### SW-846 Update V 8410 - 1 Revision 1 **October 2012 METHOD 8410** 

**GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED**

**SPECTROMETRY FOR SEMIVOLATILE ORGANICS:**

**CAPILLARY COLUMN**

**1.0 SCOPE AND APPLICATION**

**1.1 This method covers the automated identification , or compound class assignment of**  **unidentifiable compounds, of solvent-extractable se mivolatile organic compounds which are**  **amenable to analysis by gas chromatograph/Fourier t ransform-infrared spectrometer (GC/FT**  **IR). GC/FT-IR can be a useful complement to gas ch romatograph/mass spectrometer (GC/MS)**  **analysis (Method 8270). It is particularly well su ited for the identification of specific isomers tha**  **t are not differentiated using GC/MS. Compound class**  **assignments are made using infrared (IR) group absorption frequencies. The presence of an I**  **R band in the appropriate group frequency region may be taken as evidence of the possible pre**  **sence of a particular compound class, while its absence may be construed as evidence that the c**  **ompound class in question is not present. This evidence will be further strengthened by the p**  **resence of confirmatory group frequency bands. Identification limits of the following comp**  **ounds have been demonstrated by this method.**

**Compound Name CAS No.**  **a**

**Acenaphthene 83-32-9**  **Acenaphthylene 208-96-8** 
**Anthracene 120-12-7**  **Benzo(a)anthracene 56-55-3**  **Benzo(a)pyrene 50-32-8** 
**Benzoic acid 65-85-0**  **Bis(2-chloroethoxy)methane 111-91-1**  **Bis(2-chloroethyl)ether 111-44-4**  **Bis(2-chloro-1-methylethyl)ether b**  **108-60-1 Bis(2-ethylhexyl)phthalate**  **117-81-7 4-Bromophenyl phenyl ether**  **101-55-3 Butyl benzyl phthalate**  **85-68-7**
**4-Chloroaniline 106-47-8**  **4-Chloro-3-methylphenol 59-50-7**  **2-Chloronaphthalene 91-58-7**  **2-Chlorophenol 95-57-8**  **4-Chlorophenol 106-48-9**  **4-Chlorophenyl phenyl ether 7005-72-3**  **Chrysene 218-01-9** 
**Dibenzofuran 132-64-9**  **Di-n-butyl phthalate 84-74-2**  **1,2-Dichlorobenzene 95-50-1**  **1,3-Dichlorobenzene 541-73-1**  **1,4-Dichlorobenzene 106-46-7**  **2,4-Dichlorophenol 120-83-2**  **Diethyl phthalate 84-66-2**  **Dimethyl phthalate 131-11-3** 

### SW-846 Update V 8410 - 2 Revision 1 **October 2012 Compound Name**  **CAS No. a** 

**4,6-Dinitro-2-methylphenol 534-52-1**  **2,4-Dinitrophenol 51-28-5**  **2,4-Dinitrotoluene 121-14-2**  **2,6-Dinitrotoluene 606-20-2**  **Di-n-octyl phthalate 117-84-0**  **Di-n-propyl phthalate 131-16-8** 
**Fluoranthene 206-44-0** 
**Fluorene 86-73-7** 
**Hexachlorobenzene 118-74-1**  **1,3-Hexachlorobutadiene 87-68-3**  **Hexachlorocyclopentadiene 77-47-4** 
**Hexachloroethane 67-72-1**  **Isophorone 78-59-1**  **2-Methylnaphthalene 91-57-6**  **2-Methylphenol 95-48-7**  **4-Methylphenol 106-44-5**  **Naphthalene 91-20-3** 
**2-Nitroaniline 88-74-4** 
**3-Nitroaniline 99-09-2** 
**4-Nitroaniline 100-01-6** 
**Nitrobenzene 98-95-3**  **2-Nitrophenol 88-75-5**  **4-Nitrophenol 100-02-7**  **N-Nitrosodimethylamine 62-75-9**  **N-Nitrosodiphenylamine 86-30-9**  **N-Nitroso-di-n-propylamine 621-64-7**  **Pentachlorophenol 87-86-5** 
**Phenanthrene 85-01-8** 
**Phenol 108-95-2**  **Pyrene 129-00-0**  **1,2,4-Trichlorobenzene 120-82-1**  **2,4,5-Trichlorophenol 95-95-4**  **2,4,6-Trichlorophenol 88-06-2** 

**a Chemical Abstract Services (CAS) Registry Number.** 

**b Chemical name was changed by the Integrated Risk I**  **nformation System (IRIS) on November 30, 2007 from Bis(2-chloroisopropyl)ether**  **to Bis(2-chloro-1- methylethyl)ether (common name). This compound is**  **also known as 2,2’-oxybis(1- chloropropane) (CAS index name). See the link at**  **http://www.epa.gov/iris/subst/0407.htm , Section VII for the “Revision History” and**  **Section VIII, for “Synonyms” of this chemical.**

**1.2 This method is applicable to the determination of most extractable, semivolatile**  **organic compounds in wastewater, soils and sediment s, and solid wastes. Benzidine can be**  **subject to losses during solvent concentration and analysis by gas chromatograph (GC); α-BHC,**  **β-BHC, Endosulfan I and II, and Endrin are subject to decomposition under the alkaline**  **conditions of the extraction step; Endrin is subjec t to decomposition during GC analysis; and**  **Hexachlorocyclopentadiene and N-Nitrosodiphenylamin e may decompose during extraction and** 

### SW-846 Update V 8410 - 3 Revision 1 **October 2012 GC analysis. Other extraction and/or instrumentati**  **on procedures should be considered for unstable analytes.** 

**1.3 The identification limit of this method may de pend strongly upon the level and type**  **of semivolatile extractants amenable to GC analysis . The values listed in Tables 1 and 2**  **represent the minimum quantities of semivolatile or ganic compounds which have been identified**  **by the specified GC/FT-IR system, using this method and under routine environmental analysis**  **conditions. Capillary GC/FT-IR wastewater identifi cation limits of 25 μg/L may be achieved for**  **weak IR absorbers with this method, while the corre sponding identification limit for strong IR**  **absorbers is 2 μg/L. Identification limits for oth er sample matrices can be calculated from the**  **wastewater values after choice of the proper sample workup procedure (see Sec. 11.1).** 

**2.0 SUMMARY OF METHOD**

**Prior to using this method, the samples should be prepared for chromatography using the**  **appropriate sample preparation and cleanup methods. This method describes chromatographic**  **conditions that will allow for the separation of th e compounds in the extract and uses FT-IR for**  **detection and quantitation of the target analytes.**

**3.0 DEFINITIONS**

**Refer to Chapter One, the individual determinative methods, and the manufacturer's**  **instructions for definitions that may be relevant.**

**4.0 INTERFERENCES**

**4.1 Glassware and other sample processing hardware must be thoroughly cleaned to**  **prevent contamination and misinterpretation. All o f these materials must be demonstrated to be** 
**free from interferences under the conditions of the analysis by running method blanks. Specific**  **selection of reagents or purification of solvents b y distillation in all-glass systems may be**  **required.**

**4.2 Matrix interference will vary considerably fro m source to source, depending upon**  **the diversity of the residual waste being sampled. While general cleanup techniques are**  **provided as part of this method, unique samples may require additional cleanup to isolate the**  **analytes of interest from interferences in order to achieve maximum sensitivity.** 

**4.3 4-Chlorophenol and 2-nitrophenol are subject t o interference from coeluting**  **compounds.**

**4.4 Clean all glassware as soon as possible after use by rinsing with the last solvent**  **used. Glassware should be sealed/stored in a clean environment immediately after drying to**  **prevent any accumulation of dust or other contamina nts.** 

**5.0 SAFETY**

**This method does not address all safety issues asso ciated with its use. The laboratory is**  **responsible for maintaining a safe work environment and a current awareness file of**  **Occupational Safety and Health Administration (OSHA ) regulations regarding the safe handling** 

### SW-846 Update V 8410 - 4 Revision 1 **October 2012 of the chemicals and instrumentation included in th**  **is method. A reference file of material safety data sheets (MSDSs) should be available to all pers**  **onnel involved in these analyses.**

**6.0 EQUIPMENT AND SUPPLIES**

**6.1 GC/FT-IR Spectrometric Equipment**

**6.1.1 FT- IR spectrometer – A spectrometer capabl e of collecting at least one**  **scan set per second at 8 cm -1**  **resolution is required. In general, a spectromete r purchased**  **after 1985, or retrofitted to meet post-1985 FT-IR improvements, will be necessary to meet**  **needed sensitivity of this protocol. A state-of-th e-art analog/digital (A/D) converter is**  **required, since it has been shown that the signal-t o-noise ratio of single-beam GC/FT-IR**  **systems is A/D converter limited.**

**6.1.2 GC/FT-IR interface – The interface should b e lightpipe volume-optimized**  **for the selected chromatographic conditions (lightp ipe volume of 100-200 μL for capillary**  **columns). The shortest possible inert transfer lin e (preferably fused silica) should be used**  **to interface the end of the chromatographic column to the lightpipe. If fused silica capillary**  **columns are employed, the end of the GC column can serve as the transfer line if it is**  **adequately heated. It has been widely demonstrated that the optimum lightpipe volume is**  **equal to the full width at half height of the GC el uate peak.** 

**6.1.3 Capillary column – A fused silica DB-5 30 m x 0.32 mm capillary column**  **with 1.0 μm film thickness (or equivalent)**

**6.1.4 Data Acquisition – A computer system dedica ted to the GC/FT-IR system**  **to allow the continuous acquisition of scan sets fo r a full chromatographic run. Peripheral**  **data storage systems should be available (magnetic tape and/or disk) for the storage of all**  **acquired data. Software should be available to all ow the acquisition and storage of every**  **scan set to locate the file numbers and transform h igh signal/noise (S/N) scan sets, and to**  **provide a real-time reconstructed chromatogram.**

**6.1.5 Detector – A cryoscopic, medium-band mercur y/cadmium/tellurium**  **(HgCdTe or MCT) detector with the smallest practica l focal area. Typical narrow-band**  **MCT detectors operate from 3800-800 cm -1**  **, but medium-band MCT detectors can reach**
**650 cm -1**  **. A 750 cm -1**  **cutoff (or lower) is desirable since it allows the detection of typical**  **carbon-chlorine stretch and aromatic out-of-plane c arbon-hydrogen vibrations of**  **environmentally important organo-chlorine and polyn uclear aromatic compounds. The**  **MCT detector sensitivity (D)* should be ≥ 1 x 10** **10 cm.** 

**6.1.6 Lightpipe – Constructed of inert materials, gold-coated, and volume**  **optimized for the desired chromatographic condition s (see Sec. 11.3)** 

**6.1.7 GC – The FT-IR spectrometer should be inter faced to a temperature**  **programmable GC equipped with a Grob-type (or equiv alent) purged splitless injection**  **system suitable for capillary glass columns or an o n-column injector system.** 

**A short, inert transfer line should interface the GC to the FT-IR lightpipe and, if**  **applicable, to the GC detector. Fused silica GC co lumns may be directly interfaced to the**  **lightpipe inlet and outlet.**

**6.2 Dry purge gas – If the spectrometer is the pur ge-type, provisions should be made**  **to provide a suitable continuous source of dry purg e-gas to the FT-IR spectrometer.** 

### SW-846 Update V 8410 - 5 Revision 1 **October 2012 6.3 Dry carrier gas – The carrier gas should be pa**  **ssed through an efficient cartridge type drier.** 

**6.4 Syringes – 1 μL, 10 μL**

**7.0 REAGENTS AND STANDARDS**

**7.1 Reagent-grade inorganic chemicals shall be use d in all tests. Unless otherwise**  **indicated, it is intended that all reagents shall c onform to the specifications of the Committee on**  **Analytical Reagents of the American Chemical Societ y (ACS), where such specifications are**  **available. Other grades may be used, provided it i s first ascertained that the reagent is of**  **sufficiently high purity to permit its use without lessening the accuracy of the determination.** 

**7.2 Organic-free reagent water. All references to water in this method refer to organic**  **free reagent water, as defined in Chapter One.**

**7.3 Solvents**

**7.3.1 Acetone, CH 3**  **COCH 3**  **– Pesticide quality, or equivalent**

**7.3.2 Methylene chloride, CH 2**  **Cl 2**  **– Pesticide quality, or equivalent**

**7.4 Stock standard solutions (1000 mg/L) – Standar d solutions can be prepared from**  **pure standard materials or purchased as a certified solution.** 

**7.4.1 Prepare stock standard solutions by accurat ely weighing 0.1000±0.0010**  **g of pure material. Dissolve the material in pesti cide-quality acetone or other suitable** 
**solvent and dilute to volume in a 100-mL volumetric flask. Larger volumes can be used at**  **the convenience of the analyst. When compound puri ty is assayed to be 96 percent or**  **greater, the weight may be used without correction to calculate the concentration of the**  **stock standard. Commercially prepared stock standa rds may be used at any**  **concentration if they are certified by the manufact urer or by an independent source.** 

**7.4.2 Transfer the stock standard solutions into bottles with Teflon-lined screw**  **caps. Store at 4 °C and protect from light. Stock standard solutions should be checked**  **frequently for signs of degradation or evaporation, especially just prior to preparing**  **calibration standards from them.**

**7.4.3 Stock standard solutions must be replaced a fter 6 months or sooner if**  **comparison with quality control (QC) reference samp les indicates a problem.** 

**7.5 Calibration standards and internal standards - For use in situations where GC/FT**  **IR will be used for primary quantitation of analyte s rather than confirmation of GC/MS**  **identification.**

**7.5.1 Prepare calibration standards that contain the compounds of interest,**  **either singly or mixed together. The standards sho uld be prepared at concentrations that**  **will completely bracket the working range of the ch romatographic system (at least one**  **order of magnitude is suggested).**

**7.5.2 Prepare internal standard solutions. Sugge sted internal standards are 1-**  **fluoronaphthalene and p-terphenyl-d14, or deuterate d versions of 2-chlorophenol, phenol,** 

### SW-846 Update V 8410 - 6 Revision 1 **October 2012 bis(2-chloroethoxy)methane, 2,4-dichlorophenol, phe**  **nanthrene, anthracene, and butyl benzyl phthalate. If deuterated versions aren’t us**  **ed, compounds that are on the method target analyte list may be used as internal standar**  **ds as long as they aren’t an analyte for a given site, and historical data are available to en**  **sure their absence at a given site.**
**Determine the internal standard concentration level s from the minimum identifiable**  **quantities. See Tables 1 and 2.**

**8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE**

**See Chapter 4, Organic Analytes, Sec. 4.1 for more information on this topic.** 

**9.0 QUALITY CONTROL**

**9.1 General guidance**

**Refer to Chapter One for guidance on quality assura nce (QA) and QC protocols. When**  **inconsistencies exist between QC guidelines, method -specific QC criteria take precedence over**  **both technique-specific and Chapter One criteria; t echnique-specific QC criteria take**  **precedence over Chapter One criteria. Any effort i nvolving collection of analytical data should**  **include development of a structured and systematic planning document, such as a quality**  **assurance project plan (QAPP) or a sampling and ana lysis plan (SAP), which translates project**  **objectives and specifications into directions for t hose who will implement the project and assess** 
**the results.**

**Each laboratory should maintain a formal QA program . The laboratory should also maintain**  **records to document the quality of the data generat ed. Development of in-house QC limits for**  **each method is encouraged, as described in Sec. 9.6 of Method 8000. Use of instrument**  **specific QC limits is encouraged, provided such lim its will generate data appropriate for use in**  **the intended application. All data sheets and QC d ata should be maintained for reference or**  **inspection. QC to validate sample extraction is co vered in Method 3500 and in the extraction**  **method utilized. If extract cleanup was performed, follow the QC in Method 3600 and in the**  **specific cleanup method.**

**9.2 Initial demonstration of proficiency (IDP)**

**Prior to implementation of a method, each laborator y must perform an IDP consisting of at**  **least four replicate reference samples spiked into a clean matrix taken through the entire**  **sample preparation and analysis. Whenever a signif icant change to instrumentation or a**  **procedure occurs, the laboratory must demonstrate t hat acceptable precision and bias can still**  **be obtained by the changed conditions. Whenever ne w staff members are trained, an analyst**  **IDP must be performed.**

**9.2.1 Demonstration of proficiency for new analysts**

**Each laboratory should have a training program whic h documents that a new**  **analyst is capable of performing the method, or por tion of the method, for which the**  **analyst is responsible. This demonstration should document that the new analyst is**  **capable of successfully following the standard oper ating procedure (SOP) established by**  **the laboratory.**

**9.3 It is recommended that the laboratory adopt add itional QA practices for use with**  **this method. The specific practices that are most productive depend upon the needs of the** 

### SW-846 Update V 8410 - 7 Revision 1 **October 2012 laboratory and the nature of the samples. Whenever**  **possible, the laboratory should analyze standard reference materials and participate in rel**  **evant performance evaluation studies.**

**9.4 Lower limit of quantitation (LLOQ)**

**The laboratory shall establish the LLOQ as the low est point of quantitation, which**  **in most cases, is the lowest concentration in the c alibration curve. LLOQ verification is**  **recommended for each project application to validat e quantitation capability at low analyte**  **concentration levels. This verification may be acc omplished with either clean control material**  **(e.g., reagent water, solvent blank, Ottawa sand, d iatomaceous earth, etc.) or a representative**  **sample matrix, free of target compounds. Optimally , the LLOQ should be less than the desired**  **regulatory action levels based on the stated data q uality objectives (DQOs).** 

**9.5 One hundred percent line test – Set the GC/FT- IR operating conditions to those**  **employed for the sensitivity test (see Sec. 11.5). Collect 16 scans over the entire detector**  **spectral range. Plot the test and measure the peak -to-peak noise between 1800 and 2000 cm**  **-1**

**. This noise should be ≤ 0.15%. Store this plot for**  **future reference.**

**9.6 Single beam test – With the GC/FT-IR at analys is conditions, collect 16 scans in**  **the single-beam mode. Plot the co-added file and c ompare with a subsequent file acquired in** 
**the same fashion several minutes later. Note if th e spectrometer is at purge equilibrium. Also,**  **check the plot for signs of deterioration of the li ghtpipe potassium bromide windows. Store this**  **plot for future reference.**

**9.7 Align test – With the lightpipe and MCT detect or at thermal equilibrium, check the**  **intensity of the centerburst versus the signal temp erature calibration curve. Signal intensity**  **deviation from the predicted intensity may mean the rmal equilibrium has not yet been achieved,**  **loss of detector coolant, decrease in source output , or a loss in signal throughput resulting from**  **lightpipe deterioration.**

**9.8 Mirror alignment – Adjust the interferometer m irrors to attain the most intense**  **signal. Data collection should not be initiated un til the interferogram is stable. If necessary,**  **align the mirrors prior to each GC/FT-IR run.**

**9.9 Lightpipe – The lightpipe and lightpipe window s should be protected from moisture** 
**and other corrosive substances at all times. For t his purpose, maintain the lightpipe**  **temperature above the maximum GC program temperatur e but below its thermal degradation**  **limit. When not in use, maintain the lightpipe tem perature slightly above ambient. At all times,**  **maintain a flow of dry, inert, carrier gas through the lightpipe.** 

**9.10 Beamsplitter – If the spectrometer is thermos tated, maintain the beamsplitter at a**  **temperature slightly above ambient at all times. I f the spectrometer is not thermostated,**  **minimize exposure of the beamsplitter to atmospheri c water vapor.** 

**10.0 CALIBRATION AND STANDARDIZATION**

**10.1 Calibration – Refer to Method 8000 for proper calibration techniques.** 

**10.2 Calibration must take place using the same sam ple introduction method that will be**  **used to analyze actual samples.**

### SW-846 Update V 8410 - 8 Revision 1 **October 2012 11.0 PROCEDURE** 

**11.1 Sample Preparation – Samples must be prepared by one of the following**  **methods prior to GC/FT-IR analysis.**

**Matrix Methods**
**Water 3510, 3520** 

**Soil/sediment 3540, 3541, 3550** 

**Waste 3540, 3541, 3550, 3580**

**11.2 Extracts may be cleaned up by Method 3640, Ge l-Permeation Cleanup.** 

**11.3 Initial Calibration**

**Recommended GC/FT-IR conditions:**

**Scan time: At least 2 scan/sec Initial column temperature and hold time: 40 °C fo**  **r 1 minute Column temperature program: 40-280 °C at 10 °C/mi**  **n Final column temperature to hold: 280 °C**  **Injector temperature: 280-300 °C Transfer line temperature: 270 °C**  **Lightpipe: 280 °C Injector: Grob-type, splitless or on-column**  **Sample volume: 2-3 μL Carrier gas: Dry helium at about 1 mL/min** 

**11.4 With an oscilloscope, check the detector cent erburst intensity versus the**  **manufacturer’s specifications. Increase the source voltage, if necessary, to meet these**  **specifications. For reference purposes, laboratori es should prepare a plot of time versus**  **detector voltage over at least a five-day period.**

**11.5 Capillary column interface sensitivity test – Install a 30 m x 0.32 mm fused silica**  **capillary column coated with 1.0 μm of DB-5 (or equ ivalent). Set the lightpipe and transfer lines**  **at 280 °C (if used). Under splitless Grob-type or on-column injection conditions, inject 25 ng of**  **nitrobenzene, dissolved in 1 μL of methylene chlori de. The nitrobenzene should be identified by**  **the on-line library software search within the firs t five hits (nitrobenzene should be contained**  **within the search library).**

**11.6 Interferometer – If the interferometer is air driven, adjust the interferometer drive**  **air pressure to manufacturer’s specifications.**

**11.7 MCT detector check – If the centerburst inten sity is 75 percent or less of the**  **mean intensity of the plot maximum obtained by the procedure of Sec. 11.4, install a new** 
**source and check the MCT centerburst with an oscill oscope versus the manufacturer’s**  **specifications (if available). Allow at least five hours of new source operation before data**  **acquisition.**

### SW-846 Update V 8410 - 9 Revision 1 **October 2012 11.8 Frequency calibration – At the present time,**  **no consensus exists within the spectroscopic community on a suitable frequency ref**  **erence standard for vapor phase FT-IR. One reviewer has suggested the use of indene as an**  **on-the-fly standard.**

**11.9 Minimum identifiable quantities – Using the G C/FT-IR operating parameters**  **specified in Sec. 11.3, determine the minimum ident ifiable quantities for the compounds of** 
**interest.**

**11.9.1 Prepare a plot of lightpipe temperature ve rsus MCT centerburst intensity**  **(in volts or other vertical height units). This pl ot should span the temperature range**  **between ambient and the lightpipe thermal limit in increments of about 20 °C. Use this**  **plot for daily QA/QC (see Sec. 9.7). Note that mod ern GC/FT-IR interfaces (1985 and**  **later) may have eliminated most of this temperature effect.** 

**11.10 GC/FT-IR extract analysis**

**11.10.1 Analysis – Analyze the dried methylene ch loride extract using the**  **chromatographic conditions specified in Sec. 11.3 f or capillary column interfaces.** 

**11.10.2 GC/FT-IR identification – Visually compar e the analyte IR spectrum**  **versus the search library spectrum of the most prom ising on-line library search hits.**  **Report, as identified, those analytes with IR frequ encies for the five (maximum number)**  **most intense IR bands (S/N ≥ 5) which are within ± 5.0 cm**  **-1 of the corresponding bands in**  **the library spectrum. Choose IR bands which are sh arp and well resolved. The software**  **used to locate spectral peaks should employ the pea k "center of gravity" technique. In**  **addition, the IR frequencies of the analyte and lib rary spectra should be determined with**  **the same computer software.**

**11.10.3 Retention time confirmation – After visua l comparison of the analyte and**  **library spectra as described in Sec. 11.10.2, compa re the relative retention times (RRT) of**  **the analyte and an authentic standard of the most p romising library search hit. The**  **standard and analyte RRT should agree within ± 0.01 RRT units when both are**  **determined at the same chromatographic conditions.**

**11.10.4 Compound class or functionality assignmen t – If the analyte cannot be**  **unequivocally identified, report its compound class or functionality. See Table 3 for gas**  **phase group frequencies to be used as an aid for co mpound class assignment. It should**  **be noted that FT-IR gas-phase group stretching freq uencies are 0-30 cm**  **-1 higher in**  **frequency than those of the condensed phase.**

**11.10.5 Quantitation – This protocol can be used to confirm GC/MS**  **identifications, with subsequent quantitation. Two FT-IR quantitation techniques and a**  **supplemental GC detector technique are also provide d.** 

**11.10.5.1 Integrated absorbance technique - Afte r analyte identification,** 

**construct a standard calibration curve of concentra tion versus integrated IR**  **absorbance. For this purpose, choose for integrati on only those FT-IR scans**  **which are at or above the peak half-height. The ca libration curve should span at**  **least one order of magnitude and the working range should bracket the analyte** 
**concentration.**

**11.10.5.2 Maximum absorbance IR band technique – Following analyte**  **identification, construct a standard calibration cu rve of concentration versus** 

### SW-846 Update V 8410 - 10 Revision 1 **October 2012 maximum IR band intensity. For this purpose, choos**  **e an intense, symmetrical and**
**well resolved IR absorbance band.**

**NOTE : IR transmission is not proportional to concentrat**  **ion. Select the FT-IR scan**

**with the highest absorbance to plot against concent ration. The calibration**  **curve should span at least one order of magnitude a nd the working range**  **should bracket the analyte concentration. This met hod is most practical for**  **repetitive, target compound analyses. It is more s ensitive than the**  **integrated absorbance technique.**

**11.10.5.3 Supplemental GC detector technique – I f a GC detector is** 

**used in tandem with the FT-IR detector, the followi ng technique may be used:**  **following analyte identification, construct a stand ard calibration curve of**  **concentration versus integrated peak area. The cal ibration curve should span at**  **least one order of magnitude and the working range should bracket the analyte**  **concentration. This method is most practical for r epetitive, target compound**  **analyses.**

**12.0 DATA ANALYSIS AND CALCULATIONS**

**12.1 See Method 8000, Sec. 11 for information regar ding data analysis and** 
**calculations.**

**12.2 Results must be reported in units commensur ate with their intended use and all**  **dilutions must be taken into account when computing final results.** 

**13.0 METHOD PERFORMANCE**

**13.1 Method 8410 has been in use at the U.S. Envir onmental Protection Agency (EPA**  **or the Agency) Environmental Monitoring Systems Lab oratory for many years. Portions of it**  **have been reviewed by key members of the FT-IR spec troscopic community (Ref 9). Side-by**  **side comparisons with GC/MS sample analyses indicat e similar demands upon analytical**  **personnel for the two techniques. Extracts previou sly subjected to GC/MS analysis are**  **generally compatible with GC/FT-IR. However, it sh ould be kept in mind that lightpipe windows**  **are typically water soluble. Thus, extracts must b e vigorously dried prior to analysis.** 

**13.2 Table 4 provides performance data for this me thod.** 

**14.0 POLLUTION PREVENTION**

**14.1 Pollution prevention encompasses any technique that reduces or eliminates the**  **quantity and/or toxicity of waste at the point of g eneration. Numerous opportunities for pollution**  **prevention exist in laboratory operation. The EPA has established a preferred hierarchy of**  **environmental management techniques that places pol lution prevention as the management**  **option of first choice. Whenever feasible, laborat ory personnel should use pollution prevention**  **techniques to address their waste generation. When wastes cannot be feasibly reduced at the**  **source, the EPA recommends recycling as the next be st option.** 

**14.2 For information about pollution prevention th at may be applicable to laboratories** 
**and research institutions consult** Less is Better: Laboratory Chemical Management for Waste

### SW-846 Update V 8410 - 11 Revision 1 **October 2012** Reduction **, a free publication available from the ACS, Commit tee on Chemical Safety,**  **http://portal.acs.org/portal/fileFetch/C/WPCP_01229 0/pdf/WPCP_012290.pdf** 

**.**

**15.0 WASTE MANAGEMENT**

**The EPA requires that laboratory waste management p ractices be conducted consistent**  **with all applicable rules and regulations. Laborat ories are urged to protect air, water, and land**  **by minimizing and controlling all releases from hoo ds and bench operations, complying with the**  **letter and spirit of any sewer discharge permits an d regulations and complying with all solid and**  **hazardous waste regulations, particularly the hazar dous waste identification rules and land**  **disposal restrictions. For further information on waste management, consult**  The Waste Management Manual for Laboratory Personnel **available from the ACS at the web address listed in Sec. 14.2 above.** 

### SW-846 Update V 8410 - 12 Revision 1 **October 2012 16.0 REFERENCES** 

**1. U.S. Environmental Protection Agency, Environme ntal Monitoring and Support**  **Laboratory,** Handbook for Analytical Quality Control in Water an d Wastewater Laboratories, **ORD Publication Offices of Center for Environmental Research Information:**  **Cincinnati, OH, Sec. 4, EPA-600/4-79-019, March 197 9.** 

**2. R. R. Freeman, Hewlett Packard Application Note: "Quantitative Analysis Using a Purged**  **Splitless Injection Technique",** ANGC **7-76.**

**3. R. H. Cole,** Tables of Wavenumbers for the Calibration of Infrar ed Spectrometers **; Pergamon: New York, 1977.** 

**4. J. G. Grasselli, P. R. Griffiths, and R. W. Hann ah, "Criteria for Presentation of Spectra**  **from Computerized IR Instruments",** Appl. Spectrosc **., 36, 87, 1982.**

**5. R. A. Nyquist,** The Interpretation of Vapor-Phase Infrared Spectra, Group Frequency Data, Volume I, **Sadtler Laboratories: Philadelphia, PA, 1984.**

**6. G. Socrates,** Infrared Characteristic Group Frequencies **, John Wiley and Sons: New York, NY, 1980.** 

**7. L. J. Bellamy,** The Infrared Spectra of Complex Organic Molecules; 2 nd ed. **, John Wiley and Sons: New York, NY, 1958.** 

**8. H. A. Szymanski,** Infrared Band Handbook, Volumes I and II **, Plenum: New York, NY,**
**1965.**

**9. D. F. Gurka, "Interim Protocol for the Automate d Analysis of Semivolatile Organic**  **Compounds by Gas Chromatography/Fourier Transform-I nfrared Spectrometry",**  Appl. Spectrosc. **, 39, 826, 1985.**

**10. P. R. Griffiths, J. A. de Haseth and L. V. Azar raga, "Capillary GC/FT-IR",**  Anal. Chem., **55**

**, 1361A, 1983.** 

**11. P. R. Griffiths and J. A. de Haseth,** Fourier Transform-Infrared Spectrometry **, Wiley Interscience: New York, NY, 1986.** 

**12. D. F. Gurka, I. Farnham, B. B. Potter, S. Pyle, R. Titus and W. Duncan, "Quantitation**  **Capability of a Directly Linked Gas Chromatography/ Fourier Transform Infrared/Mass**  **Spectrometry System",** Anal. Chem

**., 61, 1584, 1989.** 

**17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION D ATA** 

**The following pages contain the tables referenced b y this method.** 

### SW-846 Update V 8410 - 13 Revision 1 **October 2012 TABLE 1** 

**FUSED SILICA CAPILLARY COLUMN GC/FT-IR IDENTIFICATI ON LIMITS FOR**  **BASE/NEUTRAL EXTRACTABLES**

**Compound Identification Limit** 



### ν **max, cm -1c**  **ng injected a**  **μg/L b** 

**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-chloro-1-methylethyl)ether 50(10) 25(5) 1088**  **Butyl benzyl phthalate 25(10) 12.5(5) 1748 4-Bromophenyl phenyl ether 40(5) 20(2.5) 1238**  **2-Chloronaphthalene 110 55 851**

**4-Chloroaniline 40 20 1543 4-Chlorophenyl phenyl ether 20(5) 10(2.5) 1242**  **Chrysene (100) (50) 757**  **Di-n-butyl phthalate 20(5) 10(2.5) 1748**

**Dibenzofuran 40 20 1192 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) 1748 1,2-Dichlorobenzene 50 25 1458**  **1,3-Dichlorobenzene 50 25 779 1,4-Dichlorobenzene 50 25 1474**  **2,4-Dinitrotoluene 20 10 1547 2,6-Dinitrotoluene 20 10 1551**  **Bis-(2-ethylhexyl)phthalate 25(10) 12.5(5) 1748 Fluoranthene 100(50) 50(25) 773** 

**Fluorene 40(50) 20(25) 737** 

**Hexachlorobenzene 40 20 1346 Hexachlorocyclopentadiene 120 60 814** 

**Hexachloroethane 50 25 783 1,3-Hexachlorobutadiene 120 60 853**  **Isophorone 40 20 1690 2-Methylnaphthalene 110 55 3069**  **Naphthalene 40(25) 20(12.5) 779**

**Nitrobenzene 25 12.5 1539 N-Nitrosodimethylamine 20(5) 10(2.5) 1483**  **N-Nitrosodi-n-propylamine 50(5) 25(2.5) 1485 N-Nitrosodiphenylamine**  **d 40 20 1501** 

**2-Nitroaniline 40 20 1564**

**3-Nitroaniline 40 20 1583**

### SW-846 Update V 8410 - 14 Revision 1 **October 2012 Compound**  **Identification Limit**



### ν **max, cm -1c**  **ng injected a**  **μg/L b** 

**4-Nitroaniline 40 20 1362 Phenanthrene 50(50) 25(25) 729**  **Pyrene 100(50) 50(25) 820**  **1,2,4-Trichlorobenzene 50(25) 25(12.5) 750 1-Fluoronaphthalene**  **e (100) (50) 770**  **p-Terphenyl-d14 e**  **(100) (50) 712**

**a Determined using on-column injection and the con**  **ditions of Sec. 11.3. A medium-band HgCdTe detector [3800-700 cm**  **-1** **; D*value (λpeak 1000 Hz, 1) 4.5 x 10** **10 cm Hz**  **1/2 W**  **-1 ] type** 
**with a 0.25 mm 2**  **focal chip was used. The GC/FT-IR system is a 197 6 retrofitted model.**  **Values in parentheses were determined with a newer (1986) GC/FT-IR system. A narrow**  **band HgCdTe detector [3800-750 cm -1**  **; D*value (λpeak 1000 Hz, 1) 4 x 10** **10 cm Hz**  **1/2 W**  **-1 ]**  **was used. Chromatographic conditions are those of Sec. 11.3.** 

**b Based on a 2-μL injection of a 1-L sample that h**  **as been extracted and concentrated to a volume of 1.0 mL. Values in parentheses were deter**  **mined with a newer (1986) GC/FT-IR system. A narrow band HgCdTe detector [3800-750 cm**  **-1** **; D*value (λpeak 1000 Hz, 1) 4 x**
**10 10**  **cm Hz 1/2**  **W -1**  **] was used. Chromatographic conditions are those o f Sec. 11.3.** 

**c Most intense IR peak and suggested quantitation**  **peak.**

**d Detected as diphenylamine.** 

**e Suggested internal standard. Identification lim**  **it data is not actual, but is estimated high to assure sufficient amount or concentration.** 

### SW-846 Update V 8410 - 15 Revision 1 **October 2012 TABLE 2** 

**FUSED SILICA CAPILLARY COLUMN GC/FT-IR ON-LINE AUTO MATED IDENTIFICATION**  **LIMITS FOR ACIDIC EXTRACTABLES**

**Compound Identification Limit** 



### ν **max, cm -1c**  **ng injected a**  **μg/L b** 

**Benzoic acid 70 35 1751 2-Chlorophenol 50 25 1485**  **4-Chlorophenol d**  **100 50 1500 4-Chloro-3-methylphenol 25 12.5 1177**  **2-Methylphenol 50 25 748 4-Methylphenol 50 25 1177**  **2,4-Dichlorophenol 50 25 1481 2,4-Dinitrophenol 60 30 1346**  **4,6-Dinitro-2-methylphenol 60 30 1346 2-Nitrophenol**  **d 40 20 1335**  **4-Nitrophenol 50 25 1350 Pentachlorophenol 50 25 1381** 

**Phenol 70 35 1184 2,4,6-Trichlorophenol 120 60 1470**  **2,4,5-Trichlorophenol 120 60 1458**

**a Operating conditions are the same as those cited**  **in Sec. 11.3.**

**b Based on a 2-μL injection of a 1-L sample that h**  **as been extracted and concentrated to a volume of 1.0 mL.** 

**c Most intense IR peak and suggested quantitation**  **peak.**

**d Subject to interference from co-eluting compound**  **s.**

### SW-846 Update V 8410 - 16 Revision 1 **October 2012 TABLE 3** 

**GAS-PHASE GROUP FREQUENCIES**

**Functionality Class Number of**  **Compounds Frequency** 

**Range,** 

### ν **cm -1** 

**Ether Aryl, Alkyl 14 1215-1275 Benzyl, Alkyl 3 1103-1117**  **Diaryl 5 1238-1250 Dialkyl 12 1084-1130**  **Alkyl, Vinyl 3 1204-1207**
**1128-1142**

**Ester Unsubstituted Aliphatic 29 1748-1761**
**Aromatic 11 1703-1759**
**Monosubstituted Acetate 34 1753-1788**

**Nitro Aliphatic 5 1566-1594**
**1548-1589**
**1377-1408**
**1327-1381**
**Aromatic 18 1535-1566**
**1335-1358**

**Nitrile Aliphatic 9 2240-2265**
**Aromatic 9 2234-2245**

**Ketone Aliphatic (acyclic) 13 1726-1732 (α,β unsaturated) 2 1638-1699** 
**Aromatic 16 1701-1722**

**Amide Substituted Acetamides 8 1710-1724**

**Alkyne Aliphatic 8 3323-3329**

**Acid Aliphatic 24 3574-3580**
**22 1770-1782 Dimerized-Aliphatic 2 3586-3595** 
**Aromatic 10 3574-3586**
**10 1757-1774**

**Phenol 1,4-Disubstituted 15 3645-3657**
**15 1233-1269**
**15 1171-1190 1,3-Disubstituted 10 3643-3655** 
**10 1256-1315**
**10 1157-1198 1,2-Disubstituted 6 3582-3595** 
**1255-1274**

**(continued)**

### SW-846 Update V 8410 - 17 Revision 1 **October 2012 TABLE 3** 

**(Continued)**

**Functionality Class Number of**  **Compounds Frequency** 

**Range,** 

### ν **cm -1** 

**Alcohol Primary Aliphatic 20 3630-3680**
**11 1206-1270**
**16 1026-1094 Secondary Aliphatic 17 3604-3665** 
**10 1231-1270 Tertiary Aliphatic 10 3640-3670** 
**6 1213-1245**

**Amine Primary Aromatic 15 3480-3532 Secondary Aromatic 5 3387-3480**  **Aliphatic 10 760-785**

**Alkane 14 2930-2970** 
**2851-2884**
**1450-1475**
**1355-1389**

**Aldehyde Aromatic 12 1703-1749**
**12 2820-2866**
**12 2720-2760 Aliphatic 6 1742-1744** 
**6 2802-2877**
**6 2698-2712**

**Benzene Monosubstituted 7 1707-1737**
**24 1582-1630**
**24 1470-1510**
**11 831-893**
**23 735-790**
**25 675-698**

### SW-846 Update V 8410 - 18 Revision 1 **October 2012 TABLE 4** 

**FUSED SILICA CAPILLARY COLUMN GC/FT-IR QUANTITATION RESULTS** 

**Compound Concentration**  **Range, and Identification**  **Limit, ng a**  **Maximum**

**Absorbance b** 

**Correlation Coefficient**  **d Integrated** 

**Absorbance c** 
**Correlation Coefficient**  **d**

**Acenaphthene 25-250 0.9995 0.9985 Acenaphthylene 25-250 0.9959 0.9985** 

**Anthracene 50-250 0.9969 0.9971 Benzo(a)anthracene 50-250 0.9918 0.9921** 

**Benzoic acid 50-250 0.9864 0.9892 Benzo(a)pyrene 100-250 0.9966 0.9074**  **Bis(2-chloroethoxy)methane 25-250 0.9992 0.9991 Bis(2-chloroethyl)ether 25-250 0.9955 0.9992**  **Bis(2-chloro-1-methylethyl)ether 50-250 0.9981 0.99 98**  **4-Bromophenyl phenyl ether 25-250 0.9995 0.9996 Butyl benzyl phthalate 25-250 0.9999 0.9994** 

**4-Chloroaniline 25-250 0.9991 0.9965 4-Chloro-3-methylphenol 25-250 0.9975 0.9946**  **2-Chloronaphthalene 100-250 0.9897 0.9988 2-Chlorophenol 25-250 0.9976 0.9965**  **4-Chlorophenol e** 
**- - - 4-Chlorophenyl phenyl ether 25-250 0.9999 0.9997**  **Chrysene 100-250 0.9985 0.9984**

**Dibenzofuran 25-250 0.9697 0.8579 Di-n-butyl phthalate 25-250 0.9998 0.9996**  **1,2-Dichlorobenzene 25-250 0.9937 0.9947 1,3-Dichlorobenzene 25-250 0.9985 0.9950**  **1,4-Dichlorobenzene 25-250 0.9994 0.9994 2,4-Dichlorophenol 25-250 0.9964 0.9969**  **Dimethyl phthalate 25-250 0.9998 0.9996 Dimethyl phthalate 25-250 0.9998 0.9997**  **Dinitro-2-methylphenol 50-250 0.9936 0.9967 2,4-Dinitrophenol 50-250 0.9920 0.9916**  **2,4-Dinitrotoluene 25-250 0.9966 0.9928 2,6-Dinitrotoluene 25-250 0.9947 0.9966**  **Di-n-octyl phthalate 25-250 0.9983 0.9991 Bis(2-ethylhexyl)phthalate 25-250 0.9991 0.9993** 

**Fluoranthene 25-250 0.9983 0.9966**

**Fluorene 25-250 0.9987 0.9989**

**Hexachlorobenzene 50-250 0.9981 0.9995 1,3-Hexachlorobutadiene 50-250 0.9960 0.9979**  **Hexachlorocyclopentadiene 100-250 0.9862 0.9845**

**Hexachloroethane 25-250 0.9986 0.9992 Isophorone 25-250 0.9984 0.9990** 

### SW-846 Update V 8410 - 19 Revision 1 **October 2012 Compound**  **Concentration Range, and**  **Identification Limit, ng**  **a Maximum** 

**Absorbance b** 

**Correlation**
**Coefficient d**  **Integrated**

**Absorbance c** 
**Correlation**
**Coefficient d** 

**2-Methylnaphthalene 50-250 0.9981 0.9950 2-Methylphenol 25-250 0.9972 0.9964**  **4-Methylphenol 25-250 0.9972 0.9959 Naphthalene 25-250 0.9956 0.9954** 

**2-Nitroaniline 25-250 0.9996 0.9994**

**3-Nitroaniline 25-250 0.9985 0.9990**

**4-Nitroaniline 25-250 0.9936 0.9992**

**Nitrobenzene 25-250 0.9997 0.9979 2-Nitrophenol**  **e**
**- - - 4-Nitrophenol 50-250 0.9951 0.9953**  **N-Nitrosodimethylamine 25-250 0.9982 0.9993 N-Nitrosodiphenylamine 25-250 0.9994 0.9971**  **N-Nitrosodi-n-propylamine 25-250 0.9991 0.9995 Pentachlorophenol 50-250 0.9859 0.9883** 

**Phenanthrene 25-250 0.9941 0.9989**

**Phenol 25-250 0.9978 0.9966 Pyrene 50-250 0.9971 0.9977**  **1,2,4-Trichlorobenzene 50-250 0.9969 0.991 2,4,5-Trichlorophenol 25-250 0.9952 0.9966**  **2,4,6-Trichlorophenol 25-250 0.9969 0.9965**

**a Lower end of range is at or near the identificat**  **ion limit.**

**b FT-IR scan with highest absorbance plotted again**  **st concentration.**

**c Integrated absorbance of combined FT-IR scans wh**  **ich occur at or above the chromatogram peak half-height.** 

**d Regression analysis carried out at four concentr**  **ation levels. Each level analyzed in duplicate. Chromatographic conditions are stated i**  **n Sec. 11.3.**

**e Subject to interference from co-eluting compound**  **s.**

### SW-846 Update V 8410 - 20 Revision 1 **October 2012 METHOD 8410** 

**GC/FT-IR SPECTROMETRY FOR SEMIVOLATILE ORGANICS: C APILLARY COLUMN** 

### SW-846 Update V 8410 - 21 Revision 1 **October 2012 Appendix A**  **Changes in this version from the December 1994, Rev ision 0.** 

**1. Improved overall method formatting for consisten cy with new SW-846 methods style**  **guidance. The format was updated to Microsoft Word 2007.docx. This includes the**  **additions of all sections required by the new forma t.** 

**2. Many minor editorial and technical revisions wer e made throughout to improve method**  **clarity.**

**3. The revision number was changed to 1 and the dat e published was changed to October** 
**2012.**

**4. This appendix was added showing changes from the previous revision.** 

**5. Chemical name was changed by the Integrated Risk Information System (IRIS) on**  **November 30, 2007 from Bis(2-chloroisopropyl)ether to Bis(2-chloro-1-methylethyl)ether**  **(common name). This compound is also known as 2,2’ -oxybis(1-chloropropane) (CAS**  **index name). See the link at http://www.epa.gov/iris/subst/0407.htm**  **, Section VII for the “Revision History” and Section VIII, for “Synonyms”**  **of this chemical.**

**6. This appendix was added showing changes from the previous revision.** 

**7. The flowchart on page 19 was updated to reflect the current section numbers.** 

**8. Section 7.5.2 and Table 1 was updated to clarify use of internal standards.**