1、Designation: D 6160 98 (Reapproved 2008)An American National StandardStandard Test Method forDetermination of Polychlorinated Biphenyls (PCBs) in WasteMaterials by Gas Chromatography1This standard is issued under the fixed designation D 6160; the number immediately following the designation indicate
2、s the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method2covers a two-tiered analytica
3、l ap-proach to PCB screening and quantitation of liquid and solidwastes, such as oils, sludges, aqueous solutions, and otherwaste matrices.1.2 Tier I is designed to screen samples rapidly for thepresence of PCBs.1.3 Tier II is used to determine the concentration of PCBs,typically in the range of fro
4、m 2 to 50 mg/kg. PCB concentra-tions greater than 50 mg/kg are determined through analysis ofsample dilutions.1.4 This is a pattern recognition approach, which does nottake into account individual congeners that might occur, suchas in reaction by-products. This test method describes the useof Aroclo
5、rs31016, 1221, 1232, 1242, 1248, 1254, 1260, 1262,and 1268, as reference standards, but others could also beincluded. Aroclors 1016 and 1242 have similar capillary gaschromatography (GC) patterns. Interferences or weathering areespecially problematic withAroclors 1016, 1232, and 1242 andmay make dis
6、tinction between the three difficult.1.5 This test method provides sample clean up and instru-mental conditions necessary for the determination of Aroclors.Gas chromatography (GC) using capillary column separationtechnique and electron capture detector (ECD) are described.Other detectors, such as at
7、omic emission detector (AED) andmass spectrometry (MS), may be used if sufficient performance(for example, sensitivity) is demonstrated. Further details aboutthe use of GC and ECD are provided in Practices E 355, E 697,and E 1510.1.6 Quantitative results are reported on the dry weights ofwaste sampl
8、es.1.7 Quantification limits will vary depending on the type ofwaste stream being analyzed.1.8 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.9 This standard does not purport to address all of thesafety concerns, if any, asso
9、ciated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulator limitations prior to use.2. Referenced Documents2.1 ASTM Standards:4D 4059 Test Method forAnalysis of Polychlorinated Biphe-ny
10、ls in Insulating Liquids by Gas ChromatographyE 203 Test Method for Water Using Volumetric Karl FischerTitrationE 288 Specification for Laboratory Glass Volumetric FlasksE 355 Practice for Gas Chromatography Terms and Rela-tionshipsE 697 Practice for Use of Electron-Capture Detectors inGas Chromatog
11、raphyE 969 Specification for Glass Volumetric (Transfer) PipetsE 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 U.S. EPA Standards:Method 608 Organochlorine Pesticides and PCBs5Method 680 Determination of Pesticides and PCBs in Waterand Soil/Sediment
12、 by Gas Chromatography/Mass Spec-trometry6Method 3620 Florisil Column Clean-Up7Method 3630 Silica Gel Clean-Up7Method 3660 Sulfur Clean-Up71This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L o
13、n Gas Chromatography Methods.Current edition approved May 1, 2008. Published September 2008. Originallyapproved in 1997. Last previous edition approved in 2003 as D 616098 (2003)1.2This test method is based largely on EPA 8080 (and the proposed modificationfor the use of capillary columns, EPA 8081)
14、 and EPA Report 600/481045 byBellar, T. and J. Lichtenberg, reported in 1981. The report is titled, “TheDetermination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils,”and provides significant support to the protocol in this standard.3Aroclor Standards may be purchased as 1000 g/mL i
15、n isooctane. Aroclor is aregistered trademark of the Monsanto Company, 800 N. Lindbergh Blvd., St. Louis,MO 63167.4For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to th
16、e standards Document Summary page onthe ASTM website.5EPAReport 600/4/82057, Environmental Monitoring and Support Laboratory,Cincinnati, OH.6Alford-Stevens, Ann, et al, Physical and Chemical Methods Branch, Environ-mental Monitoring and Support Laboratory Office of Research and Development,USEPA, Ci
17、ncinnati, OH.7U.S. EPA, “Test Methods for Evaluating Solid Waste,” Physical/ChemicalMethods, SW-846.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Method 8082 Determination of PCB in Water and Soil/Sediment by Gas Chromatography: Ca
18、pillary ColumnTechnique73. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 Aroclors, ncommercial mixtures of polychlorinatedbiphenyl congeners marketed and trademarked by Monsantoprior to 1977.3.1.1.1 DiscussionSpecific Aroclors are usually desig-nated by a four-digit number, wit
19、h the first two digits usuallydesignating the number of carbon atoms and the last two digitsproviding the chlorine content (for example,Aroclor 1260 is 60% (weight) chlorine).3.1.2 congeners, ncompounds related by structural simi-larities.3.1.2.1 DiscussionAll polychlorinated biphenyls (PCBs)share t
20、he same C12structure and vary only by the number andposition of the chlorine atoms attached to the aromatic rings.3.1.3 continuing calibration standard (CCS)a knownblend or one or more Aroclors at a fixed concentration that isinjected into the gas chromatograph to demonstrate the validityof the cali
21、bration.3.1.4 dry weight, nconcentration of PCBs after factoringout the water content.3.1.4.1 DiscussionThis correction assumes that all PCBsoriginated from nonaqueous sources and any water present hasbeen added subsequently, diluting the original concentration.This correction can be described using
22、 the formula:Aroclor mg/Kg!dry!5Aroclor mg/Kg!wet!100 2 % water!/100(1)3.1.5 instrument performance standard (IPS), na knownlow level of an Aroclor in a clean solvent used as a comparatorto determine which qualitative (screening) results are ofsufficient magnitude to require quantitative analyses.3.
23、1.6 surrogate, ncompound or compounds that are simi-lar to analytes of interest in chemical composition, extraction,and chromatography, but that are not normally found atsignificant levels in the matrices of interest.3.1.6.1 DiscussionSurrogates may be spiked into blanks,standards, samples, or matri
24、x spikes prior to analysis to allowa determination of a quantitative recovery rate. Surrogates arealso used to document matrix effects and method control.3.1.7 waste material, nany matter, within the scope of thistest method, that is in the process of being recycled ordisposed.4. Summary of Test Met
25、hod4.1 The sample is extracted with solvent and the extract istreated to remove interfering substances, if needed. The sampleextract is injected into a gas chromatograph. The componentsare separated as they pass through the capillary column andpolychlorinated biphenyl compounds, if present, are dete
26、ctedby an ECD.NOTE 1Portions of this test method are similar to EPA Methods 608,680, and 8082.4.2 For screening (Tier I), instrument performance is moni-tored by a 2-L injection of a standard containing Aroclors1016 and 1260. For low level work (1 ppm) the instrument ischecked with a standard concen
27、tration of 0.01 g/mL (each)and for higher level work (10 ppm), the instrument is checkedwith a 0.1 g/mL standard.4.3 Identification involves a pattern comparison of thechromatograms of an unknown sample with that of a standardobtained under identical instrumental conditions.4.4 When quantification i
28、s required (Tier II), an externalstandards method (ESTD) is used. The quantitation techniquetypically requires a comparison of five peaks (minimum ofthree) between the chromatograms of an unknown sample andthat of standard Aroclor obtained under identical conditions.Quantitation of either Aroclors 1
29、016 or 1260 is performedusing a five-point calibration of a mixed Aroclor standardcontainingAroclors 1016 and 1260.All remainingAroclors arequantitated from single point calibrations. Calibration is veri-fied daily by comparison of results obtained for analysis of themidpoint calibration standard of
30、 Aroclor 1016 and 1260 to thefive-point calibration curve. (See Appendix X1 for an examplechromatogram and calibration table.)5. Significance and Use5.1 This test method provides sufficient PCB data for manyregulatory requirements. While the most common regulatorylevel is 50 ppm (dry weight correcte
31、d), lower limits are used insome locations. Since sensitivities will vary for different typesof samples, one shall demonstrate a sufficient method detectionlimit for the matrix of interest.5.2 This test method differs from Test Method D 4059 inthat it provides for more sample clean-up options, utili
32、zes acapillary column for better pattern recognition and interferencediscrimination, and includes both a qualitative screening and aquantitative results option.6. Interferences6.1 The ECD has selective sensitivity to alkyl halides,conjugated carbonyls, nitrogen compounds, organometallics,and sulfur.
33、 Therefore, the chromatogram obtained for eachsample shall be carefully compared to chromatograms ofstandards to allow proper interpretation.6.2 Solvents, reagents, glassware, and other sample process-ing hardware may yield artifacts or interferences, or both, tostandard analysis. All these material
34、s shall be demonstrated tobe free from interferences under the conditions of analysis byanalyzing method blanks.6.3 Interferences from phthalate esters may pose a majorproblem in Aroclor determinations when using ECD. Phtha-lates generally appear in the chromatogram as broad lateeluting peaks. Since
35、 phthalates are commonly used as plasti-cizers and are easily extracted from plastic, all contact ofsamples and extracts with plastic should be avoided.6.4 While general clean-up techniques are provided as partof this test method, some samples may require additionalclean-up beyond the scope of this
36、test method before properinstrumental analysis may be performed.D 6160 98 (2008)27. Apparatus7.1 Gas Chromatograph, a temperature programmable gaschromatograph suitable for splitless injections; equipped withan ECD.7.2 Data System, a data system capable of measuring peakareas.7.3 Regulator (Make-up
37、Gas)N2or Ar:Methane (95:5);two stage regulator rated at 20 MPa (3000 psi) inlet and 35 to860 kPa (5 to 125 psi) outlet.7.4 Regulator (Carrier Gas)H2, two-stage regulator ratedat 20 MPa (3000 psi) inlet and 35 to 860 kPa (5 to 125 psi)outlet.7.5 Gas Purifiers, to remove moisture and particulates.Depe
38、nding on the levels and types of interferences encoun-tered, these might involve molecular sieves (moisture), acti-vated carbon (organics), or other commercially-available me-dia.7.6 Flow Meter, to measure gas flow. Typical range is from0.5 to 50 mL/min. 6 0.1 mL/min.7.7 Column, crosslinked 5 % phen
39、yl methyl silicone, 30 mby 0.32 mm id by 0.25 m film thickness.7.7.1 It is possible that other columns will provide sufficientseparating power, but this shall be demonstrated before use.7.8 Analytical Balance, capable of weighing to 0.0001 g.7.9 Volumetric Flasks, 10, 50, 100, 200 mL, (see Specifica
40、-tion E 288) Class A with ground-glass stoppers.7.10 Vortex Mixer:7.11 Vials, glass, 20 mL and 40 mL capacity with TFE-fluorocarbon-lined caps.7.12 Septum InsertsInserts shall be treated with a si-lynization reagent before use or after cleaning. (See Annex A2for possible procedure.) They may be purc
41、hased alreadytreated.7.13 Volumetric Pipette, 1, 5, 10 mL (see SpecificationE 969), Class A.7.14 Syringe, 500 L, mechanical guide.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to t
42、he specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.8Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determinat
43、ion.8.2 Acetone(WarningExtremely flammable. Vaporsmay cause flash fire.)8.3 Activated Magnesium Silicate (Florisil), Pesticide resi-due (PR) grade (60/100 mesh); store in glass containers withground glass stoppers or foil lined screw caps.8.3.1 Just before use, activate each batch at least4hat130C i
44、n a glass container loosely covered with aluminum foil.Alternatively, store the magnesium silicate in an oven at130C. Cool the magnesium silicate in a desiccator for 30 minbefore use.8.4 Hexane(WarningExtremely flammable. Harmful ifinhaled. May produce nerve cell damage. Vapors may causeflash fire.)
45、8.5 Isooctane(WarningExtremely flammable. Harmfulif inhaled. Vapors may cause flash fire.)8.6 Methanol(WarningFlammable. Vapor harmful.May be fatal or cause blindness if swallowed or inhaled.Cannot be made nonpoisonous.)8.7 Silynization Reagent (for example, 5 % dimethyldichlo-rosilane in toluene).
46、See Annex A2 for instructions.8.8 Sodium Sulfate, granular, anhydrous (maintained at130C for at least 24 h prior to use). Cool the sodium sulfate ina desiccator for 30 min before use.8.9 Sulfuric Acid (concentrated):8.10 Acetone/Hexane, 10 % acetone/90 % hexane (v/v).8.11 Gases, Hydrogen (zero grade
47、; 99.995 % purity) andnitrogen (zero grade; 99.998 % purity) or argon/methane (95:5;ECD grade).8.11.1 Care shall be given to ensure purity of the carrier gas.For example, an in-line filter may be required.8.12 Aroclor Standards3, Aroclor 1016, 1221, 1232, 1242,1254, 1260, 1262, 1268.8.13 Decachlorob
48、iphenyl (DCB) (surrogate) Optional:8.13.1 Surrogate Stock Standard (15 g/mL) PreparationAccurately dilute 1.5 mL of 1000 g/mL DCB concentrate in100 mL volumetric flask and fill to the mark with methanol,yielding a 15 g/mL solution.8.13.2 Surrogate Working Standard (1.5 g/mL)PreparationAccurately dil
49、ute 10 mL of the 15 g/mL DCBstock standard in a 100 mL volumetric flask and fill to the markwith methanol, yielding a 1.5 g/mL working DCB standard.NOTE 2Sample preparations will normally use 0.1 mL of this solu-tion. The resulting concentration in the sample extract is 0.005 g/mLbefore any further dilutions. The following calculations show this.1.5 g/mL 3 0.l mL 5 0.15 g0.15 g3.0 mL sample 1 27 mL!5 0.005 g/mL (2)8.14 Calibration Standards:8.14.1 Intermediate Stock Standard (50 g/mL):If high level standards (for example, comm
