1、Designation: D4059 00 (Reapproved 2010)Standard Test Method forAnalysis of Polychlorinated Biphenyls in Insulating Liquidsby Gas Chromatography1This standard is issued under the fixed designation D4059; the number immediately following the designation indicates the year oforiginal adoption or, in th
2、e 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 method describes a quantitative determinationof the concentration of polychl
3、orinated biphenyls (PCBs) inelectrical insulating liquids by gas chromatography. It alsoapplies to the determination of PCB present in mixtures knownas askarels, used as electrical insulating liquids.1.2 The PCB mixtures known as Aroclors2were used in theformulation of the PCB-containing askarels ma
4、nufactured inthe United States. This test method may be applied to thedetermination of PCBs in insulating liquids contaminated byeither individual Aroclors or mixtures of Aroclors. This tech-nique may not be applicable to the determination of PCBs fromother sources of contamination.1.3 The precision
5、 and bias of this test method have beenestablished only for PCB concentrations in electrical insulatingmineral oils and silicones. The use of this test method has notbeen demonstrated for all insulating fluids. Some insulatingliquids, such as halogenated hydrocarbons, interfere with thedetection of
6、PCBs and cannot be tested without pretreatment.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility
7、 of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D923 Practices for Sampling Electrical Insulating Liquids3. Symbols3.1 The following symbols are used
8、 in this test method:C concentration of PCB (ppm by weight) in the insulating test specimen.Ciconcentration of PCB (ppm by weight) found for the peak, i,inthechromatogram of the insulating liquid test specimen.d density of the test specimen at 25C, g/mL.firelative content of the PCB species associat
9、ed with each individualpeak, i, in the chromatogram of the standard Aroclor solution, %.M total amount of PCB in the standard test specimen injected into thechromatograph, g.Miamount of PCB represented by peak, i, in the chromatogram of thestandard Aroclor test specimen, g.Risresponse of the detecto
10、r to PCB components with relative retentiontime, i, in the chromatograms of the standard, s, solutions, responsemay be expressed as peak height, peak area, or integrator counts.Rixresponse of the detector to PCB components with relative retentiontime, i, in the chromatogram of an unknown test specim
11、en, may beexpressed as peak height, peak area, or integrator counts.Rpsresponse of the detector to PCB components in the largest or mostcleanly separated peaks, p, in chromatograms of standard solutions;may be expressed as peak height, peak area, or integrator counts.Rpxresponse of the detector to P
12、CB components in the largest or mostcleanly separated peaks, p, in the chromatogram of an unknown testspecimen contaminated by a single Aroclor; may be expressed inpeak height, peak area, or integrator counts.nsvolume of the standard test specimen injected into the chromato-graph, L.nxvolume of the
13、unknown test specimen injected into the chromato-graph, L.V original volume of the test specimen to be analyzed, L.Vstotal volume of the diluted standard, mL.Vxtotal volume of the test specimen to be analyzed, L.Wxweight of the test specimen to be analyzed, g.Wsweight of the initial standard Aroclor
14、 test specimen, g.4. Summary of Test Method4.1 The test specimen is diluted with a suitable solvent. Theresulting solution is treated by a procedure to remove interfer-ing substances after which a small portion of the resultingsolution is injected into a gas chromatographic column. Thecomponents are
15、 separated as they pass through the column withcarrier gas and their presence in the effluent is measured by anelectron capture (EC) detector and recorded as a chromato-gram. The test method is made quantitative by comparing thesample chromatogram with a chromatogram of a knownquantity of one or mor
16、e standard Aroclors, obtained under thesame analytical conditions.1This test method is under the jurisdiction of Committee D27 onElectricalInsulating Liquids and Gases and is the direct responsibility of SubcommitteeD27.03 on Analytical Tests.Current edition approved May 15, 2010. Published June 201
17、0. Originallypublished as a proposal. Last previous edition approved in 2005 asD4059 00(2005)1. DOI: 10.1520/D4059-00R10.2Registered trademark of Monsanto Co.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of A
18、STMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Significance and Use5.1 United States governmental regulations mandate thatelectrical
19、 apparatus and electrical insulating fluids containingPCB be handled and disposed of through specific procedures.The procedure to be used for a particular apparatus or quantityof insulating fluid is determined by the PCB content of thefluid. The results of this analytical technique can be useful ins
20、electing the appropriate handling and disposal procedure.5.2 Quantification in this technique requires a peak-by-peakcomparison of the chromatogram of an unknown specimenwith that of standard Aroclor test specimens obtained underidentical conditions. The amount of PCB producing each peakin the stand
21、ard chromatogram shall be known independently.5.3 The technique described is based on data for standardchromatograms of Aroclors 1242, 1254, and 1260 obtainedusing specific chromatographic column packing materials andoperating conditions.4Relevant chromatograms are reproducedin Fig. 1, Fig. 2, and F
22、ig. 35, for isothermal packed columnsand in Figs. X4.1 through X4.3) for temperature programmedmega-bore capillary columns. Each peak is identified by itsretention time relative to that of a standard. The types andamounts of PCB associated with each peak have been deter-mined by mass spectroscopy an
23、d are given in Table 1, Table 2,and Table 3.4Other chromatographic operating conditions, andin particular, other column packing materials, may give differ-ent separations. The data given in the tables should not be usedif chromatograms of the standards differ significantly fromthose shown in the fig
24、ures. The peaks in such standardchromatograms shall be independently identified and quanti-fied.5.4 Different isomers of PCB with the same number ofchlorine substituents can cause substantially different re-sponses from EC detectors. Mixtures of PCB containing thesame amount of PCB, but with a diffe
25、rent ratio of isomers, cangive quite different chromatograms. This technique is effectiveonly when the standard PCB mixtures and those found in theunknown test specimen are closely related. Aroclors 1242,1254, and 1260 are adequate standards because they have beenfound to be the most common PCB cont
26、aminant in electricalinsulating oils.4Webb, R. G., and McCall, A. C., Journal of Chromatographic Science, Vol 11,1973, p. 366.5Reproduced from the Journal of Chromatographic Science by permission ofPreston Publications, Inc.FIG. 1 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,Column Temperatu
27、re: 170C, Detector: Electron CaptureFIG. 2 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,Column Temperature: 170C, Detector: Electron CaptureFIG. 3 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,Column Temperature: 170C, Detector: Electron CaptureTABLE 1 Composition of Aroclor 12426RRTA
28、MeanWeight, %RelativeStandardDeviationBNumber ofChlorinesC1116211.12.911.335.74.23.012228 11.0 5.0 23J25 %75 %32 6.1 4.7 337 11.5 5.7 340 11.1 6.2 347 8.8 4.3 454 6.8 2.9 34J33 %67 %58 5.6 3.3 470 10.3 2.8 45J90 %10 %78 3.6 4.2 484 2.7 9.7 598 1.5 9.4 5104 2.3 16.4 5125 1.6 20.4 56J85 %15 %146 1.0 1
29、9.9 56J75 %25 %Total 98.5ARetention time relative to p,p8-DDE = 100. Measured from first appearance ofsolvent.BStandard deviation of six results as a percentage of the mean of the results (siccoefficient of variation).CFrom GC-MS data. Peaks containing mixtures of isomers of different chlorinenumber
30、s are bracketed.D4059 00 (2010)26. Interferences6.1 Electron capture detectors respond to other chlorinecontaining compounds and to certain other electrophilic mate-rials containing elements such as other halogens, nitrogen,oxygen, and sulfur. These materials may give peaks withretention times compa
31、rable to those of PCBs. Most commoninterferences will be removed by the simple pre-analysistreatment steps detailed within this test method. The chromato-gram of each analyzed test specimen should be carefullycompared with those of the standards. The results of ananalysis are suspect if major extran
32、eous or unusually largeindividual peaks are found.6.1.1 Data acquisition and treatment by electronic integra-tors or other instrumental means easily permits the unrecog-nized inclusion of interferences in the quantification of results.Visual examination of chromatograms by those skilled in themethod
33、 should be made to obtain maximum accuracy.6.2 The sensitivity of EC detectors is reduced by mineraloils. The same amount of oil must pass through the detector inboth calibration and analysis to ensure a meaningful compari-son for quantification. Sample, standard dilutions, and injectionvolumes shou
34、ld be carefully chosen in this test method tomatch the interference of the oil.6.2.1 The sensitivity of EC detectors is not significantlyaffected by silicone liquids. Evaluate the need for matrixmatching within your analytical scheme before proceeding.Mineral oil should be absent from standards and
35、dilutionsolvents used in the analysis of silicone test specimens.6.3 Residual oxygen in the carrier gas may react withcomponents of test specimens to give oxidation products towhich EC detectors will respond. Take care to ensure the purityof the carrier gas.6.3.1 The use of an oxygen scrubber and a
36、moisture trap onboth the carrier gas and the detector makeup gas is recom-mended to extend the useful column and detector life.6.4 Trichlorobenzenes (TCBs) are often present with PCBsin insulating oils and will generate a response in the ECdetector. These appear earlier than the first chlorinated bi
37、phe-nyl peak ( i = 11) in most cases and should be neglected in thisanalysis. Unusually high concentrations of TCBs may bepresent occasionally and may obscure the lower molecularweight PCB peaks.6.5 Components of high-molecular weight mineral oils mayhave longer than normal retention on the chromato
38、graphycolumn, resulting in “ghost” peaks or excessive tailing. Theseconditions interfere with the data systems ability to accuratelyquantify material at levels approaching the method detectionlimit. Inject reagent grade solvent blanks until the chromato-grams baseline returns to normal before contin
39、uing with theanalysis.7. Apparatus7.1 Instruments:7.1.1 Gas Chromatograph, equipped with oven temperaturecontrol reproducible to 1C and with heated injection port.7.1.2 Means to Record the Chromatogram, such as a penrecorder, preferably coupled to a digital integrator to determinepeak areas. An auto
40、matic sample injector may be used.7.1.3 Injector, stainless steel construction, equipped withsuitable adapters to permit use of direct column injection,packed column injection, or split/splitless capillary injection.All metal surfaces shall be lined with glass.7.1.3.1 Mega-bore capillary columns may
41、 be effectivelyutilized on a packed column injector by replacing the standardTABLE 2 Composition of Aroclor 12546RRTAMeanWeight, %RelativeStandardDeviationBNumber ofChlorinesC4754586.22.91.43.72.62.844470 13.2 2.7 45J25 %75 %849810417.37.513.61.95.33.8555125 15.0 2.4 56J70 %30 %146 10.4 2.7 56J30 %7
42、0 %160 1.3 8.4 6174 8.4 5.5 6203 1.8 18.6 6232 1.0 26.1 7Total 100.0ARetention time relative to p,p8-DDE = 100. Measured from first appearance ofsolvent.BStandard deviation of six results as a percent of the mean of the results (siccoefficient of variation).CFrom GC-MS data. Peaks containing mixture
43、s of isomers are bracketed.TABLE 3 Composition of Aroclor 12606RRTAMeanWeight %RelativeStandardDeviationBNumber ofChlorinesC70 2.7 6.3 584 4.7 1.6 5H981043.8 3.55JD60 %640%117 3.3 6.7 6125 12.3 3.3 56J15 %85 %146 14.1 3.6 6160 4.9 2.2 67J50 %50 %174 12.4 2.7 6203 9.3 4.0 67J10 %90 %H2322449.8 3.467J
44、E10 %90 %7280 11.0 2.4 8332 4.2 5.0 8372 4.0 8.6 8448 0.6 25.3528 1.5 10.2Total 98.6ARetention time relative to p,p8-DDE = 100. Measured from first appearance ofsolvent. Overlapping peaks that are quantitated as one peak are bracketed.BStandard deviation of six results as a mean of the results (sic
45、coefficient ofvariation).CFrom GC-MS data. Peaks containing mixtures of isomers of different chlorinenumbers are bracketed.DComposition determined at the center of peak 104.EComposition determined at the center of peak 232.D4059 00 (2010)3glass liner with a tapered capillary liner. While capillaryco
46、nversion kits are commercially available, this specializedhardware will not routinely be necessary when working withmega-bore columns.7.1.4 DetectorHigh-temperature63Ni electron capturedetector with sufficient sensitivity to allow 50 % full-scalerecorder deflection with a sample containing 0.6 ng or
47、 less ofphosphorothioic acid o-(2-chloro-4-nitrophenyl) o,o-dimethylester (“dicapthon”). The detector must be operatedwithin its linear response range and the detector noise levelshould be less than 2 % of full scale.NOTE 1Other detectors may be used. Refer to Appendix X1.7.2 Column, made of glass o
48、r fused silica, packed withappropriate materials. A precolumn may be used to extend theanalytical columns useful life.7.2.1 A 1.83-m (6-ft) long, 6.35-mm (0.25-in.) outsidediameter, 2 to 4-mm (0.08 to 0.16 in.) inside diameter glasscolumn packed with 3 % OV16on 80/100 mesh Chromosorb7has been found
49、useful. Other column lengths may be used,provided they give adequate separation of the PCB compo-nents. Packings OV1016and DC2008on Chromosorb WAW7also give separations with which the data in Table 1, Table 2,and Table 3 may be used.7.2.2 A fused silica wide-bore capillary column such as a15-m mega-bore (0.53-mm ID) column having a 1.5-m film ofpolydimethylsiloxane has been shown to approximate a packedcolumn system and generate chromatograms with similarseparations thus allowing the use of the Webb forAroclor1254, 47 # i # 232, and for Aroclor 126
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