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VOLATILE ORGANIC COMPOUNDS (6200)/Introduction 6-23


6200 A. Introduction

1. Source and Significance 1) Initial demonstration of capability—Conduct initial dem-
onstration of capability study at least once, before analysis of any
Many organic compounds have been detected in ground and sample, by each analyst, to demonstrate proficiency with the
surface waters. While most groundwater contamination epi- method of choice. Include at least analysis of a reagent blank and
sodes are traceable to leaking underground fuel or solvent four reagent blank samples fortified at a concentration between
storage vessels, landfills, agriculture practices, and wastewa- 10 times the minimum reporting level and the midpoint of the
ter disposal, the most probable cause for contamination of calibration curve. The blank should not contain any compound of
some aquifers and surface waters has never been firmly es- interest at a concentration greater than minimum reporting level.
tablished. Contamination may be due to past practices of Mean percent recovery for each compound calculated from the
on-site (leach field) disposal of domestic and industrial wastes four fortified samples should be 80% to 120%, and the relative
or to illegal discharges. Organohalides, particularly the triha- standard deviation (RSD) should be ⬍20%.
lomethanes, are present in most chlorinated water systems, 2) Method detection level (MDL)—The MDL is a statistical
especially those using surface waters as a source of supply. determination of the minimum concentration that can be mea-
Toxicological studies on animal models have shown that sured by the method with a confidence level of 99% that the
some of these organics have the potential for teratogenesis or analyte concentration is greater than zero. Determine MDL be-
carcinogenesis in human beings. To minimize these health fore any samples are analyzed, using the procedure described in
risks, sensitive detection and accurate and reproducible quan- Section 1030 or other appropriate procedure3 as required for
titation of organics is of paramount importance. each matrix to be analyzed. For MDL calculation, start with a
concentration about five times the estimated instrument detection
2. Selection of Method level. Perform MDL determination as an iterative process. The
values listed in Table 6200:III were generated using a concen-
Two capillary gas chromatographic methods for purgeable tration of 0.5 ␮g/L. Conduct MDL determination at least annu-
organic compounds are presented. The scope of analytes is ally. Analyze samples for MDL determination over a 3- to 5-d
detector-dependent. Method B is a gas chromatographic/ mass period to generate a more realistic value.
spectrometric (GC/MS) technique. Method C combines GC with 3) Quality-control sample—Analyze an externally generated
photoionization detection (PID)/electrolytic conductivity detec- quality-control sample as a laboratory fortified blank at least
tion (ELCD) in series. Methods B and C are applicable to a wide quarterly or whenever new stock solutions are generated. Obtain
range of purgeable organics. Both methods can be applied to this sample from sources external to the immediate laboratory,
finished drinking water, drinking water in any stage of treatment, and use it to validate the laboratory’s standards both qualitatively
source water, or wastewater. and quantitatively. Acceptance criteria are supplied by the man-
The methods presented are highly sophisticated micro-analyt- ufacturer. If all criteria are not met, determine cause of error, and
ical procedures that should be used only by analysts experienced correct it before continuing.
in chromatography and data evaluation and interpretation. While 4) Minimum quantitation level (MQL)—The MQL is the
the methods are similar, they are not interchangeable from a lowest level that can be quantified accurately. The MQL is
regulatory point of view.1,2 defined as four times the MDL.
b. Calibration:
3. Scope 1) Initial calibration—Perform initial calibration with a min-
imum of five concentrations of analytical calibration standards
Table 6200:I lists the compounds that can be determined by (CALs) for the compound(s) of interest. The lowest concentra-
these methods. All are determinable by both Method B and tion should be at the working reporting level; the highest con-
Method C. Other compounds may be amenable to these methods. centration should be at the upper end of the calibration range. Do
not report values that are outside of the defined calibration range.
4. Sampling and Storage For the calibration concentrations, there should be no more than
one order of magnitude between concentrations.
See Section 6010B.1 Use any of the following calibration functions, as appropriate:
response factor for internal standard calibration, calibration fac-
5. Method-Required Quality Control Criteria tor for external standard calibration, or calibration curve. Cali-
bration curves may be linear through the origin, linear not
a. Initial quality control: through the origin, or quadratic through or not through the
origin. Use the following recommended acceptance criteria for
the various calibration functions.
* Approved by Standard Methods Committee, 1997.
Joint Task Group: 20th Edition—Melissa S. Dale (chair), Anthony Bucciferro, If using response factors or calibration factors, relative stan-
Melly L. Fabro, T.J. Richards, William A. Saner, Robert Slater. dard deviation (RSD) for each compound of interest should be

Use continuing lytes of interest against minimum acceptance values for re- calibration. calibration factor. the analyst’s discretion. Batch quality control: is the periodic analysis of a calibration standard used to verify 1) Analytical day—An analytical day is defined as a 12-h that the instrument response has not changed significantly analytical period.2-Dichloropropane 78-87-5 p-Xylene* 106-42-3 1. described in ¶ 2) below. GC/MS analysis. dard or repeat initial calibration.2-Dibromo-3-chloropropane 96-12-8 1. centrations of analytical standards in the initial calibration. re-analyze continuing calibration stan- Use initial calibration. . When using response factors (i.2. with a minimum concentration greater each compound. every 20 samples for before sample quantitation.3-Trichlorobenzene* 87-61-6 1.3. than two times the reporting limit. whichever is more frequent. calibration and not for sample quantitation. Perform initial cal.2-Dichlorobenzene* 95-50-1 1.4-Trichlorobenzene* 120-82-1 Dibromomethane 74-95-3 1. the correlation coefficient should be for continuing calibration is 70% to 130% recovery compared ⬎0.1-Dichloropropene* 563-58-6 Bromochloromethane 74-97-5 cis-1. If the RSD is not less than 20% for any compound from the initial calibration.3-Dichloropropene* 10061-02-6 Bromoform 75-25-2 Ethylbenzene* 100-41-4 Bromomethane 74-83-9 Hexachlorobutadiene* 87-68-3 n-Butylbenzene* 104-51-8 Isopropylbenzene* 98-82-8 sec-Butylbenzene* 135-98-8 p-Isopropyltoluene* 99-87-6 tert-Butylbenzene* 98-06-6 Methyl t-butyl ether* 1634-04-4 Carbon tetrachloride 56-23-5 Methylene chloride 75-09-2 Chlorobenzene* 108-90-7 Naphthalene* 91-20-3 Chloroethane 75-00-3 n-Propylbenzene* 103-65-1 Chloroform 67-66-3 Styrene* 100-42-5 Chloromethane 74-87-3 1.1-Dichloroethane 75-34-3 1..2-Dichloroethene* 156-59-4 o-Xylene* 95-47-6 trans-1. for GC/MS analysis).e. check performance or sensitivity of the Perform continuing calibration with one or more of the con- instrument for the compound of interest against minimum ac. If the acceptance outlier(s) before sample quantitation.3-Dichlorobenzene* 541-73-1 Trichloroethene* 79-01-6 1. If any of the recalcu.2.1.4-Dichlorobenzene* 106-46-7 Trichlorofluoromethane 75-69-4 Dichlorodifluoromethane 75-71-8 1. or every 12 h.2. then identify and correct source of lack of linearity every 10 samples for GC analysis. tors. ceptance values for the response factors.5-Trimethylbenzene* 108-67-8 1.4-Trimethylbenzene* 95-63-6 1.2. Recalculate each calibration point compared to curve. less than 20%.1-Dichloroethene* 75-35-4 Vinyl chloride* 75-01-4 cis-1.3-Dichloropropane 142-28-9 * Compound can be determined using Method 6200C with PID only.2.1-Trichloroethane 71-55-6 1. or calibration curve) for quan.2-Dichloroethene* 156-60-5 m-Xylene* 108-38-3 1.3-Dichloropropene* 10061-01-5 Bromodichloromethane 75-27-4 trans-1. check performance or sensitivity of instrument for ana- titation of the analytes of interest in samples.6-24 INDIVIDUAL ORGANIC COMPOUNDS (6000) TABLE 6200:I. criteria are not met. identify and correct source of may be extended to 60% to 140% recovery).2-Dichloropropane 590-20-7 Bromobenzene* 108-86-1 1. See specific analytical Vary actual concentration of continuing calibration standard method for the acceptance criteria for the response factors for over calibration range. 2) Continuing calibration—Continuing calibration (CCAL) c. The acceptance criterion For a linear regression.2-Tetrachloroethane 630-20-6 2-Chlorotoluene* 95-49-8 79-34-5 4-Chlorotoluene* 106-43-4 Tetrachloroethene* 127-18-4 Dibromochloromethane 124-48-1 Toluene* 108-88-3 1. When using response fac- sponse factor. the acceptance criterion for the gases lated values are not within ⫾20%. 3) Closing standard—Finish all sample sets with a closing stan- ibration when instrument is set up and whenever continuing dard to demonstrate that performance was still acceptable for the calibration criteria are not met.1. Perform continuing calibration of interest.3-Trichloropropane 96-18-4 1. with any of the above functions (re.2-Dibromoethane 106-93-4 1. only for checks on initial sponse factors. Use acceptance criteria as for the CCAL.994.2-Trichloroethane 79-00-5 1. to the known or expected value of the calibration standard (at Resulting values should be within ⫾20%. last sample analyzed. COMPOUNDS DETERMINABLE BY GAS CHROMATOGRAPHIC METHODS FOR PURGEABLE ORGANIC COMPOUNDS Chemical Abstract Services Chemical Abstract Services Analyte Registry Number Analyte Registry Number Benzene 71-43-2 2.1.2-Dichloroethane 107-06-2 1.

sample fortified to the same concentration as the first. No. the IS is evaluate the precision of the method in a matrix sample. Use re. The retention time of this compound should separate from all analytes of interest and elute in a representative 6. minimum of one LFS duplicate with each sample set (batch). ing for unregulated contaminants. The detector is a mass spectrometer.. because the matrix of the sample may 5) Internal standard (IS)—An internal standard is a compound interfere with method performance. U.S. The IS sample batch acceptance on results of CCAL and LFB additions compound should mimic the chromatographic conditions of the rather than LFS duplicates. Recovery should not vary more those samples extracted in an analytical day. use additional compounds to satisfy 1. If a specific compound cannot be found to meet these criteria. 7) Laboratory-fortified sample (LFS)—A LFS is an additional ple consisting of all reagents that normally contact a sample portion of a sample to which the analytes of interest have been when carried through the entire analytical procedure. ENVIRONMENTAL PROTECTION AGENCY. addition concentrations to be about five times background level). No. General Discussion trometric principles. Base compared to the mean calibration curve area response. It the analytes of interest. 125. 1987. Include a measure all compound responses relative to this standard. Surrogate recovery should remain 1. Make LFSs at sufficient should be present in reagent blank at a level greater than the concentrations that sample background levels do not adversely MQL. added at a concentration at least two times the MRL or around agent blank to determine contribution of reagents and prepara. Principle: Volatile organic compounds are transferred b. pound added to each standard and sample at a known concen- 2. analysis. chromatograph is temperature-programmed to separate the compounds. Interferences: Impurities in the purge gas and organic efficiently from the aqueous to the gaseous phase by bubbling compounds outgassing from the plumbing upstream of the . Include a minimum of one reagent blank with each sample affect recovery calculations. and concentration of analytes in each sample volume is not collected. (If this is a known sample. analytes of interest.11. No compound of interest LFS with each sample set (batch). fortify a large enough monitor ongoing purge recovery. the IS is taken through the entire analytical process. nal standard area response should be in the range of ⫾30% Compare precision and bias to those listed in the method.VOLATILE ORGANIC COMPOUNDS (6200)/Purge & Trap Capillary-Column GC/MS Method 6-25 2) Sample set (batch)—A sample set (batch) is defined as reasonably constant over time. Prepare fortifying solution of known concentration added to each standard and sample just for blanks and samples from a different primary mix than that before sample analysis. If sufficient time. 1986. Refer to method of choice for samples. monitor- 6) Surrogate standard (SS)—A surrogate standard is a com. helium) through a water sample contained range of purgeable organic compounds (see Table 6200:I). The gas mass spectra. provided that all performance criteria are met. the middle of the calibration range. 40 CFR 141 & 142. ENVIRONMENTAL PROTECTION AGENCY. specific surrogates. a.S. adjust set (batch). However. Inter. Because of the nature of purge and trap used to develop working standard mix. If used for quantitation. final rule. Purge and Trap Capillary-Column Gas Chromatographic/Mass Spectrometric Method This method1 is applicable to the determination of a wide an inert gas (e. Federal Register 52. ENVIRONMENTAL PROTECTION AGENCY.g. just 8) LFS duplicates—A LFS duplicate is a second LFS used to as is the surrogate standard [see ¶ 6) below]. References area of the chromatogram. not to exceed 20 than 30% from the known value. 6200 B. the trap is should be used only by analysts experienced in the operation heated and back-flushed with the same inert gas to desorb the of GC/MS systems and in evaluation and interpretation of compounds onto a gas chromatographic column. When quantifying by the internal standard method. 40 CFR Part 136. Use IS to monitor retention volume to yield two sample portions for analysis. NOTE: Base sample batch acceptance on results of CCALs and LFBs For this method the LFB and CCAL are the same. use a second bottle of the same sample. 4) Laboratory-fortified blank (LFB)—See ¶ b2) above. rather than on LFSs. U. lishing test procedures for the analysis of pollutants under the Clean cally similar to the analytes and that is unlikely to be found in Water Act. Federal Register 51. Drinking Water Regulations—synthetic organic chemicals.S. U. Carry surrogate standard through entire 3. National Primary analytical needs. 40 CFR Part 136. The vapor is swept through a sorbent trap that adsorbs compounds. 3) Laboratory reagent blank (LRB)—A LRB is a blank sam. 130. Choose a compound(s) that is chemi. After purging is complete. revision recovery for each sample. 1995. Appendix B. Include a minimum of one tive analytical steps to observed value. Definition and pro- sample extraction and analytical process to monitor extraction cedure for the determination of the method detection limit. environmental samples. whereas the surrogate standard is used to sufficient sample volume is collected. Guidelines estab- tration before extraction. in a specially designed purging chamber at ambient temper- The method can be extended to include other volatile organic ature. relative response. See Section 6010C for discussion of gas chromatographic and mass spec- 1.

d. point ⬍5 mm from base of water column. vent trap to analytical column instrument-dependent. but not pounds. able columns are listed below. Four examples of accept- roethane. and dry it in an oven at 105°C between mandatory. and ensures that the purge entire system.2. The packing protects the diphenylene oxide poly- analyses. designed to accept 25-mL samples with Mention of trade names by Standard Methods does not preclude the use of other existing or as-yet-undeveloped products that give demonstrably equivalent results. Optimally. compatible with the column of choice. 1.25-mm-ID DB-624§ capillary 2.7 cm silica gel. Several complete systems * Tekmar VOCARB 4000 or equivalent. suspended solids. ensure that trap syringe with reagent water between samples. but they can b. non-TFE thread sealants. Use a adsorbents: 1. suitable for on-column injection.. during daily conditioning. carbon tetrachloride. ob. condition trap for 10 min applicable calibration range of this method is compound. Ensure that the meets these criteria. and shipping procedures as a coconut charcoal. c. Alternative sorbents may be and low-level concentration samples are analyzed sequen. tetra. Capillary GC columns: Use any capillary GC column that has not been precisely defined. † Gas chromatographic methods are extremely sensitive to the materials used. Keep gaseous headspace be- that the system is free from contamination under operational tween water column and trap to a total volume of less than 15 conditions by analyzing laboratory reagent blanks daily. analytical area is not subject to contamination from laboratory Needle spargers may be used instead of the glass frit shown in solvents. The minimum specifications for the trap are large amounts of water-soluble materials. meets all performance criteria. column with 1-␮m film thickness. the charcoal may be eliminated and the poly- Contamination by carryover can occur whenever high-level mer section lengthened to 15 cm. at least 25 cm long and with an inside diameter of ganics (particularly fluorocarbons and methylene chloride) at least 3 mm. glass components (e. illustrated in Figure 6200:2. Handle 2) Column 2: 30-m-long ⫻ 0. .. polymer is fully enclosed within the heated zone of the trap.6-26 INDIVIDUAL ORGANIC COMPOUNDS (6000) trap account for most contamination problems. Samples can be contaminated by diffusion of volatile or. used provided that all quality control criteria are met.5-␮m film thickness. or high levels of volatile com- Methyl silicone coated packing is recommended.2-dibromoethane. handling. trichloroethene. 1.2-tetrachloroethane. and desorber. and 7. instrument response. Benzene. For samples containing control criteria. Inc. Figure 6200:1. condition trap overnight following man- water and known-addition concentrations of 0.g. Determination of some geometri. are available commercially. Before daily use. fluoromethane. a.) Avoid using non-TFE plastic tub.4-dichlorobenzene. A smaller 5-mL purging ‡ Supelco. 7.4-␮m film thickness.e. rinse it with distilled water.1. Vent trap effluent to the room. therefore.7 cm through the sampling. 40 of an unusually high concentration sample with a LRB to mL/min for 11 min) and that performance will meet all quality check for carryover contamination.2-trichloroethane. trap. If analysis is not to be made for dichlorodi- check on such contamination. 1. introduce purge gas at a butyl ether (MtBE). or equivalent. run column through tem- Compounds that are inefficiently purged from water will not perature program before sample analysis. high boiling compounds. To reduce carryover. 4) Column 4: 30-m-long ⫻ 0. values are unacceptable. xylenes) may be hampered by co-elution. In a single laboratory using reagent Before initial use.2-dichlo. Deactivate all at sufficient concentration.1. device is acceptable if required method detection levels and § J&W or equivalent. Gas chromatograph (GC)†: Use a temperature-program- be measured with acceptable bias and precision when present mable GC. 1) Column 1: 60-m-long ⫻ 0. not to served MDLs were in the range of 0. Ensure that desorb flow rate is bis(1-chloroisopropyl)ether. and vinyl chloride have been capillary column with 1. Follow analysis keeps total purge gas volume and purge time constant (i. particularly methylene chloride and methyl tert. The analytical column. classified tentatively as known or suspect carcinogens.450 ␮g/L. Pass purge gas through water column as finely divided (NOTE: Use blanks for monitoring only.2 to 200 ␮g/L. Safety: The toxicity or carcinogenicity of each analyte c.0 cm methyl silicone coated packing.32-mm-ID DB-5§ capillary toxic gas respirator when handling high concentrations.75-mm-ID VOCOL‡ wide-bore chloroethene. Alternatively. agent.025 to 0. Detection levels: Method detection levels (MDLs) are thus eliminating potential cold spots. injector liners) with a silanizing cal isomers (e. in either case. 1. The purging device illustrated in Figure 6200:1 components in the purge and trap system. frequently bake and may develop during the heating process.and with back-flushing. 2) Trap.7 cm field reagent blank prepared from reagent water and carried 2. however. silanized compound-dependent and vary with purging efficiency and glass wool may be used as a spacer in the trap inlet.5 ␮g/L. Purge and trap system: The purge and trap system consists of purging device. chloroform.53-mm-ID DB-624§ mega-bore pure standard materials and stock standard solutions of these capillary column with 3-␮m film thickness.. Introduce purge gas no more than 5 mm from base of water ing. Demonstrate performance criteria are met. compounds in a hood and wear a NIOSH/MESA-approved 3) Column 3: 30-m-long ⫻ 0. a water column at least 5 cm deep. 1) Purging device. 7. ufacturer’s instructions. 1. Apparatus column with 1.6-diphenylene oxide polymer. or flow controllers with rubber column. re-coating any active site that subject to contamination. mL. The trap and other parts of the system also are mer adsorbent from aerosols. however. but is approximately 0. corrections for blank bubbles with a diameter of less than 3 mm at the origin.g. Various tially. wash purging device with a detergent solution. rinse purging device and sample sorbent traps are available commercially*. hexachlorobutadiene. be detected when present at low concentrations. packed with the following minimum lengths of through the septum seal during shipment and storage.

c. two-way. if the narrow-bore column (4) is used. Figure 6200:2. depending on which column is used.㛳 spectrum that meets all criteria in Table 6200:II when 25 ng or i. capable of scanning from 35 to 300 g. with detachable tip. d. CAUTION: Toxic substances. and 100-␮L with a 5-cm ⫻ 0. 99. 㛳 Luerlok or equivalent. Trap packings and construction to include desorb capa. e.15- less of 4-bromofluorobenzene is introduced into GC. 3) Silica gel. and producing a mass h. Prepare by pass- interface condenses desorbed materials onto an uncoated ing tap water through a carbon filter bed containing about 0. Data system: To the mass spectrometer attach a computer that allows continuous acquisition and storage of all mass spectra obtained throughout the chromatographic program. Place about 9.9% pure. utilizing 70 eV (nominal) electron energy detachable tip.5 kg fused silica pre-column and when flash-heated transfers com- activated carbon. d. This type of plot is Figure 6200:1. 60/80 mesh. Methanol. Trap packing materials: 1) 2. Syringe valves. g. 5-.# sufficient precision. The uncoated section of column is cooled to ⫺150°C during desorption and heated to 250°C to transfer condensed materials. Computer software should allow for a search of all acquired spectra for specific m/z (masses) and the plot of such m/z abundances versus time or scan number.5-. Software also should allow the integration of the abundances in any EICP over a specified time or scan limit. Purging device. the desired scan rate permits acquisition of j.㛳 in the electron impact ionization mode. at least five spectra while a sample component elutes from the GC. bility. purge-and-trap grade. a capil- a. 25-. To ensure mm-ID and 220 bevel needle. This above the MDL of the constituents of interest. Prepare stock standard solutions in methanol using assayed liquids or gases as appropriate. Vinyl chloride. Purge and trap ⫺ GC/MS interface: Use an open-split or 3. 40-mL with TFE-lined screw cap. Reagents direct-split interface. Stock standard solutions: Prepare from pure standard materials or purchase as certified solutions. 3 OV-1. Let stand unstoppered for about 10 min or until all alcohol-wetted surfaces have dried. f. an extracted ion current profile (EICP). chromato- graphic grade. BFB KEY M/Z ABUNDANCE CRITERIA Mass m/z Abundance Criteria 50 15 to 40% of mass 95 75 30 to 60% of mass 95 95 Base peak.6-Diphenylene oxide polymer. Hydrochloric acid: HCl. . 1. Alternatively.8 mL methanol in a 10-mL ground-glass- stoppered volumetric flask.1 mg. Bottles. Weigh flask to nearest 0.** b. Syringes. e. # Hamilton # 702 or equivalent. ** Millipore Super Q or equivalent. 10-. Mass spectrometer. 0.VOLATILE ORGANIC COMPOUNDS (6200)/Purge & Trap Capillary-Column GC/MS Method 6-27 TABLE 6200:II. in which no interferent is observed at or lary concentrator preceding the GC may be necessary. 1 ⫹ 1. 2) Methyl silicone packing. 100% relative abundance 96 5 to 9% of mass 95 173 ⬍2% of mass 174 174 ⬎50% of mass 95 175 5 to 9% of mass 174 176 95 to 101% of mass 174 177 5 to 9% of mass 176 pounds onto the capillary column. by distillation. Microsyringes. Ascorbic acid. and 25-mL glass hypodermic with amu every 2 s or less. 35/60 mesh. See ¶ 1d. or by using a water purification system. Reagent water.0-. f.

0 min. 50°C.150 50 rofluoromethane. Store with minimum headspace at ⫺10 to ⫺20°C away Trichlorethene 9. chlo- roethane. For Analyte min ␮g/L m/z halocarbon gases that boil below 30°C (bromomethane. 30 m. When compound purity is Bromochloromethane 6.4-Dichlorobenzene 18.055 62 bottle.0 ␮L n-Propylbenzene 16. vinyl chloride).1-Dichloroethane 5.45 0.07 0. attach a vinyl plastic†† tube Vinyl chloride 1. Secondary dilution standards: Using stock standard solu.043 97 standard from uncorrected weight.63 0.100 119 accordingly and all internal standard criteria are met.043 83 bracket working range of the analytical system.046 105 j.260 91 2-Chlorotoluene 16. 175°C.126 83 1.045 95 from light.14 0.032 128 assayed to be 96% or greater. The gas will dissolve into the methanol trans-1. Tem- †† Tygon or equivalent. Replace all other standards monthly. 1.048 131 for gases.4-␮m film. Calibration standards: Prepare at least five concentration 4-Isopropyltoluene 17.3. standard.57 0.130 96 several times.5-Trimethylbenzene 16.028 91 above.3-Dichloropropene 11.025 105 mixture to each sample.038 91 Styrene 15.090 76 Tetrachloroethene 12.047 166 dilution standards with minimal headspace in a freezer and check Dibromochloromethane 13. Prepare secondary dilution standards at concentrations trans-1.037 119 1. Internal standard/surrogate standard known addition: Pre.38 0. Alternate inter.066 83 method analyte(s).65 0.112 83 tions.450 73 Reweigh flask (difference is amount of gas dissolved into 1.131 173 1. Isopropylbenzene 15. dilute to volume.190 85 Chloromethane 1. 4 min.30 0. 1.3-Trichlorobenzene 22.21 0.34 0. Bromodichloromethane 10.120 62 to port of gas bottle containing reference material. then reweigh. Adding 5.0 ␮g/L.2-Dichloroethane 8.0-mL mark.035 93 h.85 0.2.80 0. 4 min.83 0.033 146 secondary standard solution to reagent water and inverting water 1.033 225 or a level that defines the low end of the working range and the 1.07 0. Lower 1.0 mL sample or calibration standard yields a 4-Chlorotoluene 16.46 0. Toluene 11. METHOD DETECTION LEVELS immediately add two or more drops of assayed reference Retention material to flask. 4°C/min.69 0.230 64 the tubing.047 91 gether. Methyl t-butyl ether 4. o-Xylene 15.043 180 others to correspond to the expected range of sample concentra. Preferably use commer.1. 1. Naphthalene 21.49 0.2-Dichloroethene 6. RETENTION TIMES AND using a 100-␮L syringe or disposable capillary-tip glass pipet.2-trifluoroethane 3.4-Trimethylbenzene 17.35 0.1-Trichloroethane 7. perature program: 35°C.96 0. either singly or mixed to. and blank.041 77 croliter from net gain in weight.3-Trichloropropane 16.130 96 syringe needle to within 5 mm of methanol surface and slowly 1.042 117 are certified by the manufacturer or an independent source.3-Dichlorobenzene 17.27 0. Dichlorodifluoromethane 1.25-mm ID.031 104 pare a solution containing fluorobenzene (internal standard) and Bromoform 15. insert needle of 5-mL valved gastight syringe into Trichlorofluoromethane 2.220 94 end bubbling into a beaker of methanol showing flow through Chloroethane 2. 0.04 0.1.81 0.56 0.074 105 nal standard and surrogate compounds may be used.65 0. Alternate secondary stan.24 0.40 0. 1.47 0.4-Trichlorobenzene 21.2-Tetrachloroethane 16. prepare in methanol secondary dilution standards that cis-1.049 128 1. Add this sec-Butylbenzene 17.2-Dichloropropane 6.031 146 sample twice. trichlo.048 75 contain the compounds of interest. chloromethane.44 0. 2.p-Xylene 14.00 0. Store secondary 1.2-Trichloroethane 12.1.32 0. Prepare secondary dilution standard at a 1. 10°C/min.035 105 dard concentrations can be used if addition volume is adjusted tert-Butylbenzene 17. PRIMARY QUANTITATION ION.1. TABLE 6200:III. dichlorofluoromethane.22 0.30 0. 1.57 0.200 96 and will be seen as a vortex as it dissolves into the solvent.67 0.34 0.1.44 0. Benzene 8.051 75 that will permit aqueous calibration standards (¶ j below) to 1. with open Bromomethane 2. Ensure that the drops fall Time MDL Primary directly into the alcohol without contacting flask neck. Always bring to room temperature before Chlorobenzene 14.047 63 methanol).133 129 frequently for signs of evaporation (which would indicate need 1. m.28 0.2-dichlorobenzene-d4 (surrogate) in methanol.68 0.24 0.25 0. Prepare standards fresh weekly 1.64 0.86 0.74 0.1.6-28 INDIVIDUAL ORGANIC COMPOUNDS (6000) Add assayed reference materials as follows: For liquids.032 91 comparison with check standards indicates a problem. the MDL (i. but n-Butylbenzene 18.60 0.059 101 tube and pull gas into syringe slowly to 5.77 0.79 0.2-Dichloroethene 4.2.065 101 Methylene chloride 3. and mix by inverting cis- 0.047 180 GC conditions: Column: J&W DB-624.045 146 levels for each compound by adding appropriate amounts of 1.3-Dichloropropene 12. 4 ⫻ MDL for potable-water-type samples) Hexachlorobutadiene 21. calculate concentration of stock Chloroform 7.24 0.099 49 force gas onto surface. or sooner if Ethylbenzene 14.37 0.038 91 i. .1-Dichloropropene 7.133 107 for regeneration).2.2-Dichloropropane 9.99 0.88 0.42 0.2. Calculate concentration in micrograms per mi. Prepare one standard at a concentration near.2-Dichlorobenzene 18..042 126 standard to 25.71 0.27 0.e.2-Trichloro-1.072 75 concentration of 5 ␮g/mL of each compound.036 78 Transfer stock standard solution into a TFE-sealed screw-cap 1. stopper.90 0.29 0. provided Bromobenzene 16.3-Dichloropropane 12.040 75 cially prepared stock standards at any concentration if they Carbon tetrachloride 7.77 0.2-Tetrachloroethane 14.140 156 that they meet method criteria and do not interfere with any 1.040 126 concentration equivalent to 1.1-Dichloroethene 3.89 0.41 0.14 0.2-Dibromoethane 13.053 63 Dibromomethane 10.052 112 preparing calibration standards.

or standards are analyzed. pare calibration curve for each compound. an 2) Internal standard calibration technique—Select one or appropriate amount of a standard mix dilution and internal standard/ more internal standards similar in analytical behavior to the surrogate mix.25. Sample analysis: Bring sample to ambient temperature. either the internal or the external standard technique. Ais ⫽ response for internal standard. Calibrate system by zero headspace. Condition trap and tabulate peak area responses versus concentration. no one internal standard may be applicable to all samples. discard within 1 h. temperature program: 35°C. 4) Calibration check—See ¶ A. Attach to purge device. and device and analyze as a sample. Otherwise. GC temperature program. Analyze each calibration standard ity control criteria are met. Close valves and purge sample for 11. Because of such limitations. Fluorobenzene is a recommended in- water. Operating conditions: Table 6200:III provides recom.4-␮m film. if ratio of response to concentration (calibration factor) is a constant over the working range (⬍20% RSD). Vent any air and adjust sample volume to 25. Prepare with the specified column is shown in Figure 6200:3. Con. and begin 4°C/min. . Performance tests require the compound in each calibration standard as follows: following instrument parameters: Electron energy: 70 eV (nominal) (A s)(C is) RF ⫽ Mass range: 35 to 300 amu (A is)(C s) Scan time: at least 5 scans/peak but not more than 2 s/scan Inject 25 ng BFB directly on GC column. Aqueous calibra. 4 min. pare calibration standards by injecting. Column: J&W DB-624. 0 min. because of headspace). The compounds used as a. Prepare gives estimated retention times and MDLs that can be achieved calibration standards at a minimum of five concentration under these conditions. 1. c.5b2). use a 3-min dry purge and/or a moisture control module. check GC/MS responses against concentration for each compound and in- system by a performance test with BFB before any samples. Alternatively. Analyze each calibration standard by back-flushing with inert gas at 20 mL/min.. Tabulate peak height or area period during which analyses are to be performed.VOLATILE ORGANIC COMPOUNDS (6200)/Purge & Trap Capillary-Column GC/MS Method 6-29 tions or to define the detector working range. 1. umn at 180°C while back-flushing trap for 4 min with inert gas mm ID. immediately inject water standard into purge vessel. Open sample bottle and carefully pour sample into syringe barrel to just short of overflowing. ternal standard. Pre- daily for 10 min at manufacturer’s suggested temperature. GC/MS performance tests: At the beginning of each 12-h solution directly to syringe. assume lin- earity through the origin and use average calibration factor in place of a calibration curve. An example of the separations obtained levels for each compound as described in ¶ 3j above. mL reagent water in syringe used for sample transfer to purge Cis ⫽ concentration for internal standard. GC/MS chromatogram. with a solvent flush. in duplicate if sufficient sample is available (once sample cap has been removed. 0. add 1 ␮L 25-␮g/mL BFB solution to 25 As ⫽ response for compound to be measured. 10°C/min. 175°C. mass spectrum of BFB and confirm that all key m/z criteria in Table 6200:II are achieved. If all criteria are not achieved. and close valve. directly into a 25-mL syringe filled with reagent compounds of interest. and calculate response factors (RF) for each blanks. sample cannot be stored. and open valve. Other a secondary dilution standard containing each of the internal chromatographic columns or conditions can be used if the qual.2-dichlorobenzene-d4) for quality control mended operating conditions for the gas chromatograph and also can be used successfully as internal standards. at a flow rate compatible with the column of choice. 50°C. d. If water vapor causes problems in the mass spectrometer. invert syringe. 30 m. Calibration: Calibrate system as follows: 3) External standard calibration technique—Prepare stan- 1) System setup—Condition trap initially overnight at 180°C dards as directed in ¶ 3j. pre. Alternatively. Average RF can be used if RSD is less than 20%. open valves. standards (¶ 3i above). Remove plunger from 25-mL syringe and close attached valve. adding internal standard b. ternal standard compound. surrogates (e. Desorb trapped materials onto head of chromatographic col- Figure 6200:3.0 min at ambient temperature at a flow rate of 40 mL/min (helium or nitrogen). If direct injection is where: not easily performed. nect purge and trap system to GC using recommended temper- tion standards can be stored up to 24 h if held in sealed vials with ature program and flow-rate conditions. Procedure ference. 4 min. Add an appropriate amount of surrogate/internal standard through valve bore. Obtain a background-corrected Cs ⫽ concentration of compound to be measured. according to procedure for samples. Demonstrate that measurement of internal standard is not affected by method or matrix inter- 4. re-tune mass Calculate % RSD for the average RFs for each compound.0 mL. and inject sample into purge vessel.g. spectrometer and repeat test until all criteria are met. Replace syringe plunger.

017 11 1.1.042 8 Dibromomethane 132 0.049 9 secondary m/z to quantitate.4-Dichlorobenzene 106 0.034 6 next sample into purge vessel.3.3-Dichloropropene 99 0.052 12 Bromodichloromethane 104 0.045 8 agent water to a total of 25. calculate a response factor or Dichlorodifluoromethane 80 0. Recondition trap by baking at conditioning temperature for Benzene 107 0.058 15 calibration curve using a secondary characteristic m/z.2-Dichlorobenzene 106 0.3-Trichloropropane 104 0.5 ␮g/L concentration..044 8 4-Isopropyltoluene 117 0.054 9 1.036 10 2-Chlorotoluene 111 0.033 6 reopened.037 7 1.1-Trichloroethane 106 0.049 9 1. If any ion abundances exceed system sec-Butylbenzene 113 0.049 9 1.046 8 8.p-Xylene 110 0.2-Dichloropropane 129 0. or alternatively.1.113 17 When compounds have been identified. and with a second syringe.1.2.043 8 working range.045 8 1.2.045 8 interference for the primary m/z.043 8 purge vessel.2. Report results in micrograms per 1. Methods for the Naphthalene 121 0. Quality Control 1.1. Estimate amount of dilution needed and expel Chloroethane 115 0.3-Dichloropropane 107 0. Cincinnati.068 11 Determination of Organic Compounds in Finished Drinking Water n-Propylbenzene 107 0.5. use sample syringe to Relative empty vessel.044 8 1.2-Trichloroethane 97 0.2-Dichloroethene 103 0.053 9 Isopropylbenzene 112 0.039 8 Environmental Monitoring & Support Lab.059 12 liter. cis-1.6-30 INDIVIDUAL ORGANIC COMPOUNDS (6000) TABLE 6200:IV.045 9 1. NOTE: Take care with sample because Carbon tetrachloride 119 0. U.5-Trimethylbenzene 110 0. SINGLE-LABORATORY BIAS AND PRECISION DATA IN Set system auto-drain to empty purge chamber while trap is REAGENT WATER* being desorbed into GC. Ohio. each of 0.2-Dichloroethane 102 0. U. 4-Chlorotoluene 112 0.4-Trichlorobenzene 109 0.057 10 water and analyze.048 9 and Raw Source Water. Reference Methylene chloride 85 0.057 10 o-Xylene 106 0. Hexachlorobutadiene 112 0.051 9 Vinyl chloride 85 0.S.2-Dichloropropane 106 0.044 8 *For all analytes. ENVIRONMENTAL PROTECTION AGENCY.053 10 Tetrachloroethene 106 0. end data Bromoform 107 0.064 10 1. Styrene 101 0. Be sure all areas wetted during purging are also wetted Analyte % Deviation % during rinsing to maximize flushing.040 8 1. Environmental Protection Agency.3-Dichlorobenzene 108 0.2-Trichloro- 1.2-Tetrachloroethane 104 0.2-Dibromoethane 102 0. and use 1.042 7 1.1.1-Dichloroethene 99 0. When all sample compounds Bromochloromethane 88 0. Report all quality control data with sample results.042 8 5.1-Dichloroethane 109 0.0 mL in purge vessel.037 9 m.041 9 Trichloroethene 105 0.2. .1.046 9 See Section 6200A.1-Dichloropropene 110 0.048 8 compounds can be very volatile and can be lost if sample is Chlorobenzene 108 0.044 9 trans-1.2. add necessary re- Chloromethane 74 0. Let trap cool to ambient before introduction of Bromobenzene 111 0.049 9 Dibromochloromethane 108 0. 1992.043 8 integrated area abundance from the EICP of the primary char- 1.2-Dichloroethene 113 0. inject that portion into Chloroform 108 0.046 9 Toluene 106 0.3-Trichlorobenzene 118 0. Calculation 1.4-Trimethylbenzene 116 0.046 9 5 to 7 min.049 9 Table 6200:IV.050 12 Methyl t-butyl ether 81 0. base quantitation on 1.031 6 1.2. seven samples.062 12 trans-1. dilute sample in second syringe with reagent tert-Butylbenzene 116 0.048 8 current profiles (EICP). were analyzed.042 8 acquisition and store data files.3-Dichloropropene 101 0.2-trifluoroethane 113 0.044 8 7. Washing chamber with two 25-mL flushes of Standard reagent water is useful if highly contaminated samples are being Recovery Standard Deviation analyzed. 2.049 11 display full range mass spectra and appropriate extracted ion n-Butylbenzene 115 0.034 6 1.041 8 Trichlorofluoromethane 105 0.2-Tetrachloroethane 113 0.036 7 have been eluted from chromatographic column.073 13 excess sample from second syringe. Use data system software to Bromomethane 89 0.052 10 acteristic m/z given in Table 6200:III. Precision and Bias cis-1. 1.S.038 7 Typical single-laboratory precision and bias data are shown in Ethylbenzene 109 0.045 8 6. If sample produces an 1.

especially around sample purger and detector respirator when handling high concentrations.2a2). and vinyl chloride electrolyte in detector. 2) Trap—See Section 6200B. Analysis of active sites on the GC column or to detector operation. Apparatus bration standards and laboratory control standard. paring retention time of suspect peak to retention times gener- 3) Assembly—See Figures 6200:1 and 2. Poor precision generally is traceable to pounds in a hood and wear a NIOSH/MESA-approved toxic gas pneumatic leaks.2-dichloroethane. mated retention times. Reagents where: As ⫽ response for compound to be measured. Procedure halocarbons and aromatic organic compounds (Table 6200:I) in a. calculated method detection c.2g through j. Gas chromatograph: See Section 6200B. Instrument performance: See Section 6200A. esti- treatment stage.5 ␮g/L. are poorly resolved. Tailing problems generally are traceable to depend on instrument sensitivity and matrix effects.2c.3a through h. ated by calibration standards and laboratory control standard. Examples of 1.1b. Safety: The toxicity or carcinogenicity of each reagent has not low concentrations. replace trap. If external 1) Column—See Section 6200B. If only compounds boiling 5. Other equipment: See Section 6200B. 5-mL glass hypodermic with detachable tip. c. Prepare primary standards of these com.2. A s ⫻ C is c. Ensure that levels (MDLs) for these compounds were in the range of 0. atures also can cause low bromoform response.2-trichloroethane. Carbon tetrachloride. 1. and method detection levels.2-tetrachloroethane. Report results in micrograms per liter without correction for † Luerlok or equivalent.5.05 ␮g/L. b. have been classified tentatively as known or suspected human or A properly operating system shows an average relative standard mammalian carcinogens.2b.5b. If using internal standard technique.1a. calculate 3) Photoionization detector—A high-temperature detector concentration using response factor [RF. Calibration: See Section 6200A. drinking water in any mended operating conditions for the gas chromatograph. 1. electronic problems. Excessive detector reactor temper- been defined precisely. raw source water. Ais ⫽ response for internal standard. Operating conditions: Table 6200:V summarizes recom- finished drinking water. unusually wide peak widths. or sampling and storage problems.2-di. a. non-organohalides that may be coextracted during purging. 1. Use either internal or b. If individual retention times vary by more than 10% over an 8-h period or do not a. the This problem commonly occurs in analyses of finished drinking problem usually is traceable to the trap/desorber. and wastewater. Purge and Trap Capillary-Column Gas Chromatographic Method This method1 is applicable to the determination of purgeable 4. If only brominated waters because of the relatively high trihalomethane content. Principle: See Section 6200B.1.4c2)] by the fol- equipped with a 10. calculate concentration of 2) Electrolytic conductivity or microcoulometric detector— compound being measured from peak response using calibration Halogen-specific systems eliminate misidentifications due to curve or calibration factor previously determined. reactor inlet and exit.* Insert between analytical lowing equation: column and halide detector to analyze simultaneously for aromatic and unsaturated volatile organic compounds (see Table 6200:I). and retention data variance. or are missing. . both silica gel and charcoal can be eliminated and polymer increased to fill entire trap. Several complete systems are commercially available. replace both ion-exchange column and bromoethane. recovery. Report quality control data with sample results. Monitor retention times for each compound using cali- 2. depending on the compound. 3. Some laboratories may Correct any peak tailing significantly in excess of that shown in not be able to achieve these detection levels because results method chromatograms. If negative peaks 1. Purge and trap system: The purge and trap system consists fall within 10% of an established norm. tetrachloroethene. trichloroethene. compounds show poor peak geometry or do not respond properly at d. and known additions of 0. Check precision between replicate analyses. locate and correct source of of three separate pieces of equipment: purging device.2a1). See Section 6200B.† Concentration. d. Determine concentrations of individual compounds. ¶ B. ␮g/L ⫽ A is ⫻ RF d. desorber.3i. Detection levels: In a single laboratory using reagent water prepare a dilution standard as described in Section 6200B. external calibration technique. deviation of less than 10%. b.VOLATILE ORGANIC COMPOUNDS (6200)/Purge & Trap GC Method 6-31 6200 C. If only complex mixtures containing partially resolved compounds may be compounds eluting before chloroform give random responses or hampered by concentration differences larger than a factor of 10. * Tracor Model 703 or equivalent. Sample analysis: See Section 6200B. appear in the chromatogram.2-eV (nominal) lamp. Trap failure is characterized by a pressure drop above 21 kPa across Identify each organohalide in sample chromatogram by com- trap during purging or by poor bromoform sensitivities. General Discussion separations obtained with the specified column are shown in Figures 6200:4 and 5. Calculation above 35°C are to be analyzed. 1) Purging device—See Section 6200B. standard calibration procedure is used.01 to all peaks in standard chromatograms are sharp and symmetrical. 0.5.1. chloroform. Interferences: See Section 6200B. If internal standard calibration procedure is used. trap. Syringes. and Cis ⫽ concentration of internal standard.

80 — 0.017 0.037 — See Table 6200:VI.012 0.088 Bromomethane 9.34 — 0.92 0.028 1.98 0.2-Trichloro-1.015 Water.68 0. Quality Control Method Detection Level See Section 6200A.88 0.027 Ethylbenzene 33. Environmental Mon- 1.019 1.015 0. .07 0. Method 502.75 0.21 0.020 — m.017 4-Chlorotoluene 38.057 — Toluene 29.019 2-Chlorotoluene 38.76 — 0.40 0.048 — n-Propylbenzene 37.04 0.070 — Chlorobenzene 33.38 0.53 0.019 0.1. 8 min.40 0. 185°C. RETENTION TIMES AND METHOD DETECTION LEVELS 6.067 0.64 — 0.043 1.028 1.059 0.6-32 INDIVIDUAL ORGANIC COMPOUNDS (6000) TABLE 6200:V.04 0.p-Xylene 34.3.042 — 1.068 — tors in series.2-Dibromoethane 32.2.028 1.62 0.040 — cis-1.78 0. 4°C/min. ENVIRONMENTAL PROTECTION AGENCY. U. compounds in water by purge and trap capillary column gas chro- trifluoroethane 13.018 0.2..032 Chloroform 21.029 0.57 0.411 Organic Compounds in Finished Drinking Water and Raw Source trans-1.027 Isopropylbenzene 36.1-Dichloroethane 18.032 GC conditions: Column—Supelco VOCOL.2. 1991.08 — 0.54 0.2-Dichloropropane 25. 60 m. 1.3-Trichloropropane 37.2.49 0.028 1.30 0.3-Trichlorobenzene 49. Chloromethane 7.1.67 — 0.62 0. 2.019 Naphthalene 49.034 — 1.61 — 0.008 Carbon tetrachloride 22.1.014 1.5-Trimethylbenzene 38.43 0. 1.4-Dichlorobenzene 41.83 0. Temperature program– 0°C.026 0.042 — Tetrachloroethene 31. Environmental Protection Agency.2.2-Dichlorobenzene 42.3-Dichlorobenzene 41.023 trans-1. Cincinnati.14 0.103 — 8.014 1.5.63 0.2-Dichloropropane 20.2-Dichloroethene 16.39 0.5-␮m film.012 0.061 n-Butylbenzene 42.45 0.2-Dichloroethene 20.023 Bromobenzene 37.49 — 0.80 0.220 — cis-1.046 1.2.09 0.017 1.017 0.44 — 0.018 0.025 0.86 0.018 Bromoform 36.2-Tetrachloroethane 37.028 Hexachlorobutadiene 48.75-mm ID.2 in Methods for the Determination of Methyl t-butyl ether 16.025 — 1.029 0.48 0.1.026 1. Electrolytic Photo- Retention Conductivity ionization Time Detector Detector 7.38 — 0.021 o-Xylene 35.91 0.2-Tetrachloroethane 33.3-Dichloropropane 31. U. 0.21 — 0.44 — 0.3-Dichloropropene 28.021 — Bromodichloromethane 26.S.2.074 — Trichloroethene 25.76 0.89 — 0.018 sec-Butylbenzene 40.1.041 — Vinyl chloride 7.36 0.014 — 1.2-Dichloroethane 23.026 0.030 tert-Butylbenzene 39.18 0.019 0.2-Trichloroethane 30. Volatile organic 1.039 — 1.017 — Bromochloromethane 21.022 — Benzene 23.16 — 0.031 1.020 — Dibromochloromethane 31.59 0.01 0. Ohio.27 0.04 0.023 0. Precision and Bias Analyte min ␮g/L ␮g/L Dichlorodifluoromethane 6.1.3-Dichloropropene 30.015 — itoring & Support Lab.05 — 0.92 0.1-Dichloroethene 13.5 min.018 4-Isopropyltoluene 40.025 — Trichlorofluoromethane 11.047 — matography with photoionization and electrolytic conductivity detec- Methylene chloride 15.026 0.041 Dibromomethane 28.1-Trichloroethane 22.1-Dichloropropene 22.22 0.67 0.013 0.00 0. Reference Chloroethane 9.035 1.94 — 0.4-Trichlorobenzene 48.023 — 1.4-Trimethylbenzene 39.S.024 Styrene 35.72 0.63 0.

021 5 trans-1.009 3 — — — sec-Butylbenzene 65 0.007 2 — — — o-Xylene 68 0.033 9 n-Butylbenzene 63 0.2-Dichloropropane — — — 85 0.1-Trichloroethane — — — 79 0. seven samples.008 2 m.013 3 1.015 3 1.013 5 78 0.011 2 Tetrachloroethene 54 0. were analyzed.2-Trichloroethane — — — 118 0.009 3 94 0.019 4 Dichlorodifluoromethane — — — 71 0.010 3 76 0. SINGLE-LABORATORY BIAS AND PRECISION DATA IN REAGENT WATER* Photoionization Detector Electrolytic Conductivity Detector Relative Relative Standard Standard Recovery Standard Deviation Recovery Standard Deviation Analyte % Deviation % % Deviation % Benzene 70 0.2-Dichlorobenzene 67 0.005 1 1.015 5 78 0.008 2 Isopropylbenzene 67 0.008 2 Dibromochloromethane — — — 88 0.007 2 Bromomethane — — — 73 0.1-Dichloroethene 61 0.3-Dichloropropane — — — 148 0.3-Trichloropropane — — — 87 0.005 1 1.130 3 — — — Naphthalene 73 0.2-Trichloro-1.1.006 2 76 0.006 2 cis-1.011 4 81 0.3-Trichlorobenzene 72 0.5 ␮g/L (unless otherwise noted).006 1 1.006 1 Chloromethane — — — 96 0.2-Tetrachloroethane — — — 83 0.013 4 1.4-Trichlorobenzene 70 63 0.027 8 1.009 2 97 0.004 1 Trichlorofluoromethane — — — 70 0.008 2 Bromodichloromethane — — — 135 0.2.2-Dibromoethane — — — 139 0.010 3 — — — 1.004 1 Toluene 69 0.3-Dichlorobenzene 70 0.014 4 — — — n-Propylbenzene 70 0.2-Dichloroethane — — — 78 0.005 2 79 0.045 12 1.009 3 95 0.005 1 1.006 1 cis-1.005 1 77 0.007 2 1. each at a concentration of 0.2-Tetrachloroethane — — — 88 0.4-Dichlorobenzene 70 0.2-Dichloropropane — — — 74 0.018 5 1.022 3 Dibromomethane — — — 79 0.METHANE (6211)/Purge & Trap GC Method 6-33 TABLE 6200:VI.p-Xylene 73 0.2-Dichloroethene 61 0.009 2 Ethylbenzene 70 0.009 3 — — — tert-Butylbenzene 72 0.1. .021 3 Bromoform — — — 81 0. †Sample concentration 5 ␮g/L.1-Dichloroethane — — — 82 0.2-Dichloroethene 79 0.006 2 — — — Bromobenzene — — — 89 0.4-Trimethylbenzene 65 0.007 2 1.006 2 — — — Carbon tetrachloride — — — 79 5 Methyl t-butyl ether† 75 0.022 6 67 0.005 1 4-Chlorotoluene 73 0.006 2 — — — Vinyl chloride 73 0.007 2 — — — 1.006 1 1.003 1 74 0.5-Trimethylbenzene 70 0.007 2 Chlorobenzene 70 0.001 0 1.2-trifluoroethane — — — 79 0.063 13 2-Chlorotoluene — — — 91 0.007 2 — — — Styrene 70 0.009 2 81 0.009 3 — — — 1.006 2 — — — 4-Isopropyltoluene 65 0.010 3 93 0.029 7 1.018 2 2.1.024 6 1.014 2 Trichloroethene 57 0.2.004 1 trans-1.008 2 Chloroform — — — 83 0.005 1 6 91 0.3-Dichloropropene 57 0.008 2 — — — *For all analytes.008 2 Bromochloromethane — — — 83 0.009 2 Chloroethane — — — 64 0.1-Dichloropropene 54 0.004 2 80 0.010 3 84 0.006 2 — — — Methylene chloride — — — 83 0.009 3 — — — Hexachlorobutadiene 55 0.2.

5-␮m film.5 min. 8 min: 4° C/min. 1. GC conditions: Column: Supelco VOCOL. 185° C. 185° C. 1. 1. .5-␮m film. 60 m. 4° C/min. GC conditions: Column: Supelco VOCOL. temperature program: 0° C.5 min.75-mm ID. ELCD chromatogram. 0. 8 min. Figure 6200:5. PID chromatogram.75-mm ID. 0.6-34 INDIVIDUAL ORGANIC COMPOUNDS (6000) Figure 6200:4. 60 m. temperature program: 0° C. 1.