ASTM D4059-00(2005)e1
(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
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 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.
General Information
Relations
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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.
´1
Designation: D4059 – 00 (Reapproved 2005)
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. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
´ NOTE—Editorial changes were made in June 2005.
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.
applies to the determination of PCB present in mixtures known
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.
the United States. This test method may be applied to the M —amount of PCB represented by peak, i, in the chromatogram of the
i
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
either individual Aroclors or mixtures of Aroclors. This tech-
time, i, in the chromatograms of the standard, s, solutions, response
niquemaynotbeapplicabletothedeterminationofPCBsfrom may be expressed as peak height, peak area, or integrator counts.
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
1.3 The precision and bias of this test method have been
expressed as peak height, peak area, or integrator counts.
s
R —response of the detector to PCB components in the largest or most
established only for PCB concentrations in electrical insulating
p
cleanly separated peaks, p, in chromatograms of standard solutions;
mineral oils and silicones. The use of this test method has not
may be expressed as peak height, peak area, or integrator counts.
x
been demonstrated for all insulating fluids. Some insulating
R —response of the detector to PCB components in the largest or most
p
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
detection of PCBs and cannot be tested without pretreatment.
peak height, peak area, or integrator counts.
s
1.4 This standard does not purport to address all of the
n —volume of the standard test specimen injected into the chromato-
graph, µL.
safety concerns, if any, associated with its use. It is the
x
n —volume of the unknown test specimen injected into the chromato-
responsibility of the user of this standard to establish appro-
graph, µL.
priate safety and health practices and determine the applica-
V —original volume of the test specimen to be analyzed, µL.
s
V —total volume of the diluted standard, mL.
bility of regulatory limitations prior to use.
x
V —total volume of the test specimen to be analyzed, µL.
x
W —weight of the test specimen to be analyzed, g.
2. Referenced Documents
s
W —weight of the initial standard Aroclor test specimen, g.
2.1 ASTM Standards:
4. Summary of Test Method
D923 Practices for Sampling Electrical Insulating Liquids
4.1 The test specimen is diluted with a suitable solvent. The
resulting solution is treated by a procedure to remove interfer-
This test method is under the jurisdiction of Committee D27 on Electrical
ing substances after which a small portion of the resulting
Insulating Liquids and Gases and is the direct responsibility of Subcommittee
solution is injected into a gas chromatographic column. The
D27.03 on Analytical Tests.
Current edition approved May 1, 2005. Published June 2005. Originally
componentsareseparatedastheypassthroughthecolumnwith
published as a proposal. Last previous edition approved in 2000 as D4059 – 00.
carrier gas and their presence in the effluent is measured by an
DOI: 10.1520/D4059-00R05E01.
2 electron capture (EC) detector and recorded as a chromato-
Registered trademark of Monsanto Co.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or gram. The test method is made quantitative by comparing the
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
sample chromatogram with a chromatogram of a known
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
´1
D4059 – 00 (2005)
FIG. 3 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
Column Temperature: 170°C, Detector: Electron Capture
mega-bore capillary columns. Each peak is identified by its
retention time relative to that of a standard. The types and
FIG. 1 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
amounts of PCB associated with each peak have been deter-
Column Temperature: 170°C, Detector: Electron Capture
mined by mass spectroscopy and are given in Table 1, Table 2,
andTable 3. Other chromatographic operating conditions, and
in particular, other column packing materials, may give differ-
ent 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 quanti-
fied.
5.4 Different isomers of PCB with the same number of
chlorine substituents can cause substantially different re-
sponses from EC detectors. Mixtures of PCB containing the
same amount of PCB, but with a different ratio of isomers, can
FIG. 2 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min, give quite different chromatograms. This technique is effective
Column Temperature: 170°C, Detector: Electron Capture
only when the standard PCB mixtures and those found in the
unknown test specimen are closely related. Aroclors 1242,
quantity of one or more standard Aroclors, obtained under the
same analytical conditions. TABLE 1 Composition of Aroclor 1242
Relative
Mean Number of
A
5. Significance and Use
RRT Standard
C
Weight, % Chlorines
B
Deviation
5.1 United States governmental regulations mandate that
11 1.1 35.7 1
electrical apparatus and electrical insulating fluids containing
16 2.9 4.2 2
PCB be handled and disposed of through specific procedures.
21 11.3 3.0 2
28 11.0 5.0 2 25 %
The procedure to be used for a particular apparatus or quantity
J
3 75 %
of insulating fluid is determined by the PCB content of the
32 6.1 4.7 3
fluid. The results of this analytical technique can be useful in
37 11.5 5.7 3
selecting the appropriate handling and disposal procedure. 40 11.1 6.2 3
47 8.8 4.3 4
5.2 Quantification in this technique requires a peak-by-peak
54 6.8 2.9 3 33 %
J
comparison of the chromatogram of an unknown specimen
4 67 %
with that of standard Aroclor test specimens obtained under 58 5.6 3.3 4
70 10.3 2.8 4 90 %
identical conditions. The amount of PCB producing each peak
J
5 10 %
in the standard chromatogram shall be known independently.
78 3.6 4.2 4
5.3 The technique described is based on data for standard
84 2.7 9.7 5
98 1.5 9.4 5
chromatograms of Aroclors 1242, 1254, and 1260 obtained
104 2.3 16.4 5
using specific chromatographic column packing materials and
125 1.6 20.4 5 85 %
J
operatingconditions. Relevantchromatogramsarereproduced 6 15 %
146 1.0 19.9 5 75 %
in Fig. 1, Fig. 2, and Fig. 3 , for isothermal packed columns
J
6 25 %
and in Figs. X4.1 through X4.3) for temperature programmed
Total 98.5
A
Retention time relative to p,p8-DDE = 100. Measured from first appearance of
solvent.
B
Webb, R. G., and McCall,A. C., Journal of Chromatographic Science, Vol 11,
Standard deviation of six results as a percentage of the mean of the results (sic
1973, p. 366.
coefficient of variation).
C
Reproduced from the Journal of Chromatographic Science by permission of
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
Preston Publications, Inc. numbers are bracketed.
´1
D4059 – 00 (2005)
TABLE 2 Composition of Aroclor 1254
1254, and 1260 are adequate standards because they have been
Relative found to be the most common PCB contaminant in electrical
Mean Number of
A
RRT Standard
C
insulating oils.
Weight, % Chlorines
B
Deviation
47 6.2 3.7 4
6. Interferences
54 2.9 2.6 4
6.1 Electron capture detectors respond to other chlorine
58 1.4 2.8 4
70 13.2 2.7 4 25 %
containing compounds and to certain other electrophilic mate-
J
5 75 %
rials containing elements such as other halogens, nitrogen,
84 17.3 1.9 5
oxygen, and sulfur. These materials may give peaks with
98 7.5 5.3 5
104 13.6 3.8 5
retention times comparable to those of PCBs. Most common
125 15.0 2.4 5 70 %
interferences will be removed by the simple pre-analysis
J
6 30 %
treatment steps detailed within this test method.The chromato-
146 10.4 2.7 5 30 %
J
6 70 %
gram of each analyzed test specimen should be carefully
160 1.3 8.4 6
compared with those of the standards. The results of an
174 8.4 5.5 6
analysis are suspect if major extraneous or unusually large
203 1.8 18.6 6
individual peaks are found.
232 1.0 26.1 7
6.1.1 Data acquisition and treatment by electronic integra-
Total 100.0
tors or other instrumental means easily permits the unrecog-
A
Retention time relative to p,p8-DDE = 100. Measured from first appearance of
nized inclusion of interferences in the quantification of results.
solvent.
B
Visual examination of chromatograms by those skilled in the
Standard deviation of six results as a percent of the mean of the results (sic
coefficient of variation).
method should be made to obtain maximum accuracy.
C
From GC-MS data. Peaks containing mixtures of isomers are bracketed.
6.2 The sensitivity of EC detectors is reduced by mineral
oils. The same amount of oil must pass through the detector in
TABLE 3 Composition of Aroclor 1260
both calibration and analysis to ensure a meaningful compari-
Relative
sonforquantification.Sample,standarddilutions,andinjection
Mean Number of
A
RRT Standard
C
Weight % Chlorines
B volumes should be carefully chosen in this test method to
Deviation
match the interference of the oil.
70 2.7 6.3 5
6.2.1 The sensitivity of EC detectors is not significantly
84 4.7 1.6 5
D
3.8 3.5
affected by silicone liquids. Evaluate the need for matrix
J
H 5
104 60 %
matching within your analytical scheme before proceeding.
640%
Mineral oil should be absent from standards and dilution
117 3.3 6.7 6
solvents used in the analysis of silicone test specimens.
125 12.3 3.3 5 15 %
J
6 85 %
6.3 Residual oxygen in the carrier gas may react with
146 14.1 3.6 6
components of test specimens to give oxidation products to
6 50 %
160 4.9 2.2
J
7 50 % whichECdetectorswillrespond.Takecaretoensurethepurity
of the carrier gas.
174 12.4 2.7 6
203 9.3 4.0 6 10 %
6.3.1 The use of an oxygen scrubber and a moisture trap on
J
7 90 %
both the carrier gas and the detector makeup gas is recom-
232 9.8 3.4
E
H
244 6
mended to extend the useful column and detector life.
J
10 %
90 %
6.4 Trichlorobenzenes (TCBs) are often present with PCBs
in insulating oils and will generate a response in the EC
280 11.0 2.4 8
detector. These appear earlier than the first chlorinated biphe-
332 4.2 5.0 8
nyl peak ( i = 11) in most cases and should be neglected in this
372 4.0 8.6 8
448 0.6 25.3
analysis. Unusually high concentrations of TCBs may be
528 1.5 10.2
present occasionally and may obscure the lower molecular
weight PCB peaks.
Total 98.6
A
6.5 Components of high-molecular weight mineral oils may
Retention time relative to p,p8-DDE = 100. Measured from first appearance of
solvent. Overlapping peaks that are quantitated as one peak are bracketed.
have longer than normal retention on the chromatography
B
Standard deviation of six results as a mean of the results (sic coefficient of
column, resulting in “ghost” peaks or excessive tailing. These
variation).
C
conditions interfere with the data system’s ability to accurately
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
numbers are bracketed.
quantify material at levels approaching the method detection
D
Composition determined at the center of peak 104.
limit. Inject reagent grade solvent blanks until the chromato-
E
Composition determined at the center of peak 232.
gram’s baseline returns to normal before continuing with the
analysis.
´1
D4059 – 00 (2005)
7. Apparatus Fig.2,andFig.3forAroclors1242,1254,and1260.Retention
times of the peaks should be determined relative to 1,18 bis
7.1 Instruments:
(4-chlorophenyl) ethane (p,p8-DDE) to identify the individual
7.1.1 Gas Chromatograph, equipped with oven temperature
peaks with those shown in the chromatograms and listed in the
control reproducible to 1°C and with heated injection port.
tables. General ranges of temperatures and flow rate with
7.1.2 Means to Record the Chromatogram, such as a pen
which satisfactory separations have been obtained are listed.
recorder, preferably coupled to a digital integrator to determine
8.2 Column Temperature—Isothermal temperatures be-
peak areas. An automatic sample injector may be used.
tween 165 and 200°C have been found suitable when using
7.1.3 Injector, stainless steel construction, equipped with
packed column (see Fig. 1). Temperature programming of
suitable adapters to permit use of direct column injection,
megabore columns over the range of 165 to 300°C has been
packed column injection, or split/splitless capillary injection.
found to enhance resolution and decrease the analytical run
All metal surfaces shall be lined with glass.
time, while generating a chromatogram suitable for use with
7.1.3.1 Mega-bore capillary columns may be effectively
the packed column GC/MS data (see Appendix X4).
utilized on a packed column injector by replacing the standard
glass liner with a tapered capillary liner. While capillary
NOTE 2—Typical chromatograph
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.