ASTM D4059-00

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D 4059 – 00
Standard Test Method for
Analysis of Polychlorinated Biphenyls in Insulating Liquids
by Gas Chromatography
This standard is issued under the fixed designation D 4059; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope E 260 Practice for Packed Column Gas Chromatography
E 355 Practice for Gas Chromatography Terms and Rela-
1.1 This test method describes a quantitative determination
tionships
of the concentration of polychlorinated biphenyls (PCBs) in
electrical insulating liquids by gas chromatography. It also
3. Symbols
applies to the determination of PCB present in mixtures known
3.1 The following symbols are used in this test method:
as askarels, used as electrical insulating liquids.
C —concentration of PCB (ppm by weight) in the insulating test specimen.
1.2 The PCB mixtures known asAroclors were used in the
C —concentration of PCB (ppm by weight) found for the peak, i,inthe
i
formulation of the PCB-containing askarels manufactured in
chromatogram of the insulating liquid test specimen.
the United States. This test method may be applied to the d —density of the test specimen at 25°C, g/mL.
f —relative content of the PCB species associated with each individual
i
determination of PCBs in insulating liquids contaminated by
peak, i, in the chromatogram of the standard Aroclor solution, %.
either individual Aroclors or mixtures of Aroclors. This tech-
M —total amount of PCB in the standard test specimen injected into the
niquemaynotbeapplicabletothedeterminationofPCBsfrom chromatograph, g.
M —amount of PCB represented by peak, i, in the chromatogram of the
i
other sources of contamination.
standard Aroclor test specimen, g.
1.3 The precision and bias of this test method have been s
R —response of the detector to PCB components with relative retention
i
time, i, in the chromatograms of the standard, s, solutions, response
established only for PCB concentrations in electrical insulating
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 with relative retention
i
been demonstrated for all insulating fluids. Some insulating
time, i, in the chromatogram of an unknown test specimen, may be
expressed as peak height, peak area, or integrator counts.
liquids, such as halogenated hydrocarbons, interfere with the
s
R —response of the detector to PCB components in the largest or most
p
detection of PCBs and cannot be tested without pretreatment.
cleanly separated peaks, p, in chromatograms of standard solutions;
1.4 This standard does not purport to address all of the
may be expressed as peak height, peak area, or integrator counts.
x
R —response of the detector to PCB components in the largest or most
safety concerns, if any, associated with its use. It is the p
cleanly separated peaks, p, in the chromatogram of an unknown test
responsibility of the user of this standard to establish appro-
specimen contaminated by a single Aroclor; may be expressed in
priate safety and health practices and determine the applica-
peak height, peak area, or integrator counts.
s
n —volume of the standard test specimen injected into the chromato-
bility of regulatory limitations prior to use.
graph, µL.
x
n —volume of the unknown test specimen injected into the chromato-
2. Referenced Documents
graph, µL.
V —original volume of the test specimen to be analyzed, µL.
2.1 ASTM Standards:
s
V —total volume of the diluted standard, mL.
D 923 Test Method for Sampling Electrical Insulating Liq-
x
V —total volume of the test specimen to be analyzed, µL.
x
uids
W —weight of the test specimen to be analyzed, g.
s
W —weight of the initial standard Aroclor test specimen, g.
D 2233 Specification for Chlorinated Aromatic Hydrocar-
bons (Askarels) for Capacitors
4. Summary of Test Method
D 2283 Specification for Chlorinated Aromatic Hydrocar-
3 4.1 The test specimen is diluted with a suitable solvent. The
bons (Askarels) for Transformers
resulting solution is treated by a procedure to remove interfer-
D 3534 Test Method for Polychlorinated Biphenyls (PCBs)
4 ing substances after which a small portion of the resulting
in Water
solution is injected into a gas chromatographic column. The
componentsareseparatedastheypassthroughthecolumnwith
1 carrier gas and their presence in the effluent is measured by an
This test method is under the jurisdiction of Committee D27 on Electrical
Insulating Liquids and Gases and is the direct responsibility of Subcommittee electron capture (EC) detector and recorded as a chromato-
D27.03 on Analytical Tests.
gram. The test method is made quantitative by comparing the
Current edition approved Oct. 10, 2000. Published December 2000. Originally
sample chromatogram with a chromatogram of a known
published as a proposal. Last previous edition D 4059 – 96.
Registered trademark of Monsanto Co.
Annual Book of ASTM Standards, Vol 10.03.
4 5
Annual Book of ASTM Standards, Vol 11.02. Annual Book of ASTM Standards, Vol 14.02.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 4059 – 00
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
The procedure to be used for a particular apparatus or quantity 28 11.0 5.0 2 25 %
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 %
comparison of the chromatogram of an unknown specimen J
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
chromatograms of Aroclors 1242, 1254, and 1260 obtained 98 1.5 9.4 5
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 %
in Fig. 1, Fig. 2, and Fig. 3 , for isothermal packed columns 146 1.0 19.9 5 75 %
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.
D 4059 – 00
6 6
TABLE 2 Composition of Aroclor 1254 TABLE 3 Composition of Aroclor 1260
Relative Relative
Mean Number of Mean Number of
A A
RRT Standard RRT Standard
C C
Weight, % Chlorines Weight % Chlorines
B B
Deviation Deviation
47 6.2 3.7 4 70 2.7 6.3 5
54 2.9 2.6 4 84 4.7 1.6 5
58 1.4 2.8 4 3.8 3.5 D
J
H 5
70 13.2 2.7 4 25 %
104 60 %
J
5 75 %
640%
84 17.3 1.9 5
117 3.3 6.7 6
98 7.5 5.3 5
125 12.3 3.3 5 15 %
J
104 13.6 3.8 5
6 85 %
125 15.0 2.4 5 70 %
146 14.1 3.6 6
J
6 30 %
160 4.9 2.2 6 50 %
J
146 10.4 2.7 5 30 %
7 50 %
J
6 70 %
174 12.4 2.7 6
160 1.3 8.4 6
203 9.3 4.0 6 10 %
J
174 8.4 5.5 6 7 90 %
203 1.8 18.6 6
232 9.8 3.4
E
H
232 1.0 26.1 7
244 6
J
10 %
90 %
Total 100.0
A
Retention time relative to p,p8-DDE = 100. Measured from first appearance of
280 11.0 2.4 8
solvent.
332 4.2 5.0 8
B
Standard deviation of six results as a percent of the mean of the results (sic
372 4.0 8.6 8
coefficient of variation).
448 0.6 25.3
C
From GC-MS data. Peaks containing mixtures of isomers are bracketed.
528 1.5 10.2
Total 98.6
A
Retention time relative to p,p8-DDE = 100. Measured from first appearance of
1254, and 1260 are adequate standards because they have been
solvent. Overlapping peaks that are quantitated as one peak are bracketed.
B
found to be the most common PCB contaminant in electrical
Standard deviation of six results as a mean of the results (sic coefficient of
variation).
insulating oils.
C
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
numbers are bracketed.
D
6. Interferences
Composition determined at the center of peak 104.
E
Composition determined at the center of peak 232.
6.1 Electron capture detectors respond to other chlorine
containing compounds and to certain other electrophilic mate-
rials containing elements such as other halogens, nitrogen,
Mineral oil should be absent from standards and dilution
oxygen, and sulfur. These materials may give peaks with
solvents used in the analysis of silicone test specimens.
retention times comparable to those of PCBs. Most common
interferences will be removed by the simple pre-analysis 6.3 Residual oxygen in the carrier gas may react with
treatment steps detailed within this test method.The chromato-
components of test specimens to give oxidation products to
gram of each analyzed test specimen should be carefully
whichECdetectorswillrespond.Takecaretoensurethepurity
compared with those of the standards. The results of an
of the carrier gas.
analysis are suspect if major extraneous or unusually large
6.3.1 The use of an oxygen scrubber and a moisture trap on
individual peaks are found.
both the carrier gas and the detector makeup gas is recom-
6.1.1 Data acquisition and treatment by electronic integra-
mended to extend the useful column and detector life.
tors or other instrumental means easily permits the unrecog-
6.4 Trichlorobenzenes (TCBs) are often present with PCBs
nized inclusion of interferences in the quantification of results.
in insulating oils and will generate a response in the EC
Visual examination of chromatograms by those skilled in the
detector. These appear earlier than the first chlorinated biphe-
method should be made to obtain maximum accuracy.
nyl peak ( i = 11) in most cases and should be neglected in this
6.2 The sensitivity of EC detectors is reduced by mineral
analysis. Unusually high concentrations of TCBs may be
oils. The same amount of oil must pass through the detector in
present occasionally and may obscure the lower molecular
both calibration and analysis to ensure a meaningful compari-
weight PCB peaks.
sonforquantification.Sample,standarddilutions,andinjection
6.5 Components of high-molecular weight mineral oils may
volumes should be carefully chosen in this test method to
have longer than normal retention on the chromatography
match the interference of the oil.
6.2.1 The sensitivity of EC detectors is not significantly column, resulting in “ghost” peaks or excessive tailing. These
affected by silicone liquids. Evaluate the need for matrix conditions interfere with the data system’s ability to accurately
matching within your analytical scheme before proceeding. quantify material at levels approaching the method detection
D 4059 – 00
limit. Inject reagent grade solvent blanks until the chromato- 8. Chromatograph Operation Conditions
gram’s baseline returns to normal before continuing with the
8.1 General—The characteristics of individual chromato-
analysis.
graphs and columns differ. Particular operating conditions
should be chosen so as to give the separations shown in Fig. 1,
7. Apparatus
Fig. 2, and Fig. 3 forAroclors 1242, 1254, and 1260. Retention
7.1 Instruments: times of the peaks should be determined relative to 1,18 bis
(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
...