1、Designation: D 4059 00 (Reapproved 2005)e1Standard Test Method forAnalysis of Polychlorinated Biphenyls in Insulating Liquidsby Gas Chromatography1This standard is issued under the fixed designation D 4059; the number immediately following the designation indicates the year oforiginal adoption or, i
2、n 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.e1NOTEEditorial changes were made in June 2005.1. Scope1.1 This test method describes a quant
3、itative determinationof the concentration of polychlorinated 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
4、 in theformulation of the PCB-containing askarels manufactured 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
5、fromother sources of contamination.1.3 The precision 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 halog
6、enated hydrocarbons, interfere with thedetection of PCBs and cannot be tested without pretreatment.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and healt
7、h practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:3D 923 Practices for Sampling Electrical Insulating Liquids3. Symbols3.1 The following symbols are used in this test method:C concentration of PCB (ppm by weight) in the insu
8、lating 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 associated with each individualpeak, i, in the chromatogram of the standard Aro
9、clor 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 detector to PCB components with relative retentiontime, i, in the chromatogram
10、s 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 specimen, may beexpressed as peak height, peak area, or integrator counts.Rps
11、response 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 PCB components in the largest or mostcleanly separated peaks, p, in the
12、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 unknown test specimen injected into the chromato-graph, L.V original vo
13、lume 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 test specimen, g.4. Summary of Test Method4.1 The test specimen is dil
14、uted 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 separated as they pass through the column withcarrier gas and their pr
15、esence 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 known1This test method is under the jurisdiction of Committee D27 on ElectricalInsulating Liquids
16、and Gases and is the direct responsibility of SubcommitteeD27.03 on Analytical Tests.Current edition approved May 1, 2005. Published June 2005. Originallypublished as a proposal. Last previous edition approved in 2000 as D 4059 00.2Registered trademark of Monsanto Co.3For referenced ASTM standards,
17、visit the ASTM website, 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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 1942
18、8-2959, United States.quantity of one or more standard Aroclors, obtained under thesame analytical conditions.5. Significance and Use5.1 United States governmental regulations mandate thatelectrical apparatus and electrical insulating fluids containingPCB be handled and disposed of through specific
19、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 inselecting the appropriate handling and disposal procedure.5.2 Quantification in this technique requires
20、 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 standard chromatogram shall be known independently.5.3 The technique described is based on data for standar
21、dchromatograms of Aroclors 1242, 1254, and 1260 obtainedusing specific chromatographic column packing materials andoperating conditions.4Relevant chromatograms are reproducedin Fig. 1, Fig. 2, and Fig. 35, for isothermal packed columnsand in Figs. X4.1 through X4.3) for temperature programmedmega-bo
22、re 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 and are given in Table 1, Table 2,and Table 3.4Other chromatographic operating conditions, andin particu
23、lar, 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 figures. The peaks in such standardchromatograms shall be independently identified and quanti-fied.5.4 Di
24、fferent 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 different ratio of isomers, cangive quite different chromatograms. This technique is effectiveonly when the
25、 standard PCB mixtures and those found in theunknown test specimen are closely related. Aroclors 1242,4Webb, 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 Colu
26、mn: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,Column Temperature: 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, D
27、etector: Electron CaptureTABLE 1 Composition of Aroclor 12426RRTAMeanWeight, %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
28、 9.7 598 1.5 9.4 5104 2.3 16.4 5125 1.6 20.4 56J85 %15 %146 1.0 19.9 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.
29、 Peaks containing mixtures of isomers of different chlorinenumbers are bracketed.D 4059 00 (2005)e121254, and 1260 are adequate standards because they have beenfound to be the most common PCB contaminant in electricalinsulating oils.6. Interferences6.1 Electron capture detectors respond to other chl
30、orinecontaining 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 comparable to those of PCBs. Most commoninterferences will be removed by the simple pre-analysistreatmen
31、t 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 extraneous or unusually largeindividual peaks are found.6.1.1 Data acquisition and treatment by electroni
32、c 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 should be made to obtain maximum accuracy.6.2 The sensitivity of EC detectors is reduced by minera
33、loils. 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 should be carefully chosen in this test method tomatch the interference of the oil.6.2.1 The sensitivit
34、y 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 dilutionsolvents used in the analysis of silicone test specimens.6.3 Residual oxygen in the carrier
35、 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 moisture trap onboth the carrier gas and the detector makeup gas is recom-mended to extend the usef
36、ul 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 biphe-nyl peak ( i = 11) in most cases and should be neglected in thisanalysis. Unusually high concen
37、trations 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 chromatographycolumn, resulting in “ghost” peaks or excessive tailing. Theseconditions interfere with the d
38、ata systems ability to accuratelyquantify material at levels approaching the method detectionTABLE 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 1
39、0.4 2.7 56J30 %70 %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 co
40、ntaining mixtures 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 %H
41、2322449.8 3.467JE10 %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 t
42、he results (sic 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.D 4059 00 (2005)e13limit. Inject reagent grade solvent blanks
43、 until the chromato-grams baseline returns to normal before continuing 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, preferab
44、ly coupled to a digital integrator to determinepeak areas. An automatic 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
45、 shall be lined with glass.7.1.3.1 Mega-bore capillary columns may be effectivelyutilized on a packed column injector by replacing the standardglass liner with a tapered capillary liner. While capillaryconversion kits are commercially available, this specializedhardware will not routinely be necessa
46、ry 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 less ofphosphorothioic acid o-(2-chloro-4-nitrophenyl) o,o-dimethylester (“dicapthon”). The det
47、ector 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 or fused silica, packed withappropriate materials. A precolumn may be used to extend theanalytica
48、l 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 useful. Other column lengths may be used,provided they give adequate separation of the PCB compo
49、-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 1260, 70 # i # 528.13.2.1 The higher resolving power of mega-bore columnsmay result in additional pe
