ASTM D3973-85(2024)

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: D3973 − 85 (Reapproved 2024)
Standard Test Method for
Low-Molecular Weight Halogenated Hydrocarbons in Water
This standard is issued under the fixed designation D3973; 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 mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This test method covers the analysis of drinking water.
It is also applicable to many environmental and waste waters
2. Referenced Documents
when adequate validation is included.
2.1 ASTM Standards:
1.2 This test method covers the determination of
D1129 Terminology Relating to Water
halomethanes, haloethanes, and some related extractable or-
D1193 Specification for Reagent Water
ganohalides amenable to gas chromatographic measurement.
D3871 Test Method for Purgeable Organic Compounds in
The applicable concentration range for trihalomethanes is from
Water Using Headspace Sampling
1 μg ⁄L to 200 μg ⁄L. Detection limits depend on the compound,
matrix, and on the characteristics of the gas chromatographic E355 Practice for Gas Chromatography Terms and Relation-
ships
system.
1.3 For compounds not specifically included in the precision
3. Terminology
and bias section the analyst should validate the test method by
collecting precision and bias data on actual samples.
3.1 Definitions:
1.4 Confirmation of component identities is obtained by 3.1.1 For definitions of terms used in this standard, refer to
observing retention times using gas chromatographic columns Terminology D1129 and Practice E355.
of different polarities. When concentrations are sufficiently
high (>50 μg/L) confirmation with halogen specific detectors
4. Summary of Test Method
or gas chromatography/mass spectrometry (GC/MS) may be
4.1 This test method employs liquid/liquid extraction to
used. Confirmation of purgeable compounds at levels down to
isolate compounds of interest and provide a five-fold concen-
1 μg/L can be obtained using Test Method D3871 with GC/MS
3,4,5
tration enhancement prior to measurement. A 5 mL aque-
detection.
ous sample is extracted once with 1 mL of solvent. A 3 μL
1.5 The values stated in SI units are to be regarded as
aliquot of the extract is analyzed in a gas chromatograph
standard. No other units of measurement are included in this
equipped with an electron-capture detector.
standard.
4.2 Extraction efficiencies with the 1:5 solvent/sample ratio
1.6 This standard does not purport to address all of the
for trihalomethanes average above 90 %. To compensate for
safety concerns, if any, associated with its use. It is the
extraction losses, calibration standards are extracted and ana-
responsibility of the user of this standard to establish appro-
lyzed in an identical manner.
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
4.3 The concentration of each component is calculated and
Specific precautionary statements are given in Section 8.
reported in micrograms per litre.
1.7 This international standard was developed in accor-
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Development of International Standards, Guides and Recom-
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
Mieure, J. P., “A Rapid and Sensitive Method for Determining Volatile
This test method is under the jurisdiction of ASTM Committee D19 on Water Organohalides in Water,” Journal AWWA, Vol 69, 1977, p. 60.
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for Richard, J. J., and Junk, G. A., “Liquid Extraction for Rapid Determination of
Organic Substances in Water. Halomethanes in Water,” Journal AWWA, Vol 69, 1977, p. 62.
Current edition approved April 1, 2024. Published April 2024. Originally “The Analysis of Trihalomethanes in Drinking Water by Liquid/Liquid
approved in 1980. Last previous edition approved in 2017 as D3973 – 85 (2017). Extraction,” U.S. Environmental Protection Agency, EMSL, Cincinnati, OH, Sept.
DOI: 10.1520/D3973-85R24. 9, 1977.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3973 − 85 (2024)
5. Significance and Use 8. Reagents
5.1 The incidental conversion of organic material to triha- 8.1 Purity of Reagents—Reagent grade chemicals shall be
lomethanes and other volatile organohalides during chlorina- used in all tests. Unless otherwise indicated, it is intended that
tion of water is a possible health hazard and is the object of all reagents shall conform to the specifications of the Commit-
much research. This test method can be used as a rapid, simple tee on Analytical Reagents of the American Chemical
means for determining many volatile organohalides in raw and Society, where such specifications are available. Other grades
processed water. may be used, provided it is first ascertained that the reagent is
of sufficiently high purity to permit its use without lessening
6. Interferences
the accuracy of the determination.
6.1 Volatile compounds that are extractable and responsive
8.2 Purity of Water—Unless otherwise indicated, Specifica-
to electron-capture detection may interfere with this test
tion D1193 reagent water, Type II, will be used in this test
method.
method. In addition the water is made organic-free by passing
it through a filter bed containing about 0.4 kg of activated
6.2 Impurities in the extracting solvent can be a source of
carbon (8.3), or using a commercial water purification sys-
interference. Solvent blanks should be analyzed daily and
tem.
before a new bottle of solvent is used for the first time.
Whenever interfering compounds are traced to the solvent, a
8.3 Activated Carbon.
new source of solvent should be obtained. Alternatively,
8.4 Dechlorinating Agent—Granular sodium thiosulfate or
impurities may be removed by distillation, column chromatog-
ascorbic acid.
raphy or purging with high-purity nitrogen or helium. This
8.5 Detergent, suitable for laboratory glassware.
procedure is quantitative as long as solvent interference con-
tributes less than 10 % to the component concentration in the
8.6 Isooctane, pesticide grade.
sample.
8.7 Methyl Alcohol, pesticide grade.
7. Apparatus 8.8 Sodium Chloride, granular.
7.1 Extraction Vessel, 9 mL (2 dram) vial with aluminum
8.9 Reference Standards:
foil or PTFE-lined caps. 8.9.1 Bromoform.
8.9.2 Bromodichloromethane.
7.2 Sample Containers, 40 mL screw cap vials sealed with
8.9.3 Chlorodibromomethane.
PTFE-faced silicone septa.
8.9.4 Chloroform.
7.3 Micro Syringes, 10, 100 μL.
8.9.5 Tetrachloroethylene.
7.4 Pipets, 1.0 mL and 5.0 mL transfer. 8.9.6 1,1,1-Trichloroethane.
7.5 Glass-Stoppered Volumetric Flasks, 10 mL and 100 mL. 8.10 Stock Solutions—Prepare a stock solution (2 mg ⁄mL to
10 mg ⁄mL) for each standard as follows:
7.6 Gas Chromatograph, with electron-capture detector.
8.10.1 Warning—Because of the toxicity of trihalometh-
7.7 Columns—Either of the following columns have been
anes it is necessary to prepare primary dilutions in a hood. It is
found suitable for this analysis. See Fig. 1 for chromatograms.
further recommended that a NIOSH/MESA-approved toxic gas
If other column conditions are used, it is up to the analyst to
respirator be used when the analyst handles high concentra-
demonstrate the precision and bias statements are met by
tions of such materials.
collecting precision, bias, and recovery data.
7.7.1 Nonpolar, 3 mm inside diameter by 2 m long borosili-
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
cate glass packed with 100/120 mesh support coated with a
Standard-Grade Reference Materials, American Chemical Society, Washington,
methyl silicone liquid phase and operated at 60 °C with
DC. For suggestions on the testing of reagents not listed by the American Chemical
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
45 mL ⁄min carrier flow.
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
7.7.2 Polar, 3 mm inside diameter by 2 m long borosilicate
copeial Convention, Inc. (USPC), Rockville, MD.
glass packed with 100/120 mesh support coated with a polar
Super Q water system, available from Millipore Corp. Ashby Rd., Bedford,
MA 01730, has been found suitable; other sources that are equivalent may be
liquid phase such as polyethylene glycol and operated at
substituted.
50 °C with 60 mL ⁄min carrier flow.
Filtrasorb 200, available from Calgon Corp., Box 1346, Pittsburgh, PA 15230,
has been found suitable; other sources that are equivalent may be substituted.
Pesticide grade, available from Burdick & Jackson Labs, Inc., 1953 S. Harvey
13075 vials and 12722 septa, available from Pierce Chemical Co., P.O. Box St., Muskegon, MI 49442, or Spectro Grade, available from Phillips Chemical Co.,
117, Rockford, IL 61105, have been found suitable; other sources that are equivalent Specialty Chemicals, Drawer “O”, Borger, TX 79007, have been found suitable;
may be substituted. other sources that are equivalent may be substituted.
7 14
Gas-Chrom Q, available from Applied Science Laboratory, Inc., P.O. Box 440, Pesticide grade, available from Burdick & Jackson Labs, Inc., has been found
State College, PA 16801, has been found suitable; other sources that are equivalent suitable; other sources which are equivalent may be substituted.
may be substituted. Bromodichloromethane, available from Aldrich Chemical Co., Inc., 940 W. St.
OV-101, available from Ohio Valley Specialty Chemical, Inc., Route 6, Paul Ave., Milwaukee, WI 53233, has been found suitable; other sources that are
Marietta, OH 45750, has been found suitable; other sources that are equivalent may equivalent may be substituted.
be substituted. Chlorodibromomethane, available from Chemical Service Inc., 1887 Lincoln
SP-1000, available from Supelco, Inc., Supelco Park, Bellafonte, PA 16823, has Ave., West Chester, PA, has been found suitable; other sour
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