC) regulatory limits or at concentrat ions in excess of 10,000 μg/L. It may als o 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 extra cts of soil/solids prepared by Methods 3540, 3541, 3545, 3550 or 3560. WARNING : Ultrasonic extraction (Me thod 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 ef ficiency which approaches that of Soxhlet extraction. Consul t Method 3550 for information on the critical aspe cts of this extraction procedure. 7.1.2 Purge and trap - this includes purge and trap for aqueous samp les (Method 5030) and purge and trap for solid samples (Method 5035). Method 5035 also provides techniques for extraction of solid and oily wa ste 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 aque ous samples is performed at ambient temperatures while soil/solid samples uti lize a 40 E C purge to improve extraction efficiency. Occasionally, there may be a need t o per form a heated purge for aqueous samples to lower detection limits; however, a 25-m L sample should provide the sensitivity needed in most situations. 7.1.3 Vacuum distillation - thi s 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 Automate d static headspace - this is a device for the introduction of volatil e 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: 45 E C, hold for 3 minutes Program: 45 E C to 220 E C at 8 E C/min Final temperature: 220 E C, hold for 15 minutes.CD-ROM 8015B - 8 Revision 2 December 1996 7.2.2 Column 2 Carrier gas (Helium) flow rate: 40 mL/min Temperature program: Initial temperature: 50 E C, hold for 3 minutes Program: 50 E C to 170 E C at 6 E C/min Final temperature: 170 E C, hold for 4 minutes. 7.2.3 Column 3 Carrier gas (Helium) flow rate: 15 mL/min Temperature program: Initial temperature: 45 E C, hold for 4 minutes Program: 45 E C to 220 E C at 12 E C/min Final temperature: 220 E C, 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: 200 E C Detector temperature: 340 E C Temperature program: Initial temperature: 45 E C, hold 3 minute Program: 45 E C to 275 E C at 12 E C/min Final temperature: 275 E C, 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: 200 E C Detector temperature: 340 E C Temperature program: Initial temperature: 45 E C, hold 1 minute Program: 45 E C to 100 E C at 5 E C/min Final temperature: 100 E C to 275 E C, at 8 E C/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 Se c. 7.1). A different calibration curve is necessary for each sample introduction mod e because of the differences in conditions and e quipment. Establish chromatographic operating parameters that provide instrument performance equivalent to th at documented in this method. Prepare calibration standards usin g the procedures described above (Sec. 5.8). The external standard t echnique is described below. Analysts wishing to use the internal standar d techniq ue are referred to Method 8000. Recommended internal standards for th e no n-purgeable volatiles include hexafluoro-2-propanol, hexafluoro-2-methyl-2-propanol, an d 2-chloroacrylonitrile.CD-ROM 8015B - 9 Revision 2 December 1996 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 stoc k standards to a volumet ric 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 c oncentration in the final volume specified in the preparat ion method, with no dilutions). The other concentrations should correspond to the expected range of concentrations found i n real samples or should define the working range of the detector. 7.3.2.2 Introduce each calibration standard using the technique that wil l be used to i ntroduce the actual samples into the gas chromatograph. Tabulate peak height o r 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 respon se used for calibration must represent the entire area of the chromatogram within the retention ti me range for the fuel type (DROs or GROs), including the unre solved complex mixture that lies below the individual peaks. See Sec. 7.7.2 fo r information on calculating this area.

7.3.3.1 For ea ch fuel type, prepare calibration standards at a minimum of five diff erent 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 standa rds 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 fou nd in real samples or should define the working range of the detector. NOTE : When ever possible, the calibration should be performed using th e

specific fuel that is contaminating the site (e.g., a sample of the fue l remaining in th e tank suspected of leaking). Where such samples are not a vailable or not known, use recently purchased commercially
available fuel. A qualitative screening injection and GC run may b e performed to identify unknown fuels. 7.3.3.2 Introduce each calibration standard using the technique that wil l be used to introduce the actua l 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 Th e linearity of the calibration must be assessed. This applies to both the singl e component analytes and the fuel types.CD-ROM 8015B - 10 Revision 2 December 1996 7.3.4.1 If the percent relative standard deviation (%RSD) of the calibratio n fa ctoris less than 20% over the working range, linearity through the origin can b e assumed, and the average calibra tion 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, line arity through the origin cannot be assumed. See Method 8000 for other calibration options that may be employed. 7.4 Retention time windows Single compo nent 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 retentio n times for characteristic components in each type of fuel. 7.4.1 Before establishing retention time wi ndows, make sure that the chromatographic syste m 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 retentio n time windows for single comp onent 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. Tw o 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 r etention time range is then calculated b a sed 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 esta blished from the retention times of the C and C alkanes. Use the procedur e 10 28 des cribed in Sec. 7.0 of Method 8000 to establish the retention time windows for these tw o 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 th e beginning of each 12-hour work shift as aminimum requirement. Verification is accomplished by the measurement of one or more calibration standards (normally mid-concentration) tha t contain all of the target analytes and surrogates when individual target analytes are bein g anal yzed. Verification is accomplished by the measurement of the fuel standard and th e hydro carbon retention time standard when petroleum hydrocarbons are being analyzed

. Addi tional analyses of the verification standard(s) throughout a 12-hour shift are strongl y recommended, especially for samples thatcontain visible concentrations of oily material. See Sec. 7.0 "calibration verification" of Method 8000 for more detailed information. 7.5.2 Calcula te the % difference as detailed in Sec. 7.0 of Method 8000. If th e response for any analyte is with in ±15% of the response obtained during the initial calibration, th en 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 analyse s em ploying 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 moreCD-ROM 8015B - 11 Revision 2 December 1996 th an ±15% (±20% for azeotropic distillation), corrective action must be taken to restore th e system or a new calibration curve must be prepared for that compound. 7.5.3 All tar get analytes and surrogates or n-alkanes in the calibration verificatio n analyses mu st fall within previously established retention time windows. If the retention time of any analyte does not fall w ithin the ± 3 Fwindow, 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 metho d 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 Sample s are analyzed in a set referred to as an analysis sequence. Th e sequence begins with calibration verification followed by sample extract analyses. Additional analyses of the verification stan dard(s) throughout a 12-hour shift are strongly recommended, especially for samples that contain visible concentrations of oily material. A verificatio n 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 perfo rmed using external standard calibration must be bracketed with acceptable data quality analyses (e.g., calibration a nd retention time criteria). Therefore, all sa mples must be reanalyzed that fall within the standard that exceeded criteria and the last standard that was acceptable. 7.6.2 Samples are analy zed with the same instrument configuration as is used during calibration. When using Method 5030 for sample introduction, analysts are cautioned tha t opening a sampl e vial or drawing an aliquot from a sealed vial (thus creating headspace) will compromis e samples analyzed for volatiles. Therefore, it is recommended that analyst s 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 th e analys is of the first sample is unsuccessful or if results exceed the calibration range of th e instrument. Disti llates from Method 5031 may be split into two portions and held at 4 E C prior to anal ysis. 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 concentrat ions are calculated by comparing sample response data with the initial calibration of the system (Sec. 7.3). Therefore, if samp le response exceeds the limits of the initial cali bration range, a dilution of the sample must be analyzed. For volatile organic aqueous samples, the dilution must be performed on a second ali quot 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 peaksare not always evident when peaks are off scale. Computer reproduction of chro matograms, manipulated to ensure all peaks are on scale over a 100-fol d range, are acceptable as long as calibration limits are not exceeded. Peak height measurements a re recommended over peak area integration when overlapping peaks cause errors in area integration. 7.6.4 Tentative i dentification of a single component analyte occurs when a peak from a sample extra ct 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 highlyCD-ROM 8015B - 12 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 Secon d column confirmation is generally not necessary for petroleu m hydr ocarbon analysis. However, if analytical interferences are indicated, analysis using th e second GC colu mn is required. Also, the analyst must ensure that the sample hydrocarbons fall within the retention time range established during the initial calibration. NOTE : Ident ification of fuels, especially gasoline, is complicated by their inheren t

volatility. The early eluting compounds in fuels are ob viously the most volatile and the most likely to have we athered unless sampled immediately following a sp ill. The most highly volatile fraction of gasoline constitutes 50% of th e total peak area of a gasoline chromatogra m. This fraction is least likely to be present in an environmental sample or pr esent in only very low concentration in relation to the remainder of a gasoline chromatogram. 7.6.6 Th e performance of the entire analytical system should be checked every 1 2 hours, using data gathered from analyses of blanks, standards, and replicate samples

. Significant pe ak tailing must be corrected. Tailing problems are generally traceable to active s i tes 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 m anufacturer's instructions for maintenance of the introduction device. 7.7 Calculations 7.7.1 The conce ntration of each analyte in the sample may be determined b y calc ulating the amount of standard purged or injected, from the peak response, using th e 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 wi ll produce well resolved peaks in a GC/FID chromatogram, both fuels contain many othe r compon ents that are not chromatographically resolved. This unresolved complex mixtur e re sults 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 el uting between C 10 and C . This area is generated by projecting a horizonta l baseline between the retention

28 times of C and C

.

10 28 7.7.2.2 Because the chromatographic conditions employed for DRO analysi s can result in significant column bleed and a resulting rise in the baseline, it is appropriate to p erform 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 i n the same fashion as is used for samples (see Sec. 7 .7.2.1), by projecting a horizontal baseline across the retention time range fo r DROs. This area is then subtracted from the area measured for the sample and th e difference in areas is used to calculate the DRO concentration, using the equations in Method 8000.CD-ROM 8015B - 13 Revision 2 December 1996 7.7.2.3 For the analysis of GROs, sum the a rea of all peaks eluting between 2- met hylpentane and 1,2,4-trimethyl benzene. This area is used to calculate the GR O concentration, using the equations in Method 8000. Column bleed subtraction is no t generally required for GRO analysis. 7.7.3 Refer to Method 8000, Sec. 7.0 for calculation formulae. The formulae cove r external and internal s tandard calibration, aqueous and non-aqueous samples and linear and non-linear calibration curves. 7.8 Screening 7.8.1 Method 8015 with single-point calibratio n can also be used for GC/FID screening in order to reduce instrument down-time when highly contaminated sample s 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 Establis h that the system response and chromatographic retention times ar e stable. Analyze the high-point GC/MS calibration standard. 7.8.4 Analyze s amples or sample extracts. Compare peak heights in the sampl e chr omatograms with the high-point standard to establish that no compound with the sam e 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 abov e comparison is not an absolute certainty. 7.8.5 It is recommended that the high-point standard should be run at least every 12 ho urs 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 sam ple extracts from waste sites often leaves a high boiling residue in: the inj ection port area, splitters when used, and the injection port end of th e chromatographic column. This residue effects chromatography in many wa ys (i.e., peak tailing, retention time shifts, analyte degradatio n, etc.) and, therefore, instrument maintenance is very i m portant. Residue buildup in a splitter may limit flow through one leg and therefore change the split ra tios. If this occurs during an analytical run, the quantitative data may be incorrect. Proper cl eanup techniques will minimize the problem and instrument QC will indicate whe n instrument maintenance is required. 7.9.2 Suggested chromatograph maintenance Corrective measures may require any one or more of the following remed ial actions. Also see Sec. 7.0 in Method 8000 for additio nal guidance on corrective action for capillary columns and the injection port.

7.9.2.1 Split ter connections - For dual columns which are connected using a press-fit Y-shaped glass splitter or a Y-shaped fused-silica connector, clean an d 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 th eCD-ROM 8015B - 14 Revision 2 December 1996 columns and solvent backflush according to the manufacturer's instructions. If thes e procedures fail toeliminate 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 colum n volumes of an appropriate solvent. Both polar and nonpolar solvents are recommended. Depending on the nature of the sample residues ex pected, 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 wit h methylene chloride and allowed to rema in flooded overnight to allow materials within the stationaryphase to migrate into the solvent. The column is then flushed with fres h 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 proceduresto 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 t o document the quality of the data generated. 8.2 Quality control proc edures 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 labo ratory must demonstrate initial proficiency with each sample prepa ration and determinative method combination it utilizes, by generating data of acceptable accuracy and precision for target an alytes in a clean matrix. The laboratory must also repeat the following operations whenever new staff are trained or significant changes i n instrumentation are made. See Method 8000, Sec. 8.0 for information on how to accomplish this demonstration. 8.4 Sample Q uality Control for Preparation and Analysis - The laboratory must also hav e 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 metho d 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 Documen ting the effect of the matrix should include the analysis of at least one matrix spike and one duplicate unspiked sample or one matrix spike/ma trix spike duplicate pair. The decision on whether to prepare and analyze duplicate samples or a matrix spike/matri x 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 analy sis 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 sam e concentrations as the matrix spike. When the results of the matrix spike analysis indicate aCD-ROM 8015B - 15 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 Surr ogate recoveries - The laboratory must evaluate surrogate recovery data fro m individual samples versus the surrogate control limits developed by the laboratory. See Metho d 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 assur ance practices for use with this me thod. The specific practices that are most productive depend upon the needs of th e laborato ry

and the nature of the samples. Whenever possible, the laboratory should analyz e standard reference materials and participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE 9.1 Specific method performance informatio n for non-purgeable volatiles prepared using the azeotropic microdistillation technique from Method 5031 is in cluded 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 i n 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 Indus trial Waters for Purgeable Volatile Organic Compounds", in Van Hall, ed. , Measurement of Or ganic Pollutants in Water and Wastewater, ASTM STP 686, pp. 108-129, 1979. 3. De velopment and Application of Test Procedures for Specific Organic Toxic Substances i n Waste waters: Category 11 - Purgeables and Category 12 - Acrolein, Acrylonitrile, an d 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 RIS c kit for TPH", Report for Ensys, Inc., Research Triangle Park, NC, 27709, 1992. 6. "Interlaboratory S tudy of Three Methods for Analyzing Petroleum Hydrocarbons in Soils," API Publication Number 4599, American Petroleum Institute, March 1994.CD-ROM 8015B - 16 Revision 2 December 1996 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 a nalysis of 7 aliquots of water spiked at 25 μg/L, using internal standar d a calibration. Problematic due to transient laboratory contamination. bCD-ROM 8015B - 17 Revision 2 December 1996 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 0.5 0 mg/kg, using internal standard calibration.CD-ROM 8015B - 18 Revision 2 December 1996 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 availableCD-ROM 8015B - 19 Revision 2 December 1996 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 availableCD-ROM 8015B - 20 Revision 2 December 1996 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 cCD-ROM 8015B - 21 Revision 2 December 1996 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 we re prepared using 2 g aliquots of sandy loam soil spiked with know n a amounts of low aromatic diesel. Extractions were accomplished using methylen e 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 wer e prepared using 10 g aliquots of sandy loam soil spiked with know n a amounts of regular #2 diesel purchased at a gas station in Northern Virginia

. Extractions were accomplished using methylene chloride as a so lvent (Method 3550).CD-ROM 8015B-22 Revision 2 December 1996 FIGURE 1 CHROMATOGRAM OF A 300 PPM GASOLINE STANDARDCD-ROM 8015B - 23 Revision 2 December 1996 FIGURE 2 CHROMATOGRAM OF A 30 PPM DIESEL STANDARDCD-ROM 8015B - 24 Revision 2 December 1996 FIGURE 3 CHROMATOGRAM OF A 30 PPM DIESEL STANDARD WITH THE

BASELINE PROJECTED BETWEEN C AND C 10 18CD-ROM 8015B - 25 Revision 2 December 1996 FIGURE 4 CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)CD-ROM 8015B - 26 Revision 2 December 1996 FIGURE 5 CHROMATOGRAM OF SEVERAL NONPURGEABLE VOLATILE COMPOUNDS IN SPIKED REAGENT WATER USING AZEOTROPIC MICRODISTILLATION (METHOD 5031)CD-ROM 8015B - 27 Revision 2 December 1996 METHOD 8015B NONHALOGENATED ORGANICS USING GC/FIDCD-ROM 8015B - 28 Revision 2 December 1996 METHOD 8015B (continued)