1、Designation: D 6160 98 (Reapproved 2003)e1An 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 indica
2、tes 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 (e) indicates an editorial change since the last revision or reapproval.e1NOTEWarning notes were editorially moved into the sta
3、ndard text in August 2003.1. Scope1.1 This test method2is a two-tiered analytical approach toPCB screening and quantitation of liquid and solid wastes,such as oils, sludges, aqueous solutions, and other wastematrices.1.2 Tier I is designed to screen samples rapidly for thepresence of PCBs.1.3 Tier I
4、I is used to determine the concentration of PCBs,typically in the range of from 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 occu
5、r, suchas in reaction by-products. This test method describes the useof Aroclors31016, 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 weatheri
6、ng areespecially problematic with Aroclors 1016, 1232, and 1242 andmay make distinction 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 separationtechniqu
7、e and electron capture detector (ECD) are described.Other detectors, such as atomic 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,an
8、d E 1510.1.6 Quantitative results are reported on the dry weights ofwaste samples.1.7 Quantification limits will vary depending on the type ofwaste stream being analyzed.1.8 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility
9、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:D 4059 Test Method for Analysis of Polychlorinated Biphe-nyls in Insulating Liquids by Gas Chromatograph
10、y4E 203 Test Method for Water Using Karl Fischer Titration5E 288 Specification for Laboratory Glass VolumetricFlasks6E 355 Practice for Gas Chromatography Terms and Rela-tionships7E 697 Practice for Use of Electron-capture Detectors in GasChromatography7E 969 Specification for Glass Volumetric (Tran
11、sfer) Pipet6E 1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatography72.2 U.S. EPA Standards:Method 608 Organochlorine Pesticides and PCBs8Method 680 Determination of Pesticides and PCBs in Waterand Soil/Sediment by Gas Chromatography/Mass Spec-trometry9Method 3
12、620 Florisil Column Clean-Up101This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved May 10, 2003. Published August 2003. Originallyapproved in 1997.
13、 Last previous edition approved in 1998 as D 616098.2This test method is based largely on EPA 8080 (and the proposed modificationfor the use of capillary columns, EPA 8081) and EPA Report 600/481045 byBellar, T. and J. Lichtenberg, reported in 1981. The report is titled,“ TheDetermination of Polychl
14、orinated Biphenyls in Transformer Fluid and Waste Oils”and provides significant support to the protocol below.3Aroclor Standards may be purchased as 1000 g/mL in isooctane. Aroclor is aregistered trademark of Monsanto.4ASTM Annual Book of Standards, Vol 10.03.5ASTM Annual Book of Standards, Vol 15.0
15、5.6ASTM Annual Book of Standards, Vol 14.04.7Annual Book of ASTM Standards, Vol 03.06.8EPA Report 600/4/82057, Environmental Monitoring and Support Laboratory,Cincinnati, OH.9Alford-Stevens, Ann, et al, Physical and Chemical Methods Branch, Environ-mental Monitoring and Support Laboratory Office of
16、Research and Development,USEPA, Cincinnati, OH.10U.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 3630 Silica Gel Clean-Up10Method 3660 Sulfu
17、r Clean-Up10Method 8082 Determination of PCB in Water and Soil/Sediment by Gas Chromatography: Capillary ColumnTechnique103. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 Aroclors, ncommercial mixtures of polychlorinatedbiphenyl congeners marketed and trademarked by Monsantopri
18、or to 1977.3.1.1.1 DiscussionSpecific Aroclors are usually desig-nated by a four-digit number, with 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, ncompound
19、s related by structural simi-larities.3.1.2.1 DiscussionAll polychlorinated biphenyls (PCBs)share the 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 fi
20、xed concentration that isinjected into the gas chromatograph to demonstrate the validityof the calibration.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 has
21、been added subsequently, diluting the original concentration.This correction can be described using 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 w
22、hich qualitative (screening) results are ofsufficient magnitude to require quantitative analyses.3.1.6 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 matri
23、ces of interest.3.1.6.1 DiscussionSurrogates may be spiked into blanks,standards, samples, or matrix 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 s
24、cope of thistest method, that is in the process of being recycled ordisposed.4. Summary of Test Method4.1 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
25、 they pass through the capillary column andpolychlorinated biphenyl compounds, if present, are detectedby 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 containin
26、g Aroclors1016 and 1260. For low level work (1 ppm) the instrument ischecked with a standard concentration 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 sampl
27、e with that of a standardobtained under identical instrumental conditions.4.4 When quantification is 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 sampl
28、e andthat of standard Aroclor obtained under identical conditions.Quantitation of either Aroclors 1016 or 1260 is performedusing a five-point calibration of a mixed Aroclor standardcontaining Aroclors 1016 and 1260. All remaining Aroclors arequantitated from single point calibrations. Calibration is
29、 veri-fied daily by comparison of results obtained for analysis of themidpoint calibration standard of 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
30、 for manyregulatory requirements. While the most common regulatorylevel is 50 ppm (dry weight corrected), 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
31、test method differs from Test Method D 4059 inthat it provides for more sample clean-up options, utilizes acapillary column for better pattern recognition and interferencediscrimination, and includes both a qualitative screening and aquantitative results option.6. Interferences6.1 The ECD has select
32、ive sensitivity to alkyl halides,conjugated carbonyls, nitrogen compounds, organometallics,and sulfur. 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 proce
33、ss-ing hardware may yield artifacts or interferences, or both, tostandard analysis. All these materials 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 determinati
34、ons when using ECD. Phtha-lates generally appear in the chromatogram as broad lateeluting peaks. Since 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 prov
35、ided as partof this test method, some samples may require additionalclean-up beyond the scope of this test method before properinstrumental analysis may be performed.D 6160 98 (2003)e127. Apparatus7.1 Gas Chromatograph, a temperature programmable gaschromatograph suitable for splitless injections; e
36、quipped withan ECD.7.2 Data System, a data system capable of measuring peakareas.7.3 Regulator (Make-up 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)
37、inlet and 35 to 860 kPa (5 to 125 psi)outlet.7.5 Gas Purifiers, to remove moisture and particulates.Depending 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, t
38、o measure gas flow. Typical range is from0.5 to 50 mL/min. 6 0.1 mL/min.7.7 Column, crosslinked 5 % phenyl 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 Analyt
39、ical Balance, capable of weighing to 0.0001 g.7.9 Volumetric Flasks, 10, 50, 100, 200 mL, (see Specifica-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
40、-lynization reagent before use or after cleaning. (See Annex A2for possible procedure.) They may be purchased alreadytreated.7.13 Volumetric Pipette, 1, 5, 10 mL (see Specification E969), Class A.7.14 Syringe, 500 L, mechanical guide.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemi
41、cals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.11Other grades may be used,provided it is first ascertained that th
42、e reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.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 withgro
43、und glass stoppers or foil lined screw caps.8.3.1 Just before use, activate each batch at least4hat130C in 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(W
44、arningExtremely flammable. Harmful ifinhaled. May produce nerve cell damage. Vapors may causeflash fire.)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.Cann
45、ot be made nonpoisonous.)8.7 Silynization Reagent (for example, 5 % dimethyldichlo-rosilane in toluene). 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
46、 Acid (concentrated):8.10 Acetone/Hexane, 10 % acetone/90 % hexane (v/v).8.11 Gases, Hydrogen (zero grade; 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
47、 required.8.12 Aroclor Standards3, Aroclor 1016, 1221, 1232, 1242,1254, 1260, 1262, 1268.8.13 Decachlorobiphenyl (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 m
48、ethanol,yielding a 15 g/mL solution.8.13.2 Surrogate Working Standard (1.5 g/mL)PreparationAccurately dilute 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
49、 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, commercially availablestandards at 2000 to 5000 g/mL) have been purchased,prepare solutions of 50 g/mL concentration.8.14.1.1 The surrogate calibration standard may be added(optional) to the Aroclor 1
