ASTM D4059-00(2010)
(Test Method)Standard Test Method for Analysis of Polychlorinated Biphenyls in Insulating Liquids by Gas Chromatography
Standard Test Method for Analysis of Polychlorinated Biphenyls in Insulating Liquids by Gas Chromatography
SIGNIFICANCE AND USE
United States governmental regulations mandate that electrical apparatus and electrical insulating fluids containing PCB be handled and disposed of through specific procedures. The procedure to be used for a particular apparatus or quantity of insulating fluid is determined by the PCB content of the fluid. The results of this analytical technique can be useful in selecting the appropriate handling and disposal procedure.
Quantification in this technique requires a peak-by-peak comparison of the chromatogram of an unknown specimen with that of standard Aroclor test specimens obtained under identical conditions. The amount of PCB producing each peak in the standard chromatogram shall be known independently.
The technique described is based on data for standard chromatograms of Aroclors 1242, 1254, and 1260 obtained using specific chromatographic column packing materials and operating conditions. Relevant chromatograms are reproduced in Fig. 1, Fig. 2, and Fig. 3 , for isothermal packed columns and in Figs. X4.1 through X4.3) for temperature programmed mega-bore capillary columns. Each peak is identified by its retention time relative to that of a standard. The types and amounts of PCB associated with each peak have been determined by mass spectroscopy and are given in Table 1, Table 2, and Table 3. Other chromatographic operating conditions, and in particular, other column packing materials, may give different separations. The data given in the tables should not be used if chromatograms of the standards differ significantly from those shown in the figures. The peaks in such standard chromatograms shall be independently identified and quantified.
Different isomers of PCB with the same number of chlorine substituents can cause substantially different responses from EC detectors. Mixtures of PCB containing the same amount of PCB, but with a different ratio of isomers, can give quite different chromatograms. This technique is effective only when the standard PCB m...
SCOPE
1.1 This test method describes a quantitative determination of the concentration of polychlorinated biphenyls (PCBs) in electrical insulating liquids by gas chromatography. It also applies to the determination of PCB present in mixtures known as askarels, used as electrical insulating liquids.
1.2 The PCB mixtures known as Aroclors were used in the formulation of the PCB-containing askarels manufactured in the United States. This test method may be applied to the determination of PCBs in insulating liquids contaminated by either individual Aroclors or mixtures of Aroclors. This technique may not be applicable to the determination of PCBs from other sources of contamination.
1.3 The precision and bias of this test method have been established only for PCB concentrations in electrical insulating mineral oils and silicones. The use of this test method has not been demonstrated for all insulating fluids. Some insulating liquids, such as halogenated hydrocarbons, interfere with the detection of PCBs and cannot be tested without pretreatment.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4059 − 00 (Reapproved 2010)
Standard Test Method for
Analysis of Polychlorinated Biphenyls in Insulating Liquids
by Gas Chromatography
This standard is issued under the fixed designation D4059; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 3. Symbols
1.1 This test method describes a quantitative determination 3.1 The following symbols are used in this test method:
of the concentration of polychlorinated biphenyls (PCBs) in
C —concentration of PCB (ppm by weight) in the insulating test specimen.
C —concentration of PCB (ppm by weight) found for the peak, i,inthe
electrical insulating liquids by gas chromatography. It also i
chromatogram of the insulating liquid test specimen.
appliestothedeterminationofPCBpresentinmixturesknown
d —density of the test specimen at 25°C, g/mL.
as askarels, used as electrical insulating liquids.
f —relative content of the PCB species associated with each individual
i
peak, i, in the chromatogram of the standard Aroclor solution, %.
1.2 The PCB mixtures known asAroclors were used in the
M —total amount of PCB in the standard test specimen injected into the
formulation of the PCB-containing askarels manufactured in chromatograph, g.
M —amount of PCB represented by peak, i, in the chromatogram of the
i
the United States. This test method may be applied to the
standard Aroclor test specimen, g.
determination of PCBs in insulating liquids contaminated by s
R —response of the detector to PCB components with relative retention
i
time, i, in the chromatograms of the standard, s, solutions, response
either individual Aroclors or mixtures of Aroclors. This tech-
may be expressed as peak height, peak area, or integrator counts.
niquemaynotbeapplicabletothedeterminationofPCBsfrom
x
R —response of the detector to PCB components with relative retention
i
other sources of contamination.
time, i, in the chromatogram of an unknown test specimen, may be
expressed as peak height, peak area, or integrator counts.
1.3 The precision and bias of this test method have been
s
R —response of the detector to PCB components in the largest or most
p
establishedonlyforPCBconcentrationsinelectricalinsulating cleanly separated peaks, p, in chromatograms of standard solutions;
may be expressed as peak height, peak area, or integrator counts.
mineral oils and silicones. The use of this test method has not
x
R —response of the detector to PCB components in the largest or most
p
been demonstrated for all insulating fluids. Some insulating
cleanly separated peaks, p, in the chromatogram of an unknown test
liquids, such as halogenated hydrocarbons, interfere with the specimen contaminated by a single Aroclor; may be expressed in
peak height, peak area, or integrator counts.
detection of PCBs and cannot be tested without pretreatment.
s
ν —volume of the standard test specimen injected into the
chromatograph, µL.
1.4 The values stated in SI units are to be regarded as
x
ν —volume of the unknown test specimen injected into the
standard. No other units of measurement are included in this
chromatograph, µL.
standard.
V —original volume of the test specimen to be analyzed, µL.
s
V —total volume of the diluted standard, mL.
1.5 This standard does not purport to address all of the
x
V —total volume of the test specimen to be analyzed, µL.
x
safety concerns, if any, associated with its use. It is the
W —weight of the test specimen to be analyzed, g.
s
W —weight of the initial standard Aroclor test specimen, g.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use.
4.1 Thetestspecimenisdilutedwithasuitablesolvent.The
resulting solution is treated by a procedure to remove interfer-
2. Referenced Documents
ing substances after which a small portion of the resulting
2.1 ASTM Standards:
solution is injected into a gas chromatographic column. The
D923Practices for Sampling Electrical Insulating Liquids
componentsareseparatedastheypassthroughthecolumnwith
carrier gas and their presence in the effluent is measured by an
This test method is under the jurisdiction of Committee D27 onElectrical
electron capture (EC) detector and recorded as a chromato-
Insulating Liquids and Gasesand is the direct responsibility of Subcommittee
gram. The test method is made quantitative by comparing the
D27.03 on Analytical Tests.
sample chromatogram with a chromatogram of a known
Current edition approved May 15, 2010. Published June 2010. Originally
quantity of one or more standardAroclors, obtained under the
published as a proposal. Last previous edition approved in 2005 as
ε1
D4059–00(2005) . DOI: 10.1520/D4059-00R10.
same analytical conditions.
Registered trademark of Monsanto Co.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
5. Significance and Use
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
5.1 United States governmental regulations mandate that
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. electrical apparatus and electrical insulating fluids containing
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4059 − 00 (2010)
FIG. 3 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
Column Temperature: 170°C, Detector: Electron Capture
TABLE 1 Composition of Aroclor 1242
Relative
Mean Number of
A
RRT Standard
FIG. 1 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
C
Weight, % Chlorines
B
Deviation
Column Temperature: 170°C, Detector: Electron Capture
11 1.1 35.7 1
16 2.9 4.2 2
21 11.3 3.0 2
28 11.0 5.0
2 25 %
J
3 75 %
32 6.1 4.7 3
37 11.5 5.7 3
40 11.1 6.2 3
47 8.8 4.3 4
54 6.8 2.9
3 33 %
J
4 67 %
58 5.6 3.3 4
70 10.3 2.8
FIG. 2 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min, 4 90 %
J
Column Temperature: 170°C, Detector: Electron Capture
5 10 %
78 3.6 4.2 4
PCB be handled and disposed of through specific procedures.
84 2.7 9.7 5
98 1.5 9.4 5
The procedure to be used for a particular apparatus or quantity
104 2.3 16.4 5
of insulating fluid is determined by the PCB content of the
125 1.6 20.4
5 85 %
fluid. The results of this analytical technique can be useful in
J
6 15 %
selecting the appropriate handling and disposal procedure.
5.2 Quantificationinthistechniquerequiresapeak-by-peak 146 1.0 19.9
5 75 %
J
comparison of the chromatogram of an unknown specimen
6 25 %
with that of standard Aroclor test specimens obtained under
Total 98.5
identical conditions. The amount of PCB producing each peak
A
in the standard chromatogram shall be known independently. Retention time relative to p ,p'-DDE = 100. Measured from first appearance of
solvent.
B
5.3 The technique described is based on data for standard
Standard deviation of six results as a percentage of the mean of the results (sic
coefficient of variation).
chromatograms of Aroclors 1242, 1254, and 1260 obtained
C
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
using specific chromatographic column packing materials and
numbers are bracketed.
operatingconditions. Relevantchromatogramsarereproduced
in Fig. 1, Fig. 2, and Fig. 3 , for isothermal packed columns
and in Figs. X4.1 through X4.3) for temperature programmed
entseparations.Thedatagiveninthetablesshouldnotbeused
mega-bore capillary columns. Each peak is identified by its
if chromatograms of the standards differ significantly from
retention time relative to that of a standard. The types and
those shown in the figures. The peaks in such standard
amounts of PCB associated with each peak have been deter-
chromatograms shall be independently identified and quanti-
mined by mass spectroscopy and are given in Table 1, Table 2,
fied.
andTable3. Otherchromatographicoperatingconditions,and
5.4 Different isomers of PCB with the same number of
in particular, other column packing materials, may give differ-
chlorine substituents can cause substantially different re-
sponses from EC detectors. Mixtures of PCB containing the
Webb, R. G., and McCall,A. C., Journal of Chromatographic Science, Vol 11,
same amount of PCB, but with a different ratio of isomers, can
1973, p. 366.
give quite different chromatograms.This technique is effective
Reproduced from the Journal of Chromatographic Science by permission of
Preston Publications, Inc. only when the standard PCB mixtures and those found in the
D4059 − 00 (2010)
6 6
TABLE 2 Composition of Aroclor 1254 TABLE 3 Composition of Aroclor 1260
Relative Mean Relative Standard
A C
Mean Number of RRT Number of Chlorines
A B
RRT Standard Weight % Deviation
C
Weight, % Chlorines
B
Deviation
70 2.7 6.3 5
47 6.2 3.7 4 84 4.7 1.6 5
54 2.9 2.6 4 3.8 3.5
58 1.4 2.8 4 D
J
70 13.2 2.7 H
104 60 %
4 25 %
J
5 75 %
640%
117 3.3 6.7 6
84 17.3 1.9 5
125 12.3 3.3
98 7.5 5.3 5
5 15 %
104 13.6 3.8 5
J
6 85 %
125 15.0 2.4
5 70 %
J
146 14.1 3.6 6
6 30 %
160 4.9 2.2
6 50 %
146 10.4 2.7 J
7 50 %
5 30 %
J
6 70 %
174 12.4 2.7 6
203 9.3 4.0
160 1.3 8.4 6
6 10 %
174 8.4 5.5 6 J
7 90 %
203 1.8 18.6 6
232 1.0 26.1 7
9.8 3.4
H
Total 100.0
E
244 6
J
A
Retention time relative to p,p'-DDE = 100. Measured from first appearance of 10 %
solvent.
90 %
B
Standard deviation of six results as a percent of the mean of the results (sic
coefficient of variation).
C
From GC-MS data. Peaks containing mixtures of isomers are bracketed.
280 11.0 2.4 8
332 4.2 5.0 8
372 4.0 8.6 8
448 0.6 25.3
unknown test specimen are closely related. Aroclors 1242,
528 1.5 10.2
1254,and1260areadequatestandardsbecausetheyhavebeen
Total 98.6
found to be the most common PCB contaminant in electrical
A
Retention time relative to p,p'-DDE = 100. Measured from first appearance of
insulating oils.
solvent. Overlapping peaks that are quantitated as one peak are bracketed.
B
Standard deviation of six results as a mean of the results (sic coefficient of
6. Interferences
variation).
C
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
6.1 Electron capture detectors respond to other chlorine
numbers are bracketed.
D
containing compounds and to certain other electrophilic mate- Composition determined at the center of peak 104.
E
Composition determined at the center of peak 232.
rials containing elements such as other halogens, nitrogen,
oxygen, and sulfur. These materials may give peaks with
retention times comparable to those of PCBs. Most common
interferences will be removed by the simple pre-analysis
Mineral oil should be absent from standards and dilution
treatmentstepsdetailedwithinthistestmethod.Thechromato-
solvents used in the analysis of silicone test specimens.
gram of each analyzed test specimen should be carefully
6.3 Residual oxygen in the carrier gas may react with
compared with those of the standards. The results of an
components of test specimens to give oxidation products to
analysis are suspect if major extraneous or unusually large
whichECdetectorswillrespond.Takecaretoensurethepurity
individual peaks are found.
of the carrier gas.
6.1.1 Data acquisition and treatment by electronic integra-
6.3.1 The use of an oxygen scrubber and a moisture trap on
tors or other instrumental means easily permits the unrecog-
both the carrier gas and the detector makeup gas is recom-
nized inclusion of interferences in the quantification of results.
mended to extend the useful column and detector life.
Visual examination of chromatograms by those skilled in the
method should be made to obtain maximum accuracy. 6.4 Trichlorobenzenes (TCBs) are often present with PCBs
in insulating oils and will generate a response in the EC
6.2 The sensitivity of EC detectors is reduced by mineral
detector. These appear earlier than the first chlorinated biphe-
oils.The same amount of oil must pass through the detector in
nylpeak( i=11)inmostcasesandshouldbeneglectedinthis
both calibration and analysis to ensure a meaningful compari-
analysis. Unusually high concentrations of TCBs may be
sonforquantification.Sample,standarddilutions,andinjection
present occasionally and may obscure the lower molecular
volumes should be carefully chosen in this test method to
weight PCB peaks.
match the interference of the oil.
6.2.1 The sensitivity of EC detectors is not significantly 6.5 Componentsofhigh-molecularweightmineraloilsmay
affected by silicone liquids. Evaluate the need for matrix have longer than normal retention on the chromatography
matching within your analytical scheme before proceeding. column, resulting in “ghost” peaks or excessive tailing. These
D4059 − 00 (2010)
conditionsinterferewiththedatasystem’sabilitytoaccurately 7.6 Analytical Balance or Hydrometer, capable of measur-
quantify material at levels approaching the method detection ing densities of approximately 0.9 g/mL.
limit. Inject reagent grade solvent blanks until the chromato-
8. Chromatograph Operation Conditions
gram’s baseline returns to normal before continuing with the
analysis.
8.1 General—The characteristics of individual chromato-
graphs and columns differ. Particular operating conditions
7. Apparatus
should be chosen so as to give the separations shown inFig. 1,
Fig.2,andFig.3forAroclors1242,1254,and1260.Retention
7.1 Instruments:
times of the peaks should be determined relative to 1,1' bis
7.1.1 Gas Chromatograph, equipped with oven temperature
(4-chlorophenyl) ethane (p,p'-DDE) to identify the individual
control reproducible to 1°C and with heated injection port.
peakswiththoseshowninthechromatogramsandlistedinthe
7.1.2 Means to Record the Chromatogram, such as a pen
tables. General ranges of temperatures and flow rate with
recorder,preferablycoupledtoadigitalintegratortodetermine
which satisfactory separations have been obtained are listed.
peak areas. An automatic sample injector may be used.
7.1.3 Injector, stainless steel construction, equipped with
8.2 Column Temperature—Isothermal temperatures be-
suitable adapters to permit use of direct column injection,
tween 165 and 200°C have been found suitable when using
packed column injection, or split/splitless capillary injection.
packed column (see Fig. 1). Temperature programming of
All metal surfaces shall be lined with glass.
megabore columns over the range of 165 to 300°C has been
7.1.3.1 Mega-bore capillary columns may be effectively
found to enhance resolution and decrease the analytical ru
...
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