ASTM D6160-98(2013)
(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
5.1 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.
5.2 This test method differs from Test Method D4059 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 method2 covers 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 of Aroclors3 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 E355, E697, and E1510.
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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.9 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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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: D6160 − 98 (Reapproved 2013)
Standard Test Method for
Determination of Polychlorinated Biphenyls (PCBs) in Waste
Materials by Gas Chromatography
This standard is issued under the fixed designation D6160; 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.
1. Scope 1.6 Quantitative results are reported on the dry weights of
2 waste samples.
1.1 This test method covers a two-tiered analytical ap-
proach to PCB screening and quantitation of liquid and solid 1.7 Quantification limits will vary depending on the type of
wastes, such as oils, sludges, aqueous solutions, and other waste stream being analyzed.
waste matrices.
1.8 The values stated in SI units are to be regarded as
1.2 Tier I is designed to screen samples rapidly for the standard. No other units of measurement are included in this
presence of PCBs. standard.
1.9 This standard does not purport to address all of the
1.3 Tier II is used to determine the concentration of PCBs,
safety concerns, if any, associated with its use. It is the
typically in the range of from 2 to 50 mg/kg. PCB concentra-
responsibility of the user of this standard to establish appro-
tions greater than 50 mg/kg are determined through analysis of
priate safety and health practices and determine the applica-
sample dilutions.
bility of regulator limitations prior to use.
1.4 This is a pattern recognition approach, which does not
take into account individual congeners that might occur, such
2. Referenced Documents
as in reaction by-products. This test method describes the use
2.1 ASTM Standards:
ofAroclors 1016, 1221, 1232, 1242, 1248, 1254, 1260, 1262,
D4059 Test Method for Analysis of Polychlorinated Biphe-
and 1268, as reference standards, but others could also be
nyls in Insulating Liquids by Gas Chromatography
included. Aroclors 1016 and 1242 have similar capillary gas
E203 Test Method for Water Using Volumetric Karl Fischer
chromatography (GC) patterns. Interferences or weathering are
Titration
especiallyproblematicwithAroclors1016,1232,and1242and
E288 Specification for Laboratory Glass Volumetric Flasks
may make distinction between the three difficult.
E355 Practice for Gas ChromatographyTerms and Relation-
1.5 This test method provides sample clean up and instru-
ships
mental conditions necessary for the determination ofAroclors.
E697 Practice for Use of Electron-Capture Detectors in Gas
Gas chromatography (GC) using capillary column separation
Chromatography
technique and electron capture detector (ECD) are described.
E969 Specification for Glass Volumetric (Transfer) Pipets
Other detectors, such as atomic emission detector (AED) and
E1510 Practice for Installing Fused Silica Open Tubular
massspectrometry(MS),maybeusedifsufficientperformance
Capillary Columns in Gas Chromatographs
(forexample,sensitivity)isdemonstrated.Furtherdetailsabout
2.2 U.S. EPA Standards:
the use of GC and ECD are provided in Practices E355, E697,
Method 608 Organochlorine Pesticides and PCBs
and E1510.
Method 680 Determination of Pesticides and PCBs in Water
1 and Soil/Sediment by Gas Chromatography/Mass Spec-
This test method is under the jurisdiction of ASTM Committee D02 on
trometry
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.04.0L on Gas Chromatography Methods.
Current edition approved May 1, 2013. Published August 2013. Originally
approved in 1997. Last previous edition approved in 2008 as D6160 – 98 (2008).
DOI: 10.1520/D6160-98R13. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is based largely on EPA8080 (and the proposed modification contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
for the use of capillary columns, EPA 8081) and EPA Report 600/4–81–045 by Standards volume information, refer to the standard’s Document Summary page on
Bellar, T. and J. Lichtenberg, reported in 1981. The report is titled, “The the ASTM website.
Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils,” EPAReport 600/4/82–057, Environmental Monitoring and Support Laboratory,
and provides significant support to the protocol in this standard. Cincinnati, OH.
Aroclor Standards may be purchased as 1000 µg/mL in isooctane.Aroclor is a Alford-Stevens, Ann, et al, Physical and Chemical Methods Branch, Environ-
registered trademark of the Monsanto Company, 800 N. Lindbergh Blvd., St. Louis, mental Monitoring and Support Laboratory Office of Research and Development,
MO 63167. USEPA, Cincinnati, OH.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D6160 − 98 (2013)
Method 3620 Florisil Column Clean-Up extract is injected into a gas chromatograph. The components
Method 3630 Silica Gel Clean-Up are separated as they pass through the capillary column and
Method 3660 Sulfur Clean-Up polychlorinated biphenyl compounds, if present, are detected
Method 8082 Determination of PCB in Water and Soil/ by an ECD.
Sediment by Gas Chromatography: Capillary Column
NOTE 1—Portions of this test method are similar to EPAMethods 608,
Technique
680, and 8082.
4.2 For screening (Tier I), instrument performance is moni-
3. Terminology
tored by a 2-µL injection of a standard containing Aroclors
3.1 Definitions of Terms Specific to This Standard:
1016 and 1260. For low level work (1 ppm) the instrument is
3.1.1 Aroclors, n—commercial mixtures of polychlorinated
checked with a standard concentration of 0.01 µg/mL (each)
biphenyl congeners marketed and trademarked by Monsanto
and for higher level work (10 ppm), the instrument is checked
prior to 1977.
with a 0.1 µg/mL standard.
3.1.1.1 Discussion—Specific Aroclors are usually desig-
4.3 Identification involves a pattern comparison of the
nated by a four-digit number, with the first two digits usually
chromatograms of an unknown sample with that of a standard
designating the number of carbon atoms and the last two digits
obtained under identical instrumental conditions.
providingthechlorinecontent(forexample,Aroclor1260is60
4.4 When quantification is required (Tier II), an external
% (weight) chlorine).
standards method (ESTD) is used. The quantitation technique
3.1.2 congeners, n—compounds related by structural simi-
typically requires a comparison of five peaks (minimum of
larities.
three) between the chromatograms of an unknown sample and
3.1.2.1 Discussion—All polychlorinated biphenyls (PCBs)
that of standard Aroclor obtained under identical conditions.
share the same C structure and vary only by the number and
Quantitation of either Aroclors 1016 or 1260 is performed
position of the chlorine atoms attached to the aromatic rings.
using a five-point calibration of a mixed Aroclor standard
3.1.3 continuing calibration standard (CCS) —a known
containingAroclors1016and1260.AllremainingAroclorsare
blend or one or more Aroclors at a fixed concentration that is
quantitated from single point calibrations. Calibration is veri-
injected into the gas chromatograph to demonstrate the validity
fied daily by comparison of results obtained for analysis of the
of the calibration.
midpoint calibration standard ofAroclor 1016 and 1260 to the
3.1.4 dry weight, n—concentration of PCBs after factoring
five-point calibration curve. (See Appendix X1 for an example
out the water content.
chromatogram and calibration table.)
3.1.4.1 Discussion—This correction assumes that all PCBs
originated from nonaqueous sources and any water present has
5. Significance and Use
been added subsequently, diluting the original concentration.
5.1 This test method provides sufficient PCB data for many
This correction can be described using the formula:
regulatory requirements. While the most common regulatory
Aroclor ~mg/Kg!~wet!
level is 50 ppm (dry weight corrected), lower limits are used in
Aroclor mg/Kg dry 5 (1)
~ !~ !
100 2 % water /100
~ !
some locations. Since sensitivities will vary for different types
3.1.5 instrument performance standard (IPS), n—a known
ofsamples,oneshalldemonstrateasufficientmethoddetection
low level of anAroclor in a clean solvent used as a comparator
limit for the matrix of interest.
to determine which qualitative (screening) results are of
5.2 ThistestmethoddiffersfromTestMethodD4059inthat
sufficient magnitude to require quantitative analyses.
it provides for more sample clean-up options, utilizes a
3.1.6 surrogate, n—compound or compounds that are simi-
capillary column for better pattern recognition and interference
lar to analytes of interest in chemical composition, extraction,
discrimination, and includes both a qualitative screening and a
and chromatography, but that are not normally found at
quantitative results option.
significant levels in the matrices of interest.
3.1.6.1 Discussion—Surrogates may be spiked into blanks,
6. Interferences
standards, samples, or matrix spikes prior to analysis to allow
6.1 The ECD has selective sensitivity to alkyl halides,
a determination of a quantitative recovery rate. Surrogates are
conjugated carbonyls, nitrogen compounds, organometallics,
also used to document matrix effects and method control.
and sulfur. Therefore, the chromatogram obtained for each
3.1.7 waste material, n—anymatter,withinthescopeofthis
sample shall be carefully compared to chromatograms of
test method, that is in the process of being recycled or
standards to allow proper interpretation.
disposed.
6.2 Solvents,reagents,glassware,andothersampleprocess-
ing hardware may yield artifacts or interferences, or both, to
4. Summary of Test Method
standard analysis. All these materials shall be demonstrated to
4.1 The sample is extracted with solvent and the extract is
be free from interferences under the conditions of analysis by
treatedtoremoveinterferingsubstances,ifneeded.Thesample
analyzing method blanks.
6.3 Interferences from phthalate esters may pose a major
problem in Aroclor determinations when using ECD. Phtha-
U.S. EPA, “Test Methods for Evaluating Solid Waste,” Physical/Chemical
Methods, SW-846. lates generally appear in the chromatogram as broad late
D6160 − 98 (2013)
eluting peaks. Since phthalates are commonly used as plasti- such specifications are available. Other grades may be used,
cizers and are easily extracted from plastic, all contact of provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of
samples and extracts with plastic should be avoided.
the determination.
6.4 While general clean-up techniques are provided as part
8.2 Acetone—(Warning— Extremely flammable. Vapors
of this test method, some samples may require additional
may cause flash fire.)
clean-up beyond the scope of this test method before proper
8.3 Activated Magnesium Silicate (Florisil), Pesticide resi-
instrumental analysis may be performed.
due (PR) grade (60/100 mesh); store in glass containers with
ground glass stoppers or foil lined screw caps.
7. Apparatus
8.3.1 Just before use, activate each batch at least4hat
7.1 Gas Chromatograph, a temperature programmable gas
130°C in a glass container loosely covered with aluminum foil.
chromatograph suitable for splitless injections; equipped with
Alternatively, store the magnesium silicate in an oven at
an ECD.
130°C. Cool the magnesium silicate in a desiccator for 30 min
before use.
7.2 Data System, a data system capable of measuring peak
areas.
8.4 Hexane—(Warning— Extremely flammable. Harmful
if 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
8.5 Isooctane—(Warning— Extremely flammable. Harm-
860 kPa (5 to 125 psi) outlet.
ful if inhaled. Vapors may cause flash fire.)
7.4 Regulator (Carrier Gas)—H , two-stage regulator rated
8.6 Methanol—(Warning— Flammable. Vapor harmful.
at 20 MPa (3000 psi) inlet and 35 to 860 kPa (5 to 125 psi)
May be fatal or cause blindness if swallowed or inhaled.
outlet.
Cannot be made nonpoisonous.)
7.5 Gas Purifiers, to remove moisture and particulates.
8.7 Silynization Reagent (for example, 5 % dimethyldichlo-
Depending on the levels and types of interferences
rosilane in toluene). See Annex A2 for instructions.
encountered, these might involve molecular sieves (moisture),
8.8 Sodium Sulfate, granular, anhydrous (maintained at
activated carbon (organics), or other commercially-available
130°C for at least 24 h prior to use). Cool the sodium sulfate in
media.
a desiccator for 30 min before use.
7.6 Flow Meter, to measure gas flow. Typical range is from
8.9 Sulfuric Acid (concentrated):
0.5 to 50 mL/min. 6 0.1 mL/min.
8.10 Acetone/Hexane, 10 % acetone/90 % hexane (v/v).
7.7 Column, crosslinked 5 % phenyl methyl silicone, 30 m
8.11 Gases, Hydrogen (zero grade; 99.995 % purity) and
by 0.32 mm id by 0.25 µm film thickness.
nitrogen(zerograde;99.998%purity)orargon/methane(95:5;
7.7.1 It is possible that other columns will provide sufficient
ECD grade).
separating power, but this shall be demonstrated before use.
8.11.1 Careshallbegiventoensurepurityofthecarriergas.
For example, an in-line filter may be required.
7.8 Analytical Balance, capable of weighing to 0.0001 g.
8.12 Aroclor Standards , Aroclor 1016, 1221, 1232, 1242,
7.9 Volumetric Flasks, 10, 50, 100, 200 mL, (see Specifica-
1254, 1260, 1262, 1268.
tion E288) Class A with ground-glass stoppers.
8.13 Decachlorobiphenyl (DCB) (surrogate) Optional:
7.10 Vortex Mixer:
8.13.1 Surrogate Stock Standard (15 µg/mL) Preparation—
Accurately dilute 1.5 mL of 1000 µg/mL DCB concentrate in
7.11 Vials, glass, 20 mL and 40 mL capacity with TFE-
100 mL volumetric flask and fill to the mark with methanol,
fluorocarbon-lined caps.
yielding a 15 µg/mL solution.
7.12 Septum Inserts— Inserts shall be treated with a silyni-
8.13.2 Surrogate Working Standard (1.5 µg/mL)
zation reagent before use or after cleaning. (See AnnexA2 for
Preparation—Accurately dilute 10 mL of the 15 µg/mL DCB
possible procedure.) They may be purchased already treated.
stockstandardina100mLvolumetricflaskandfilltothemark
with methanol, yielding a 1.5 µg/mL working DCB standard.
7.13 Volumetric Pipette, 1, 5, 10 mL (see Specification
E969), Class A. NOTE2—Samplepreparationswillnormallyuse0.1mLofthissolution.
The resulting concentration in the sample extract is 0.005 µg/mL before
7.14 Syringe, 500 µL, mechanical guide.
any further dilutions. The following calculations show this.
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