METHOD 8410 GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED (GC/FT-IR) SPECTROMETRY FOR SEMIVOLATILE ORGANICS: CAPILLARY COLUMN

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1 METHOD 8410 GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED (GC/FT-IR) SPECTROMETRY FOR SEMIVOLATILE ORGANICS: CAPILLARY COLUMN 1.0 SCOPE AND APPLICATION 1.1 This metho covers the automate ientification, or compoun class assignment of unientifiable compouns, of solvent extractable semivolatile organic compouns which are amenable to gas chromatography, by GC/FT-IR. GC/FT-IR can be a useful complement to GC/MS analysis (Metho 8270). It is particularly well suite for the ientification of specific isomers that are not ifferentiate using GC/MS. Compoun class assignments are mae using infrare group absorption frequencies. The presence of an infrare ban in the appropriate group frequency region may be taken as evience of the possible presence of a particular compoun class, while its absence may be construe as evience that the compoun class in question is not present. This evience will be further strengthene by the presence of confirmatory group frequency bans. Ientification limits of the following compouns have been emonstrate by this metho. Compoun Name CAS No. a Acenaphthene Acenaphthylene Anthracene Benzo(a)anthracene Benzo(a)pyrene Benzoic aci Bis(2-chloroethoxy)methane Bis(2-chloroethyl) ether Bis(2-chloroisopropyl) ether Bis(2-ethylhexyl) phthalate Bromophenyl phenyl ether Butyl benzyl phthalate Chloroaniline Chloro-3-methylphenol Chloronaphthalene Chlorophenol Chlorophenol Chlorophenyl phenyl ether Chrysene Dibenzofuran Di-n-butyl phthalate ,2-Dichlorobenzene ,3-Dichlorobenzene ,4-Dichlorobenzene ,4-Dichlorophenol CD-ROM Revision 0

2 Compoun Name CAS No. a Dimethyl phthalate Diethyl phthalate ,6-Dinitro-2-methylphenol ,4-Dinitrophenol ,4-Dinitrotoluene ,6-Dinitrotoluene Di-n-octyl phthalate Di-n-propyl phthalate Fluoranthene Fluorene Hexachlorobenzene ,3-Hexachlorobutaiene Hexachlorocyclopentaiene Hexachloroethane Isophorone Methylnaphthalene Methylphenol Methylphenol Naphthalene Nitroaniline Nitroaniline Nitroaniline Nitrobenzene Nitrophenol Nitrophenol N-Nitrosoimethylamine N-Nitrosoiphenylamine N-Nitroso-i-n-propylamine Pentachlorophenol Phenanthrene Phenol Pyrene ,2,4-Trichlorobenzene ,4,5-Trichlorophenol ,4,6-Trichlorophenol a Chemical Abstract Services Registry Number. 1.2 This metho is applicable to the etermination of most extractable, semivolatile-organic compouns in wastewater, soils an seiments, an soli wastes. Benziine can be subject to losses uring solvent concentration an GC analysis; -BHC, -BHC, Enosulfan I an II, an Enrin are subject to ecomposition uner the alkaline conitions of the extraction step; Enrin is subject to ecomposition uring GC analysis; an Hexachlorocyclopentaiene an N-Nitrosoiphenylamine may ecompose uring extraction an GC analysis. Other extraction an/or instrumentation proceures shoul be consiere for unstable analytes. CD-ROM Revision 0

3 1.3 The ientification limit of this metho may epen strongly upon the level an type of gas chromatographable (GC) semivolatile extractants. The values liste in Tables 1 an 2 represent the minimum quantities of semivolatile organic compouns which have been ientifie by the specifie GC/FT-IR system, using this metho an uner routine environmental analysis conitions. Capillary GC/FT-IR wastewater ientification limits of 25 µg/l may be achieve for weak infrare absorbers with this metho, while the corresponing ientification limits for strong infrare absorbers is 2 µg/l. Ientification limits for other sample matrices can be calculate from the wastewater values after choice of the proper sample workup proceure (see Sec. 7.1). 2.0 SUMMARY OF METHOD 2.1 Prior to using this metho, the samples shoul be prepare for chromatography using the appropriate sample preparation an cleanup methos. This metho escribes chromatographic conitions that will allow for the separation of the compouns in the extract an uses FT-IR for etection an quantitation of the target analytes. 3.0 INTERFERENCES 3.1 Glassware an other sample processing harware must be thoroughly cleane to prevent contamination an misinterpretation. All of these materials must be emonstrate to be free from interferences uner the conitions of the analysis by running metho blanks. Specific selection of reagents or purification of solvents by istillation in all-glass systems may be require. 3.2 Matrix interference will vary consierably from source to source, epening upon the iversity of the resiual waste being sample. While general cleanup techniques are provie as part of this metho, unique samples may require aitional cleanup to isolate the analytes of interest from interferences in orer to achieve maximum sensitivity Chlorophenol an 2-nitrophenol are subject to interference from coeluting compouns. 3.4 Clean all glassware as soon as possible after use by rinsing with the last solvent use. Glassware shoul be seale/store in a clean environment immeiately after rying to prevent any accumulation of ust or other contaminants. 4.0 APPARATUS AND MATERIALS 4.1 Gas Chromatographic/Fourier Transform Infrare Spectrometric Equipment Fourier Transform-Infrare Spectrometer - A spectrometer -1 capable of collecting at least one scan set per secon at 8 cm resolution is require. In general, a spectrometer purchase after 1985, or retrofitte to meet post-1985 FT-IR improvements, will be necessary to CD-ROM Revision 0

4 meet the etection limits of this protocol. A state-of-the-art A/D converter is require, since it has been shown that the signal-tonoise ratio of single beam GC/FT-IR systems is A/D converter limite GC/FT-IR Interface - The interface shoul be lightpipe volumeoptimize for the selecte chromatographic conitions (lightpipe volume of µl for capillary columns). The shortest possible inert transfer line (preferably fuse silica) shoul be use to interface the en of the chromatographic column to the lightpipe. If fuse silica capillary columns are employe, the en of the GC column can serve as the transfer line if it is aequately heate. It has been emonstrate that the optimum lightpipe volume is equal to the full with at half height of the GC eluate peak Capillary Column - A fuse silica DB-5 30 m x 0.32 mm capillary column with 1.0 µm film thickness (or equivalent) Data Acquisition - A computer system eicate to the GC/FT-IR system to allow the continuous acquisition of scan sets for a full chromatographic run. Peripheral ata storage systems shoul be available (magnetic tape an/or isk) for the storage of all acquire ata. Software shoul be available to allow the acquisition an storage of every scan set to locate the file numbers an transform high S/N scan sets, an to provie a real time reconstructe chromatogram Detector - A cryoscopic, meium-ban HgCTe (MCT) etector with the smallest practical focal area. Typical narrow-ban MCT etectors -1 operate from cm, but meium-ban MCT etectors can reach cm. A 750 cm cutoff (or lower) is esirable since it allows the etection of typical carbon-chlorine stretch an aromatic out-of-plane carbon-hyrogen vibrations of environmentally important organo-chlorine an polynuclear aromatic compouns. The MCT etector sensitivity (D) * 10 shoul be $ 1 x 10 cm Lightpipe - Constructe of inert materials, gol coate, an volume-optimize for the esire chromatographic conitions (see Sec. 7.3) Gas Chromatograph - The FT-IR spectrometer shoul be interface to a temperature programmable gas chromatograph equippe with a Grob-type (or equivalent) purge splitless injection system suitable for capillary glass columns or an on-column injector system. A short, inert transfer line shoul interface the gas chromatograph to the FT-IR lightpipe an, if applicable, to the GC etector. Fuse silica GC columns may be irectly interface to the lightpipe inlet an outlet. 4.2 Dry Purge Gas - If the spectrometer is the purge-type, provisions shoul be mae to provie a suitable continuous source of ry purge-gas to the FT-IR spectrometer. CD-ROM Revision 0

5 4.3 Dry Carrier Gas - The carrier gas shoul be passe through an efficient cartrige-type rier. 4.4 Syringes - 1-µL, 10-µL. 5.0 REAGENTS 5.1 Reagent grae inorganic chemicals shall be use in all tests. Unless otherwise inicate, it is intene that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Other graes may be use, provie it is first ascertaine that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the etermination. 5.2 Organic-free reagent water. All references to water in this metho refer to organic-free reagent water, as efine in Chapter One. 5.3 Solvents Acetone, CH C0CH - Pesticie quality, or equivalent Methylene chlorie, CH Cl - Pesticie quality, or equivalent Stock Stanar Solutions (1000 mg/l) - Stanar solutions can be prepare from pure stanar materials or purchase as a certifie solution Prepare stock stanar solutions by accurately weighing g of pure material. Dissolve the material in pesticie quality acetone or other suitable solvent an ilute to volume in a 100 ml volumetric flask. Larger volumes can be use at the convenience of the analyst. When compoun purity is assaye to be 96 percent or greater, the weight may be use without correction to calculate the concentration of the stock stanar. Commercially prepare stock stanars may be use at any concentration if they are certifie by the manufacturer or by an inepenent source Transfer the stock stanar solutions into bottles with Teflon o line screw-caps. Store at 4 C an protect from light. Stock stanar solutions shoul be checke frequently for signs of egraation or evaporation, especially just prior to preparing calibration stanars from them Stock stanar solutions must be replace after 6 months or sooner if comparison with quality control reference samples inicates a problem. 5.5 Calibration Stanars an Internal Stanars - For use in situations where GC/FT-IR will be use for primary quantitation of analytes rather than confirmation of GC/MS ientification Prepare calibration stanars that contain the compouns of interest, either singly or mixe together. The stanars shoul be CD-ROM Revision 0

6 prepare at concentrations that will completely bracket the working range of the chromatographic system (at least one orer of magnitue is suggeste) Prepare internal stanar solutions. Suggeste internal stanars are 1-Fluoronaphthalene, Terphenyl, 2-Chlorophenol, Phenol, Bis(2-chloroethoxy)methane, 2,4-Dichlorophenol, Phenanthrene, Anthracene, an Butyl benzyl phthalate. Determine the internal stanar concentration levels from the minimum ientifiable quantities. See Tables 1 an SAMPLE COLLECTION, PRESERVATION, AND HANDLING See the introuctory material to this chapter, Organic Analytes, Sec. 7.0 PROCEDURE 7.1 Sample Preparation - Samples must be prepare by one of the following methos prior to GC/FT-IR analysis. Matrix Methos Water 3510, 3520 Soil/seiment 3540, 3541, 3550 Waste 3540, 3541, 3550, Extracts may be cleane up by Metho 3640, Gel-Permeation Cleanup. 7.3 Initial Calibration - Recommene GC/FT-IR conitions: Scan time: At least 2 scan/sec. o Initial column temperature an hol time: 40 C for 1 minute. Column temperature program: o o C at 10 C/min. Final column temperature hol: o 280 C. Injector temperature: o C. Transfer line temperature: o 270 C. Lightpipe: o 280 C. Injector: Grob-type, splitless or on-column. Sample volume: 2-3 µl. Carrier gas: Dry helium at about 1 ml/min. 7.4 With an oscilloscope, check the etector centerburst intensity versus the manufacturer's specifications. Increase the source voltage, if necessary, to meet these specifications. For reference purposes, laboratories shoul prepare a plot of time versus etector voltage over at least a 5 ay perio. 7.5 Capillary Column Interface Sensitivity Test - Install a 30 m x 0.32 mm fuse silica capillary column coate with 1.0 µm of DB-5 (or equivalent). CD-ROM Revision 0

7 o o Set the lightpipe an transfer lines at 280 C, the injector at 225 C an the GC o etector at 280 C (if use). Uner splitless Grob-type or on-column injection conitions, inject 25 ng of nitrobenzene, issolve in 1 µl of methylene chlorie. The nitrobenzene shoul be ientifie by the on-line library software search within the first five hits (nitrobenzene shoul be containe within the search library). 7.6 Interferometer - If the interferometer is air-riven, ajust the interferometer rive air pressure to manufacturer's specifications. 7.7 MCT Detector Check - If the centerburst intensity is 75 percent or less of the mean intensity of the plot maximum obtaine by the proceure of Sec. 7.4, install a new source an check the MCT centerburst with an oscilloscope versus the manufacturer's specifications (if available). Allow at least five hours of new source operation before ata acquisition. 7.8 Frequency Calibration - At the present time, no consensus exists within the spectroscopic community on a suitable frequency reference stanar for vapor-phase FT-IR. One reviewer has suggeste the use of inene as an on-the-fly stanar. 7.9 Minimum Ientifiable Quantities - Using the GC/FT-IR operating parameters specifie in Sec. 7.3, etermine the minimum ientifiable quantities for the compouns of interest Prepare a plot of lightpipe temperature versus MCT centerburst intensity (in volts or other vertical height units). This plot shoul span the temperature range between ambient an the lightpipe thermal limit o in increments of about 20 C. Use this plot for aily QA/QC (see Sec. 8.4). Note that moern GC/FT-IR interfaces (1985 an later) may have eliminate most of this temperature effect GC/FT-IR Extract Analysis Analysis - Analyze the rie methylene chlorie extract using the chromatographic conitions specifie in Sec. 7.3 for capillary column interfaces GC/FT-IR Ientification - Visually compare the analyte infrare (IR) spectrum versus the search library spectrum of the most promising on-line library search hits. Report, as ientifie, those analytes with IR frequencies for the five (maximum number) most intense IR -1 bans (S/N $ 5) which are within cm of the corresponing bans in the library spectrum. Choose IR bans which are sharp an well resolve. The software use to locate spectral peaks shoul employ the peak "center of gravity" technique. In aition, the IR frequencies of the analyte an library spectra shoul be etermine with the same computer software Retention Time Confirmation - After visual comparison of the analyte an library spectrum as escribe in Sec , compare the relative retention times (RRT) of the analyte an an authentic stanar of the most promising library search hit. The stanar an analyte RRT CD-ROM Revision 0

8 shoul agree within RRT units when both are etermine at the same chromatographic conitions Compoun Class or Functionality Assignment - If the analyte cannot be unequivocally ientifie, report its compoun class or functionality. See Table 3 for gas-phase group frequencies to be use as an ai for compoun class assignment. It shoul be note that FT-IR gasphase group stretching frequencies are 0-30 cm higher in frequency than -1 those of the conense phase Quantitation - This protocol can be use to confirm GC/MS ientifications, with subsequent quantitation. Two FT-IR quantitation an a supplemental GC etector technique are also provie Integrate Absorbance Technique - After analyte ientification, construct a stanar calibration curve of concentration versus integrate infrare absorbance. For this purpose, choose for integration only those FT-IR scans which are at or above the peak half-height. The calibration curve shoul span at least one orer of magnitue an the working range shoul bracket the analyte concentration Maximum Absorbance Infrare Ban Technique - Following analyte ientification, construct a stanar calibration curve of concentration versus maximum infrare ban intensity. For this purpose, choose an intense, symmetrical an well resolve IR absorbance ban. (Note that IR transmission is not proportional to concentration). Select the FT-IR scan with the highest absorbance to plot against concentration. The calibration curve shoul span at least one orer of magnitue an the working range shoul bracket the analyte concentration. This metho is most practical for repetitive, target compoun analyses. It is more sensitive than the integrate absorbance technique Supplemental GC Detector Technique - If a GC etector is use in tanem with the FT-IR etector, the following technique may be use: following analyte ientification, construct a stanar calibration curve of concentration versus integrate peak area. The calibration curve shoul span at least one orer of magnitue an the working range shoul bracket the analyte concentration. This metho is most practical for repetitive, target compoun analyses. 8.0 QUALITY CONTROL 8.1 Refer to Chapter One for specific quality control proceures. Quality control to valiate sample extraction is covere in Metho 3500 an in the extraction metho utilize. If extract cleanup was performe, follow the QC in Metho 3600 an in the specific cleanup metho. CD-ROM Revision 0

9 8.2 One Hunre Percent Line Test - Set the GC/FT-IR operating conitions to those employe for the Sensitivity Test (see Sec. 7.5). Collect 16 scans over the entire etector spectral range. Plot the test an measure the peak-to-peak -1 noise between 1800 an 2000 cm. This noise shoul be # 0.15%. Store this plot for future reference. 8.3 Single Beam Test - With the GC/FT-IR at analysis conitions, collect 16 scans in the single beam moe. Plot the co-ae file an compare with a subsequent file acquire in the same fashion several minutes later. Note if the spectrometer is at purge equilibrium. Also check the plot for signs of eterioration of the lightpipe potassium bromie winows. Store this plot for future reference. 8.4 Align Test - With the lightpipe an MCT etector at thermal equilibrium, check the intensity of the centerburst versus the signal temperature calibration curve. Signal intensity eviation from the preicte intensity may mean thermal equilibrium has not yet been achieve, loss of etector coolant, ecrease in source output, or a loss in signal throughput resulting from lightpipe eterioration. 8.5 Mirror Alignment - Ajust the interferometer mirrors to attain the most intense signal. Data collection shoul not be initiate until the interferogram is stable. If necessary, align the mirrors prior to each GC/FT-IR run. 8.6 Lightpipe - The lightpipe an lightpipe winows shoul be protecte from moisture an other corrosive substances at all times. For this purpose, maintain the lightpipe temperature above the maximum GC program temperature but below its thermal egraation limit. When not in use, maintain the lightpipe temperature slightly above ambient. At all times, maintain a flow of ry, inert, carrier gas through the lightpipe. 8.7 Beamsplitter - If the spectrometer is thermostate, maintain the beamsplitter at a temperature slightly above ambient at all times. If the spectrometer is not thermostate, minimize exposure of the beamsplitter to atmospheric water vapor. 9.0 METHOD PERFORMANCE 9.1 Metho 8410 has been in use at the U.S. Environmental Protection Agency Environmental Monitoring Systems Laboratory for more than two years. Portions of it have been reviewe by key members of the FT-IR spectroscopic community (9). Sie-by-sie comparisons with GC/MS sample analyses inicate similar emans upon analytical personnel for the two techniques. Extracts previously subjecte to GC/MS analysis are generally compatible with GC/FT-IR. However, it shoul be kept in min that lightpipe winows are typically water soluble. Thus, extracts must be vigorously rie prior to analysis. 9.2 Table 4 provies performance ata for this metho. CD-ROM Revision 0

10 10.0 REFERENCES 1. Hanbook for Analytical Quality Control in Water an Wastewater Laboratories; U.S. Environmental Protection Agency. Environmental Monitoring an Support Laboratory. ORD Publication Offices of Center for Environmental Research Information: Cincinnati, OH, March 1979; Sec. 4, EPA-600/ Freeman, R.R. Hewlett Packar Application Note: Quantitative Analysis Using a Purge Splitless Injection Technique; ANGC Cole, R.H. Tables of Wavenumbers for the Calibration of Infrare Spectrometers; Pergamon: New York, Grasselli, J.G.; Griffiths, P.R.; Hannah, R.W. "Criteria for Presentation of Spectra from Computerize IR Instruments"; Appl. Spectrosc. 1982, 36, Nyquist, R.A. The Interpretation of Vapor-Phase Infrare Spectra. Group Frequency Data; Volume I. Satler Laboratories: Philaelphia, PA, Socrates, G. Infrare Characteristic Group Frequencies; John Wiley an Sons: New York, NY, Bellamy, L.J. The Infrare Spectra of Complex Organic Molecules; 2n e.; John Wiley an Sons: New York, NY, Szymanski, H.A. Infrare Ban Hanbook, Volumes I an II; Plenum: New York, NY, Gurka, D.F. "Interim Protocol for the Automate Analysis of Semivolatile Organic Compouns by Gas Chromatography/Fourier Transform-Infrare Spectrometry"; Appl. Spectrosc. 1985, 39, Griffiths, P.R.; e Haseth, J.A.; Azarraga, L.V. "Capillary GC/FT-IR"; Anal. Chem. 1983, 55, 1361A. 11. Griffiths, P.R.; e Haseth, J.A. Fourier Transform-Infrare Spectrometry; Wiley-Interscience: New York, NY, Gurka, D. F.; Farnham, I.; Potter, B. B.; Pyle, S.; Titus, R. an Duncan, W. "Quantitation Capability of a Directly Linke Gas Chromatography/Fourier Transform Infrare/Mass Spectrometry System"; Anal. Chem., 1989, 61, CD-ROM Revision 0

11 TABLE 1. FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHIC/FOURIER TRANSFORM INFRARED IDENTIFICATION LIMITS FOR BASE/NEUTRAL EXTRACTABLES Ientification Limit a b -1c Compoun ng injecte µg/l max, cm Acenaphthene 40(25) 20(12.5) 799 Acenaphthylene 50(50) 25(25) 799 Anthracene 40(50) 20(25) 874 Benzo(a)anthracene (50) (25) 745 Benzo(a)pyrene (100) (50) 756 Bis(2-chloroethyl) ether 70(10) 35(5) 1115 Bis(2-chloroethoxy)methane 50(10) 25(5) 1084 Bis(2-chloroisopropyl) ether 50(10) 25(5) 1088 Butyl benzyl phthalate 25(10) 12.5(5) Bromophenyl phenyl ether 40(5) 20(2.5) Chloronaphthalene Chloroaniline Chlorophenyl phenyl ether 20(5) 10(2.5) 1242 Chrysene (100) (50) 757 Di-n-butyl phthalate 20(5) 10(2.5) 1748 Dibenzofuran Diethyl phthalate 20(5) 10(2.5) 1748 Dimethyl phthalate 20(5) 10(2.5) 1751 Di-n-octyl phthalate 25(10) 12.5(5) 1748 Di-n-propyl phthalate 25(5) 12.5(2.5) ,2-Dichlorobenzene ,3-Dichlorobenzene ,4-Dichlorobenzene ,4-Dinitrotoluene ,6-Dinitrotoluene Bis-(2-ethylhexyl) phthalate 25(10) 12.5(5) 1748 Fluoranthene 100(50) 50(25) 773 Fluorene 40(50) 20(25) 737 Hexachlorobenzene Hexachlorocyclopentaiene Hexachloroethane ,3-Hexachlorobutaiene Isophorone Methylnaphthalene Naphthalene 40(25) 20(12.5) 779 Nitrobenzene N-Nitrosoimethylamine 20(5) 10(2.5) 1483 N-Nitrosoi-n-propylamine 50(5) 25(2.5) 1485 N-Nitrosoiphenylamine Nitroaniline Nitroaniline CD-ROM Revision 0

12 TABLE 1. (Continue) Ientification Limit a b -1c Compoun ng injecte µg/l max, cm 4-Nitroaniline Phenanthrene 50(50) 25(25) 729 Pyrene 100(50) 50(25) 820 1,2,4-Trichlorobenzene 50(25) 25(12.5) 750 a b c Determine using on-column injection an the conitions of Sec A meium -1 * 10 ban HgCTe etector [ cm ; D value ( peak 1000 Hz, 1) 4.5 x 10 cm 1/2-1 2 Hz W ] type with a 0.25 mm focal chip was use. The GC/FT-IR system is a 1976 retrofitte moel. Values in parentheses were etermine with a new -1 * (1986) GC/FT-IR system. A narrow ban HgCTe etector [ cm ; D value 10 1/2-1 ( peak 1000 Hz, 1) 4 x 10 cm Hz W ] was use. Chromatographic conitions are those of Sec Base on a 2 µl injection of a one liter sample that has been extracte an concentrate to a volume of 1.0 ml. Values in parentheses were etermine with a new (1986) GC/FT-IR system. A narrow ban HgCTe etector [ cm - 1 * 10 1/2-1 ; D value ( peak 1000 Hz, 1) 4 x 10 cm Hz W ] was use. Chromatographic conitions are those of Sec Most intense IR peak an suggeste quantitation peak. Detecte as iphenylamine. CD-ROM Revision 0

13 TABLE 2. FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHIC/FOURIER TRANSFORM INFRARED ON-LINE AUTOMATED IDENTIFICATION LIMITS FOR ACIDIC EXTRACTABLES Ientification Limit a b -1c Compoun ng injecte µg/l max, cm Benzoic aci Chlorophenol Chlorophenol Chloro-3-methylphenol Methylphenol Methylphenol ,4-Dichlorophenol ,4-Dinitrophenol ,6-Dinitro-2-methylphenol Nitrophenol Nitrophenol Pentachlorophenol Phenol ,4,6-Trichlorophenol ,4,5-Trichlorophenol a b c Operating conitions are the same as those cite in Sec Base on a 2 µl injection of a one liter sample that has been extracte an concentrate to a volume of 1.0 ml. Most intense IR peak an suggeste quantitation peak. Subject to interference from co-eluting compouns. CD-ROM Revision 0

14 TABLE 3. GAS-PHASE GROUP FREQUENCIES Number of Frequency Functionality Class Compouns Range, cm -1 Ether Aryl, Alkyl Benzyl, Alkyl Diaryl Dialkyl Alkyl, Vinyl Ester Unsubstitute Aliphatic Aromatic Monosubstitute Acetate Nitro Aliphatic Aromatic Nitrile Aliphatic Aromatic Ketone Aliphatic (acyclic) (, unsaturate) Aromatic Amie Substitute Acetamies Alkyne Aliphatic Aci Aliphatic Dimerize-Aliphatic Aromatic Phenol 1,4-Disubstitute ,3-Disubstitute ,2-Disubstitute (continue) CD-ROM Revision 0

15 TABLE 3. (Continue) Number of Frequency Functionality Class Compouns Range, cm -1 Alcohol Primary Aliphatic Seconary Aliphatic Tertiary Aliphatic Amine Primary Aromatic Seconary Aromatic Aliphatic Alkane Alehye Aromatic Aliphatic Benzene Monosubstitute CD-ROM Revision 0

16 TABLE 4. FUSED SILICA CAPILLARY COLUMN GC/FT-IR QUANTITATION RESULTS Concentration Maximum Integrate Range, an b Absorbance c Absorbance Ientification Correlation Correlation Compoun a Limit, ng Coefficient Coefficient Acenaphthene Acenaphthylene Anthracene Benzo(a)anthracene Benzoic aci Benzo(a)pyrene Bis(2-chloroethoxy)methane Bis(2-chloroethyl) ether Bis(2-chloroisopropyl) ether Bromophenyl phenyl ether Butyl benzyl phthalate Chloroaniline Chloro-3-methylphenol Chloronaphthalene Chlorophenol Chlorophenol e 4-Chlorophenyl phenyl ether Chrysene Dibenzofuran Di-n-butyl phthalate ,2-Dichlorobenzene ,3-Dichlorobenzene ,4-Dichlorobenzene ,4-Dichlorophenol Dimethyl phthalate Dimethyl phthalate Dinitro-2-methylphenol ,4-Dinitrophenol ,4-Dinitrotoluene ,6-Dinitrotoluene Di-n-octyl phthalate Bis(2-ethylhexyl) phthalate Fluoranthene Fluorene Hexachlorobenzene ,3-Hexachlorobutaiene Hexachlorocyclopentaiene Hexachloroethane Isophorone Methylnaphthalene (continue) CD-ROM Revision 0

17 TABLE 4. (Continue) Concentration Maximum Integrate Range, an b Absorbance c Absorbance Ientification Correlation Correlation Compoun a Limit, ng Coefficient Coefficient 2-Methylphenol Methylphenol Naphthalene Nitroaniline Nitroaniline Nitroaniline Nitrobenzene Nitrophenol e 4-Nitrophenol N-Nitrosoimethylamine N-Nitrosoiphenylamine N-Nitrosoi-n-propylamine Pentachlorophenol Phenanthrene Phenol Pyrene ,2,4-Trichlorobenzene ,4,5-Trichlorophenol ,4,6-Trichlorophenol a b c e Lower en of range is at or near the ientification limit. FT-IR scan with highest absorbance plotte against concentration. Integrate absorbance of combine FT-IR scans which occur at or above the chromatogram peak half-height. Regression analysis carrie out at four concentration levels. Each level analyze in uplicate. Chromatographic conitions are state in Sec Subject to interference from co-eluting compouns. CD-ROM Revision 0

18 METHOD 8410 GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED (GC/FT-IR) SPECTROMETRY FOR SEMIVOLATILE ORGANICS: CAPILLARY COLUMN CD-ROM Revision 0