ASTM D6160-98(2003)e1
(Test Method)Standard Test Method for Determination of Polychlorinated Biphenyls (PCBs) in Waste Materials by Gas Chromatography
Standard Test Method for Determination of Polychlorinated Biphenyls (PCBs) in Waste Materials by Gas Chromatography
SIGNIFICANCE AND USE
This test method provides sufficient PCB data for many regulatory requirements. While the most common regulatory level is 50 ppm (dry weight corrected), lower limits are used in some locations. Since sensitivities will vary for different types of samples, one shall demonstrate a sufficient method detection limit for the matrix of interest.
This test method differs from Test Method D 4059 in that it provides for more sample clean-up options, utilizes a capillary column for better pattern recognition and interference discrimination, and includes both a qualitative screening and a quantitative results option.
SCOPE
1.1 This test method is a two-tiered analytical approach to PCB screening and quantitation of liquid and solid wastes, such as oils, sludges, aqueous solutions, and other waste matrices.
1.2 Tier I is designed to screen samples rapidly for the presence of PCBs.
1.3 Tier II is used to determine the concentration of PCBs, typically in the range of from 2 to 50 mg/kg. PCB concentrations greater than 50 mg/kg are determined through analysis of sample dilutions.
1.4 This is a pattern recognition approach, which does not take into account individual congeners that might occur, such as in reaction by-products. This test method describes the use or Aroclors 1016, 1221, 1232, 1242, 1248, 1254, 1260, 1262, and 1268, as reference standards, but others could also be included. Aroclors 1016 and 1242 have similar capillary gas chromatography (GC) patterns. Interferences or weathering are especially problematic with Aroclors 1016, 1232, and 1242 and may make distinction between the three difficult.
1.5 This test method provides sample clean up and instrumental conditions necessary for the determination of Aroclors. Gas chromatography (GC) using capillary column separation technique and electron capture detector (ECD) are described. Other detectors, such as atomic emission detector (AED) and mass spectrometry (MS), may be used if sufficient performance (for example, sensitivity) is demonstrated. Further details about the use of GC and ECD are provided in Practices E 355, E 697, and E 1510.
1.6 Quantitative results are reported on the dry weights of waste samples.
1.7 Quantification limits will vary depending on the type of waste stream being analyzed.
1.8 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 regulator limitations prior to use.
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An American National Standard
e1
Designation:D6160–98 (Reapproved 2003)
Standard Test Method for
Determination of Polychlorinated Biphenyls (PCBs) in Waste
Materials by Gas Chromatography
This standard is issued under the fixed designation D 6160; 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.
e NOTE—Warning notes were editorially moved into the standard text in August 2003.
1. Scope 1.6 Quantitative results are reported on the dry weights of
2 waste samples.
1.1 This test method is a two-tiered analytical approach to
1.7 Quantification limits will vary depending on the type of
PCB screening and quantitation of liquid and solid wastes,
waste stream being analyzed.
such as oils, sludges, aqueous solutions, and other waste
1.8 This standard does not purport to address all of the
matrices.
safety concerns, if any, associated with its use. It is the
1.2 Tier I is designed to screen samples rapidly for the
responsibility of the user of this standard to establish appro-
presence of PCBs.
priate safety and health practices and determine the applica-
1.3 Tier II is used to determine the concentration of PCBs,
bility of regulator limitations prior to use.
typically in the range of from 2 to 50 mg/kg. PCB concentra-
tions greater than 50 mg/kg are determined through analysis of
2. Referenced Documents
sample dilutions.
2.1 ASTM Standards:
1.4 This is a pattern recognition approach, which does not
D 4059 Test Method forAnalysis of Polychlorinated Biphe-
take into account individual congeners that might occur, such
nyls in Insulating Liquids by Gas Chromatography
as in reaction by-products. This test method describes the use
3 E 203 Test Method for Water Using Karl Fischer Titration
ofAroclors 1016, 1221, 1232, 1242, 1248, 1254, 1260, 1262,
E 288 Specification for Laboratory Glass Volumetric
and 1268, as reference standards, but others could also be
Flasks
included. Aroclors 1016 and 1242 have similar capillary gas
E 355 Practice for Gas Chromatography Terms and Rela-
chromatography (GC) patterns. Interferences or weathering are
tionships
especiallyproblematicwithAroclors1016,1232,and1242and
E 697 Practice for Use of Electron-capture Detectors in Gas
may make distinction between the three difficult.
Chromatography
1.5 This test method provides sample clean up and instru-
E 969 Specification for Glass Volumetric (Transfer) Pipet
mental conditions necessary for the determination ofAroclors.
E 1510 Practice for Installing Fused Silica Open Tubular
Gas chromatography (GC) using capillary column separation
Capillary Columns in Gas Chromatography
technique and electron capture detector (ECD) are described.
2.2 U.S. EPA Standards:
Other detectors, such as atomic emission detector (AED) and
Method 608 Organochlorine Pesticides and PCBs
massspectrometry(MS),maybeusedifsufficientperformance
Method 680 Determination of Pesticides and PCBs inWater
(forexample,sensitivity)isdemonstrated.Furtherdetailsabout
and Soil/Sediment by Gas Chromatography/Mass Spec-
theuseofGCandECDareprovidedinPracticesE355,E697,
trometry
and E 1510.
Method 3620 Florisil Column Clean-Up
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee ASTM Annual Book of Standards, Vol 10.03.
D02.04 on Hydrocarbon Analysis. ASTM Annual Book of Standards, Vol 15.05.
Current edition approved May 10, 2003. Published August 2003. Originally ASTM Annual Book of Standards, Vol 14.04.
approved in 1997. Last previous edition approved in 1998 as D 6160–98. Annual Book of ASTM Standards, Vol 03.06.
2 8
This test method is based largely on EPA8080 (and the proposed modification EPAReport 600/4/82–057, Environmental Monitoring and Support Laboratory,
for the use of capillary columns, EPA 8081) and EPA Report 600/4–81–045 by Cincinnati, OH.
Bellar, T. and J. Lichtenberg, reported in 1981. The report is titled,“ The Alford-Stevens, Ann, et al, Physical and Chemical Methods Branch, Environ-
Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils” mental Monitoring and Support Laboratory Office of Research and Development,
and provides significant support to the protocol below. USEPA, Cincinnati, OH.
3 10
Aroclor Standards may be purchased as 1000 µg/mL in isooctane.Aroclor is a U.S. EPA, “Test Methods for Evaluating Solid Waste,” Physical/Chemical
registered trademark of Monsanto. Methods, SW-846.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D6160–98 (2003)
Method 3630 Silica Gel Clean-Up 4.2 For screening (Tier I), instrument performance is moni-
Method 3660 Sulfur Clean-Up tored by a 2-µL injection of a standard containing Aroclors
Method 8082 Determination of PCB in Water and Soil/ 1016 and 1260. For low level work (1 ppm) the instrument is
Sediment by Gas Chromatography: Capillary Column checked with a standard concentration of 0.01 µg/mL (each)
Technique and for higher level work (10 ppm), the instrument is checked
with a 0.1 µg/mL standard.
3. Terminology
4.3 Identification involves a pattern comparison of the
3.1 Definitions of Terms Specific to This Standard:
chromatograms of an unknown sample with that of a standard
3.1.1 Aroclors, n—commercial mixtures of polychlorinated
obtained under identical instrumental conditions.
biphenyl congeners marketed and trademarked by Monsanto
4.4 When quantification is required (Tier II), an external
prior to 1977.
standards method (ESTD) is used. The quantitation technique
3.1.1.1 Discussion—Specific Aroclors are usually desig-
typically requires a comparison of five peaks (minimum of
nated by a four-digit number, with the first two digits usually
three) between the chromatograms of an unknown sample and
designating the number of carbon atoms and the last two digits
that of standard Aroclor obtained under identical conditions.
providingthechlorinecontent(forexample,Aroclor1260is60
Quantitation of either Aroclors 1016 or 1260 is performed
% (weight) chlorine).
using a five-point calibration of a mixed Aroclor standard
3.1.2 congeners, n—compounds related by structural simi-
containingAroclors1016and1260.AllremainingAroclorsare
larities.
quantitated from single point calibrations. Calibration is veri-
3.1.2.1 Discussion—All polychlorinated biphenyls (PCBs)
fied daily by comparison of results obtained for analysis of the
share the same C structure and vary only by the number and
midpoint calibration standard ofAroclor 1016 and 1260 to the
position of the chlorine atoms attached to the aromatic rings.
five-point calibration curve. (SeeAppendix X1 for an example
3.1.3 continuing calibration standard (CCS)—a known
chromatogram and calibration table.)
blend or one or more Aroclors at a fixed concentration that is
injected into the gas chromatograph to demonstrate the validity
5. Significance and Use
of the calibration.
5.1 This test method provides sufficient PCB data for many
3.1.4 dry weight, n—concentration of PCBs after factoring
regulatory requirements. While the most common regulatory
out the water content.
level is 50 ppm (dry weight corrected), lower limits are used in
3.1.4.1 Discussion—This correction assumes that all PCBs
some locations. Since sensitivities will vary for different types
originated from nonaqueous sources and any water present has
of samples, one shall demonstrate a sufficient method detection
been added subsequently, diluting the original concentration.
limit for the matrix of interest.
This correction can be described using the formula:
5.2 This test method differs from Test Method D 4059 in
Aroclor ~mg/Kg!~wet!
Aroclor ~mg/Kg!~dry!5 (1)
that it provides for more sample clean-up options, utilizes a
~100 2 % water!/100
capillary column for better pattern recognition and interference
3.1.5 instrument performance standard (IPS), n—a known
discrimination, and includes both a qualitative screening and a
low level of anAroclor in a clean solvent used as a comparator
quantitative results option.
to determine which qualitative (screening) results are of
sufficient magnitude to require quantitative analyses.
6. Interferences
3.1.6 surrogate, n—compound or compounds that are simi-
6.1 The ECD has selective sensitivity to alkyl halides,
lar to analytes of interest in chemical composition, extraction,
conjugated carbonyls, nitrogen compounds, organometallics,
and chromatography, but that are not normally found at
and sulfur. Therefore, the chromatogram obtained for each
significant levels in the matrices of interest.
sample shall be carefully compared to chromatograms of
3.1.6.1 Discussion—Surrogates may be spiked into blanks,
standards to allow proper interpretation.
standards, samples, or matrix spikes prior to analysis to allow
a determination of a quantitative recovery rate. Surrogates are 6.2 Solvents,reagents,glassware,andothersampleprocess-
also used to document matrix effects and method control. ing hardware may yield artifacts or interferences, or both, to
3.1.7 wastematerial,n—anymatter,withinthescopeofthis standard analysis. All these materials shall be demonstrated to
test method, that is in the process of being recycled or be free from interferences under the conditions of analysis by
disposed. analyzing method blanks.
6.3 Interferences from phthalate esters may pose a major
4. Summary of Test Method
problem in Aroclor determinations when using ECD. Phtha-
4.1 The sample is extracted with solvent and the extract is
lates generally appear in the chromatogram as broad late
treatedtoremoveinterferingsubstances,ifneeded.Thesample
eluting peaks. Since phthalates are commonly used as plasti-
extract is injected into a gas chromatograph. The components
cizers and are easily extracted from plastic, all contact of
are separated as they pass through the capillary column and
samples and extracts with plastic should be avoided.
polychlorinated biphenyl compounds, if present, are detected
6.4 While general clean-up techniques are provided as part
by an ECD.
of this test method, some samples may require additional
clean-up beyond the scope of this test method before proper
NOTE 1—Portions of this test method are similar to EPAMethods 608,
680, and 8082. instrumental analysis may be performed.
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D6160–98 (2003)
7. Apparatus 8.3.1 Just before use, activate each batch at least4hat
130°C in a glass container loosely covered with aluminum foil.
7.1 Gas Chromatograph, a temperature programmable gas
Alternatively, store the magnesium silicate in an oven at
chromatograph suitable for splitless injections; equipped with
130°C. Cool the magnesium silicate in a desiccator for 30 min
an ECD.
before use.
7.2 Data System, a data system capable of measuring peak
8.4 Hexane—(Warning—Extremelyflammable.Harmfulif
areas.
inhaled. May produce nerve cell damage. Vapors may cause
7.3 Regulator (Make-up Gas)—N or Ar:Methane (95:5);
flash fire.)
two stage regulator rated at 20 MPa (3000 psi) inlet and 35 to
860 kPa (5 to 125 psi) outlet. 8.5 Isooctane—(Warning—Extremelyflammable.Harmful
if inhaled. Vapors may cause flash fire.)
7.4 Regulator (Carrier Gas)—H , two-stage regulator rated
at 20 MPa (3000 psi) inlet and 35 to 860 kPa (5 to 125 psi)
8.6 Methanol—(Warning—Flammable. Vapor harmful.
outlet. May be fatal or cause blindness if swallowed or inhaled.
7.5 Gas Purifiers, to remove moisture and particulates.
Cannot be made nonpoisonous.)
Depending on the levels and types of interferences encoun-
8.7 Silynization Reagent (for example, 5 % dimethyldichlo-
tered, these might involve molecular sieves (moisture), acti-
rosilane in toluene). See Annex A2 for instructions.
vated carbon (organics), or other commercially-available me-
8.8 Sodium Sulfate, granular, anhydrous (maintained at
dia.
130°C for at least 24 h prior to use). Cool the sodium sulfate in
7.6 Flow Meter, to measure gas flow. Typical range is from
a desiccator for 30 min before use.
0.5 to 50 mL/min. 6 0.1 mL/min.
8.9 Sulfuric Acid (concentrated):
7.7 Column, crosslinked 5 % phenyl methyl silicone, 30 m
8.10 Acetone/Hexane, 10 % acetone/90 % hexane (v/v).
by 0.32 mm id by 0.25 µm film thickness.
8.11 Gases, Hydrogen (zero grade; 99.995 % purity) and
7.7.1 It is possible that other columns will provide sufficient
nitrogen(zerograde;99.998%purity)orargon/methane(95:5;
separating power, but this shall be demonstrated before use.
ECD grade).
7.8 Analytical Balance, capable of weighing to 0.0001 g.
8.11.1 Careshallbegiventoensurepurityofthecarriergas.
7.9 Volumetric Flasks, 10, 50, 100, 200 mL, (see Specifica-
For example, an in-line filter may be required.
tion E 288) Class A with ground-glass stoppers.
8.12 Aroclor Standards , Aroclor 1016, 1221, 1232, 1242,
7.10 Vortex Mixer:
1254, 1260, 1262, 1268.
7.11 Vials, glass, 20 mL and 40 mL capacity with TFE-
8.13 Decachlorobiphenyl (DCB) (surrogate) Optional:
fluorocarbon-lined caps.
7.12 Septum Inserts—Inserts shall be treated with a si-
8.13.1 Surrogate Stock Standard (15 µg/mL) Preparation—
lynization reagent before use or after cleaning. (SeeAnnexA2
Accurately dilute 1.5 mL of 1000 µg/mL DCB concentrate in
for possible procedure.) They may be purchased already
100 mL volumetric flask and fill to the mark with methanol,
treated.
yielding a 15 µg/mL solution.
7.13 Volumetric Pipette, 1, 5, 10 mL (see Specification E
8.13.2 Surrogate Working Standard (1.5 µg/mL)
969), Class A.
Preparation—Accurately dilute 10 mL of the 15 µg/mL DCB
7.14 Syringe, 500 µL, mechanical guide.
stockstandardina100mLvolumetricflaskandfilltothemark
with methanol, yielding a 1.5 µg/mL working DCB standard.
8. Reagents and Materials
NOTE 2—Sample preparations will normally use 0.1 mL of this solu-
8.1 Purity of Reagents—Reagent grade chemicals shall be
tion. The resulting concentration in the sample extract is 0.005 µg/mL
used in all tests. Unless otherwise indicated, it is intended that
before any further dilutions. The following calculations show this.
all reagents conform to the specifications of the Committee on
1.5 µg/mL 3 0.l mL 5 0.15 µg
Analytical Reagents of the American Chemical Society where
0.15 µg
such specifications are available. Other grades may be used,
5 0.005 µg/mL (2)
~3.0 mL sample 1 27 mL!
provided it is first ascertained that the reagent is of sufficiently
8.14 Calibration Standards:
high purity to permit its use without lessening the accuracy of
the determination. 8.14.1 Intermediate Stock Standard (50 µg/mL):
8.2 Aceto
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