ASTM D4059-00(2018)

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4059 − 00 (Reapproved 2018)
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 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method describes a quantitative determination
of the concentration of polychlorinated biphenyls (PCBs) in D923Practices for Sampling Electrical Insulating Liquids
electrical insulating liquids by gas chromatography. It also
3. Symbols
appliestothedeterminationofPCBpresentinmixturesknown
as askarels, used as electrical insulating liquids.
3.1 The following symbols are used in this test method:
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
determination of PCBs in insulating liquids contaminated by
i
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
other sources of contamination.
i
standard Aroclor test specimen, g.
s
1.3 The precision and bias of this test method have been R —response of the detector to PCB components with relative retention
i
time, i, in the chromatograms of the standard, s, solutions, response
establishedonlyforPCBconcentrationsinelectricalinsulating
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
time, i, in the chromatogram of an unknown test specimen, may be
been demonstrated for all insulating fluids. Some insulating
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;
may be expressed as peak height, peak area, or integrator counts.
1.4 The values stated in SI units are to be regarded as
x
R —response of the detector to PCB components in the largest or most
p
standard. No other units of measurement are included in this cleanly separated peaks, p, in the chromatogram of an unknown test
specimen contaminated by a single Aroclor; may be expressed in
standard.
peak height, peak area, or integrator counts.
s
1.5 This standard does not purport to address all of the ν —volume of the standard test specimen injected into the
chromatograph, µL.
safety concerns, if any, associated with its use. It is the
x
ν —volume of the unknown test specimen injected into the
responsibility of the user of this standard to establish appro-
chromatograph, µL.
V —original volume of the test specimen to be analyzed, µL.
priate safety, health, and environmental practices and deter-
s
V —total volume of the diluted standard, mL.
mine the applicability of regulatory limitations prior to use.
x
V —total volume of the test specimen to be analyzed, µL.
x
1.6 This international standard was developed in accor-
W —weight of the test specimen to be analyzed, g.
s
W —weight of the initial standard Aroclor test specimen, g.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
4. Summary of Test Method
Development of International Standards, Guides and Recom-
4.1 Thetestspecimenisdilutedwithasuitablesolvent.The
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee. resulting solution is treated by a procedure to remove interfer-
ing substances after which a small portion of the resulting
solution is injected into a gas chromatographic column. The
componentsareseparatedastheypassthroughthecolumnwith
This test method is under the jurisdiction of Committee D27 onElectrical
Insulating Liquids and Gasesand is the direct responsibility of Subcommittee
D27.03 on Analytical Tests.
Current edition approved Dec. 1, 2018. Published December 2018. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
published as a proposal. Last previous edition approved in 2010 as D4059–00 contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
(2010). DOI: 10.1520/D4059-00R18. Standards volume information, refer to the standard’s Document Summary page on
Registered trademark of Monsanto Co. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4059 − 00 (2018)
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
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 deter-
mined by mass spectroscopy and are given in Table 1, Table 2,
andTable3. Otherchromatographicoperatingconditions,and
in particular, other column packing materials, may give differ-
entseparations.Thedatagiveninthetablesshouldnotbeused
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
FIG. 1 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
chlorine substituents can cause substantially different re-
Column Temperature: 170°C, Detector: Electron Capture
sponses 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 mixtures and those found in the
unknown test specimen are closely related. Aroclors 1242,
1254,and1260areadequatestandardsbecausetheyhavebeen
found to be the most common PCB contaminant in electrical
insulating oils.
6. Interferences
6.1 Electron capture detectors respond to other chlorine
containing compounds and to certain other electrophilic mate-
FIG. 2 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min, rials containing elements such as other halogens, nitrogen,
Column Temperature: 170°C, Detector: Electron Capture
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
treatmentstepsdetailedwithinthistestmethod.Thechromato-
gram of each analyzed test specimen should be carefully
carrier gas and their presence in the effluent is measured by an
compared with those of the standards. The results of an
electron capture (EC) detector and recorded as a chromato-
analysis are suspect if major extraneous or unusually large
gram. The test method is made quantitative by comparing the
individual peaks are found.
sample chromatogram with a chromatogram of a known
6.1.1 Data acquisition and treatment by electronic integra-
quantity of one or more standardAroclors, obtained under the
tors or other instrumental means easily permits the unrecog-
same analytical conditions.
nized inclusion of interferences in the quantification of results.
5. Significance and Use
5.1 United States governmental regulations mandate that 4
Webb, R. G., and McCall,A. C., Journal of Chromatographic Science, Vol 11,
1973, p. 366.
electrical apparatus and electrical insulating fluids containing
Reproduced from the Journal of Chromatographic Science by permission of
PCB be handled and disposed of through specific procedures.
Preston Publications, Inc.
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.
5.2 Quantificationinthistechniquerequiresapeak-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.
5.3 The technique described is based on data for standard
chromatograms of Aroclors 1242, 1254, and 1260 obtained
FIG. 3 Column: 3 % OV-1, Carrier Gas: Nitrogen at 60 mL/min,
using specific chromatographic column packing materials and Column Temperature: 170°C, Detector: Electron Capture
D4059 − 00 (2018)
6 6
TABLE 1 Composition of Aroclor 1242 TABLE 2 Composition of Aroclor 1254
Relative Relative
Mean Number of Mean Number of
A A
RRT Standard RRT Standard
C C
Weight, % Chlorines Weight, % Chlorines
B B
Deviation Deviation
11 1.1 35.7 1 47 6.2 3.7 4
16 2.9 4.2 2 54 2.9 2.6 4
21 11.3 3.0 2 58 1.4 2.8 4
28 11.0 5.0 70 13.2 2.7
2 25 % 4 25 %
J J
3 75 % 5 75 %
32 6.1 4.7 3 84 17.3 1.9 5
37 11.5 5.7 3 98 7.5 5.3 5
104 13.6 3.8 5
40 11.1 6.2 3
47 8.8 4.3 4 125 15.0 2.4
5 70 %
54 6.8 2.9
J
3 33 %
6 30 %
J
4 67 %
146 10.4 2.7
5 30 %
58 5.6 3.3 4
J
6 70 %
70 10.3 2.8
4 90 %
J
5 10 %
160 1.3 8.4 6
174 8.4 5.5 6
203 1.8 18.6 6
78 3.6 4.2 4
84 2.7 9.7 5 232 1.0 26.1 7
98 1.5 9.4 5
104 2.3 16.4 5 Total 100.0
125 1.6 20.4
A
5 85 % Retention time relative to p,p'-DDE = 100. Measured from first appearance of
J
solvent.
6 15 %
B
Standard deviation of six results as a percent of the mean of the results (sic
coefficient of variation).
146 1.0 19.9
C
5 75 %
From GC-MS data. Peaks containing mixtures of isomers are bracketed.
J
6 25 %
Total 98.5
A
Retention time relative to p ,p'-DDE = 100. Measured from first appearance of
nylpeak( i=11)inmostcasesandshouldbeneglectedinthis
solvent.
B
Standard deviation of six results as a percentage of the mean of the results (sic analysis. Unusually high concentrations of TCBs may be
coefficient of variation).
present occasionally and may obscure the lower molecular
C
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
weight PCB peaks.
numbers are bracketed.
6.5 Componentsofhigh-molecularweightmineraloilsmay
have longer than normal retention on the chromatography
column, resulting in “ghost” peaks or excessive tailing. These
Visual examination of chromatograms by those skilled in the
conditionsinterferewiththedatasystem’sabilitytoaccurately
method should be made to obtain maximum accuracy.
quantify material at levels approaching the method detection
6.2 The sensitivity of EC detectors is reduced by mineral
limit. Inject reagent grade solvent blanks until the chromato-
oils.The same amount of oil must pass through the detector in
gram’s baseline returns to normal before continuing with the
both calibration and analysis to ensure a meaningful compari-
analysis.
sonforquantification.Sample,standarddilutions,andinjection
volumes should be carefully chosen in this test method to
7. Apparatus
match the interference of the oil.
7.1 Instruments:
6.2.1 The sensitivity of EC detectors is not significantly
7.1.1 Gas Chromatograph, equipped with oven temperature
affected by silicone liquids. Evaluate the need for matrix
control reproducible to 1°C and with heated injection port.
matching within your analytical scheme before proceeding.
7.1.2 Means to Record the Chromatogram, such as a pen
Mineral oil should be absent from standards and dilution
recorder,preferablycoupledtoadigitalintegratortodetermine
solvents used in the analysis of silicone test specimens.
peak areas. An automatic sample injector may be used.
6.3 Residual oxygen in the carrier gas may react with
7.1.3 Injector, stainless steel construction, equipped with
components of test specimens to give oxidation products to
suitable adapters to permit use of direct column injection,
whichECdetectorswillrespond.Takecaretoensurethepurity
packed column injection, or split/splitless capillary injection.
of the carrier gas.
All metal surfaces shall be lined with glass.
6.3.1 The use of an oxygen scrubber and a moisture trap on
7.1.3.1 Mega-bore capillary columns may be effectively
both the carrier gas and the detector makeup gas is recom-
utilized on a packed column injector by replacing the standard
mended to extend the useful column and detector life.
glass liner with a tapered capillary liner. While capillary
6.4 Trichlorobenzenes (TCBs) are often present with PCBs conversion kits are commercially available, this specialized
in insulating oils and will generate a response in the EC hardware will not routinely be necessary when working with
detector. These appear earlier than the first chlorinated biphe- mega-bore columns.
D4059 − 00 (2018)
6 6 8 7
TABLE 3 Composition of Aroclor 1260
nents. Packings OV101 and DC200 on Chromosorb WAW
Mean Relative Standard also give separations with which the data in Table 1, Table 2,
A C
RRT Number of Chlorines
B
Weight % Deviation
and Table 3 may be used.
70 2.7 6.3 5
7.2.2 A fused silica wide-bore capillary column such as a
84 4.7 1.6 5
15-mmega-bore(0.53-mmID)columnhavinga1.5-µmfilmof
3.8 3.5
D
polydimethylsiloxanehasbeenshowntoapproximateapacked
J
H
104 60 % column system and generate chromatograms with similar
separations thus allowing the use of the Webb & McCall
640%
calibration data.
117 3.3 6.7 6
125 12.3 3.3
7.3 Volumetric Flasks and Pipettes, appropriate for making
5 15 %
J
6 85 %
dilutions.
7.4 Precision Syringe, glass, graduated to 0.1 µL.
146 14.1 3.6 6
160 4.9 2.2
6 50 %
7.5 Vials, glass, with PTFE-lined aluminum caps.
J
7 50 %
7.6 Analytical Balance or Hydrometer, capable of measur-
174 12.4 2.7 6 ing densities of approximately 0.9 g/mL.
203 9.3 4.0
6 10 %
J
7 90 %
8. Chromatograph Operation Conditions
8.1 General—The characteristics of individual chromato-
9.8 3.4
graphs and columns differ. Particular operating conditions
H
E
244 6
J
should be chosen so as to give the separations shown inFig. 1,
10 %
Fig.2,andFig.3forAroclors1242,1254,and1260.Retention
90 %
times of the peaks should be determined relative to 1,1' bis
(4-chlorophenyl) ethane (p,p'-DDE) to identify the individual
280 11.0 2.4 8
peakswiththoseshowninthechromatogramsandlistedinthe
332 4.2 5.0 8
372 4.0 8.6 8 tables. General ranges of temperatures and flow rate with
448 0.6 25.3
which satisfactory separations have been obtained are listed.
528 1.5 10.2
8.2 Column Temperature—Isothermal temperatures be-
Total 98.6
tween 165 and 200°C have been found suitable when using
A
Retention time relative to p,p'-DDE = 100. Measured from first appearance of
packed column (see Fig. 1). Temperature programming of
solvent. Overlapping peaks that are quantitated as one peak are bracketed.
B megabore columns over the range of 165 to 300°C has been
Standard deviation of six results as a mean of the results (sic coefficient of
variation). found to enhance resolution and decrease the analytical run
C
From GC-MS data. Peaks containing mixtures of isomers of different chlorine
time, while generating a chromatogram suitable for use with
numbers are bracketed.
D the packed column GC/MS data (see Appendix X4).
Composition determined at the center of peak 104.
E
Composition determined at the center of peak 232.
NOTE 2—Typical chromatographic conditions for a temperature pro-
grammed mega-bore capillary column are included in Appendix X4 with
the sample chromatograms.
7.1.4 Detector—High-temperature Ni electron capture 8.3 Detector Temperature—Control the detector isother-
detector with sufficient sensitivity to allow 50% full-scale mally above the maximum oven analysis temperature. A
suitable temperature is typically between 280 and 400°C.
recorder deflection with a sample containing 0.6 ng or less of
phosphorothioic acid o-(2-chloro-4-nitrophenyl) o,o- Follow instrument manufacturer’s instructions to prevent ex-
ceeding the maximum allowable temperature for the radioac-
dimethylester (“dicapthon”). The detector must be operated
within its linear response range and the detector noise level tive foil.
should be less than 2% of full scale.
8.4 Injection Port Temperature —Maintain the injection
port isothermally above a minimum of 250°C.
NOTE 1—Other detectors may be used. Refer to Appendix X1.
7.2 Column, made of glass or fused silica, packed with 8.5 Carrier Gas—Ultrahigh purity 5% methane-95% ar-
appropriate materials.Aprecolumn may be used to extend the gon mixture (P-5) or nitrogen shall be utilized for packed
analytical column’s useful life.
column chromatography. Optimum performance for mega-
7.2.1 A 1.83-m (6-ft) long, 6.35-mm (0.25-in.) outside bore/capillary columns is achieved with ultrahigh purity hy-
diameter, 2 to 4-mm (0.08 to 0.16 in.) inside diameter glass
drogen or helium as the carrier gas and P-5 or nitrogen for
6 7
column packed with 3% OV1 on 80/100 mesh Chromosorb detector makeup.Adevice that will remove oxygen and water
has been found useful. Other column lengths may be used,
vaporfromthecarriergasshouldbeusedinordertomaximize
provided they give adequate separation of the PCB compo- detector sensitivity.
Registered trademark of Ohio Valley Specialty Co.
7 8
Registered trademark of Johns-Manville Product Corp. Registered trademark of Dow-Corning Co.
D4059 − 00 (2018)
8.6 Flow Rates—Column flow rates of 8 to 60 mL/min and, solution for preparation of working standards. The exact
if used, a detector makeup flow of 15 to 30 mL/min have been weightoftheAroclorandthetotalvolumeofthefinalsolution
s s
found satisfactory. When hydrogen or helium are used as a should be recorded as W , g and V , mL.
carrier gas, a makeup flow two to three times the carrier flow 11.3.1 Mineral Insulating Oil Test Specimens—Use a stock
will be required to obtain sufficient detector sensitivity. solution of mineral oil in solvent to prepare standards for
analysis of mineral oil test specimens, made by dissolving 10
9. Reagents and Materials
to 20 g of the appropriate mineral insulating oil per 1 L of
pesticide-grade solvent. The precise amount of oil should be
9.1 Standards—Sample quantities, or analyzed solutions, of
chosentogivethesamesolvent-to-oilratioinstandardsasthat
Aroclors 1242, 1254, and 1260.
to be obtained on diluting test specimens to be analyzed (see
9.2 Insulating Oil,freshunused,ofthetypebeinganalyzed,
12.3). The ratio of solvent-to-oil should not be less than 50:1.
PCB-free.
11.3.2 Silicone Insulating Liquid Test Specimens—Use
NOTE 3—Mineral insulating oils with a viscosity approximately 10 cSt pesticide-grade solvent alone to prepare standards for analysis
at40°Careproducedbyanumberofpetroleumcompaniesandhavebeen
of silicone liquid test specimens.
found suitable for this purpose.
11.3.2.1 The most convenient method of preparing the
9.3 Solvent—n-Hexane, Heptane or 2,2,4-trimethylpentane
standard for injection is to dilute a commercially available
(isooctane), pesticide grade.
solution of known concentration. Otherwise, it is necessary to
prepare the standard by progressive dilutions. The amount of
9.4 Sulfuric Acid, concentrated, AR grade.
oil in the stock solution may require adjustment if the com-
9.5 Adsorbent for polar, electrophilic impurities.
mercial standard solution is very dilute.
NOTE 4—Florisil® (60/100 mesh) has been found suitable for this s
11.4 Injectavolume,ν ,µL,ofthedilutedAroclorstandard
purpose. Before use, activate each batch by heating overnight at 130°C in
into the chromatograph. Recommended injection volumes
a foil-covered glass container. Florisil® heated to appreciably higher
range from 1 to 5 µL, depending on individual detector
temperaturescanabsorbsomePCB.Testtheeffectofeachactivatedbatch
on a standard Aroclor solution. response and anticipated sample injection volume (12.5). The
quantity of PCB injected, M, g, is as follows:
9.6 Dicapthon [phosphorothioic acid-O(2-chloro-4-nitre-
s
phenyl)-O,O-dimethylester] to determine detector sensitivity.
W
s 23
M 5 3ν 10 g (1)
s
V
9.7 p, p'-DDE [1,1'-bis(4-chlorophenyl)ethane] to establish
relative retention times.
Identify each peak by comparison with the relative retention
times given in Table 1, Table 2, and Table 3 or by comparison
NOTE 5—Mixtures of Aroclors 1242, 1254, and 1260 may be used
with the chromatograms in Fig. 1, Fig. 2, and Fig. 3. The
conveniently for standards.
quantity of PCB represented by each peak, M,g,is
i
10. Sampling
M 5 M 3f 310 (2)
i i
10.1 Obtain the test specimen of oil in accordance with
11.4.1 Values of f are given in Table 1, Table 2, and Table
i
Practices D923.
3.
11.4.2 Values of M should be less than 10 ng to avoid
11. Calibration
overloading the detector with a resulting loss in sensitivity.
11.1 Chromatograms of Aroclors 1242, 1254, and 1260
together contain all the peaks normally found in Aroclor
12. Procedure
mixtures. These three materials may, therefore, be used as
12.1 Preparation—Equilibrate the chromatograph to the
standards for routine quantitative analysis of PCB contamina-
conditions recommended in Section 8. Clean all glassware and
tion of insulating fluids. Other Aroclors (for example 1016,
syringes by repeated rinsing in pesticide grade solvent. Ensure
1248,etc.)standardsmaybeusefulforidentificationpurposes,
that a satisfactory level of cleanliness has been obtained by
but are not needed in quantifying the results.
injecting aliquots of the solvent washings into the chromato-
11.2 Aroclor 1242 contains virtually no PCB substituted
graph.
...