ASTM D6160-98(2017) Standard Test Method for Determination of Polychlorinated Biphenyls (PCBs) in Waste Materials by Gas Chromatography.pdf

1、Designation: D6160 98 (Reapproved 2017)Standard Test Method forDetermination of Polychlorinated Biphenyls (PCBs) in WasteMaterials by Gas Chromatography1This standard is issued under the fixed designation D6160; the number immediately following the designation indicates the year oforiginal adoption

2、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 analytical ap-proach to PCB screening an

3、d 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 from 2 mg kg to 50 mg kg. PCBconce

4、ntrations greater than 50 mg/kg are determined throughanalysis of sample 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 Aroclors31016, 1221, 1232, 1242,

5、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 distinction between the three

6、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 atomic emission detector (AED

7、) 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 E355, E697,and E1510.1.6 Quantitative results are reported on the dry weights ofwaste samples.1.7 Quantification limits w

8、ill 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, associated with its use. It is the

9、responsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.10 This international standard was developed in accor-dance with internationally recognized principles on standa

10、rd-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:4D4059 Test Method for Analysis of Polychlorinat

11、ed Biphe-nyls in Insulating Liquids by Gas ChromatographyE203 Test Method for Water Using Volumetric Karl FischerTitrationE288 Specification for Laboratory Glass Volumetric FlasksE355 Practice for Gas Chromatography Terms and Relation-shipsE697 Practice for Use of Electron-Capture Detectors in GasCh

12、romatographyE969 Specification for Glass Volumetric (Transfer) PipetsE1510 Practice for Installing Fused Silica Open TubularCapillary Columns in Gas Chromatographs2.2 U.S. EPA Standards:Method 608 Organochlorine Pesticides and PCBs51This test method is under the jurisdiction of ASTM Committee D02 on

13、Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0L on Gas Chromatography Methods.Current edition approved Oct. 1, 2017. Published November 2017. Originallyapproved in 1997. Last previous edition approved in 2013 as D6160 98 (2013).DOI: 10.1520/

14、D6160-98R17.2This 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 Polychlorinated Biphenyls in Transformer Fluid

15、and Waste Oils,”and provides significant support to the protocol in this standard.3Aroclor Standards may be purchased as 1000 g/mL in 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

16、, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.5EPAReport 600/4/82057, Environmental Monitoring and Support Laboratory,Cincinnati, OH.Copyright ASTM International

17、, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides a

18、nd Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1Method 680 Determination of Pesticides and PCBs in Waterand Soil/Sediment by Gas Chromatography/Mass Spec-trometry6Method 3620 Florisil Column Clean-Up7Method 3630 Silica Gel Clean-Up7Method 3660 S

19、ulfur Clean-Up7Method 8082 Determination of PCB in Water and Soil/Sediment by Gas Chromatography: Capillary ColumnTechnique73. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 Aroclors, ncommercial mixtures of polychlorinatedbiphenyl congeners marketed and trademarked by Monsantop

20、rior 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 is60 % (weight) chlorine).3.1.2 congeners, ncompou

21、nds 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

22、fixed 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 h

23、asbeen 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 determin

24、e which 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 ma

25、trices 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 th

26、e scope 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

27、 as 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 contai

28、ning 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 sa

29、mple 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 sa

30、mple 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 standardcontainingAroclors 1016 and 1260.All remainingAroclors arequantitated from single point calibrations. Calibration is

31、 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

32、 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

33、test method differs from Test Method D4059 in thatit 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 selecti

34、ve 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 proces

35、s-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.6Alford-Stevens, Ann, et al, Physical and Chemical Methods Branch, Environ-mental Monit

36、oring and Support Laboratory Office of Research and Development,USEPA, Cincinnati, OH.7U.S. EPA, “Test Methods for Evaluating Solid Waste,” Physical/ChemicalMethods, SW-846.D6160 98 (2017)26.3 Interferences from phthalate esters may pose a majorproblem in Aroclor determinations when using ECD. Phtha

37、-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 provided as partof this test

38、method, some samples may require additionalclean-up beyond the scope of this test method before properinstrumental analysis may be performed.7. Apparatus7.1 Gas Chromatograph, a temperature programmable gaschromatograph suitable for splitless injections; equipped withan ECD.7.2 Data System, a data s

39、ystem 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) inlet and 35 to 860 kPa (5 to 125 psi)outlet

40、.7.5 Gas Purifiers, to remove moisture and particulates.Depending on the levels and types of interferencesencountered, these might involve molecular sieves (moisture),activated carbon (organics), or other commercially-availablemedia.7.6 Flow Meter, to measure gas flow. Typical range is from0.5 mL mi

41、n. 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 Analytical Balance, capable of weighing to 0.000

42、1 g.7.9 Volumetric Flasks, 10 mL, 50 mL, 100 mL, 200 mL,(see Specification E288) 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 silyni-zation reagent before use or af

43、ter cleaning. (See Annex A2 forpossible procedure.) They may be purchased already treated.7.13 Volumetric Pipette, 1 mL, 5 mL, 10 mL (see Specifi-cation E969), Class A.7.14 Syringe, 500 L, mechanical guide.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tes

44、ts. 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.8Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyh

45、igh 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 withground glass stoppers or foil li

46、ned screw caps.8.3.1 Just before use, activate each batch at least 4 h at130 C in a glass container loosely covered with aluminumfoil. Alternatively, store the magnesium silicate in an oven at130 C. Cool the magnesium silicate in a desiccator for 30 minbefore use.8.4 Hexane(WarningExtremely flammabl

47、e. 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.Cannot be made nonpoisonous.

48、)8.7 Silynization Reagent (for example, 5 % dimethyldichlo-rosilane in toluene). See Annex A2 for instructions.8.8 Sodium Sulfate, granular, anhydrous (maintained at130 C for at least 24 h prior to use). Cool the sodium sulfatein a desiccator for 30 min before use.8.9 Sulfuric Acid (concentrated):8.

49、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 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 in1