ASTM D5316-98
(Test Method)Standard Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and Gas Chromatography
Standard Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and Gas Chromatography
SCOPE
1.1 This test method covers the determination of 1,2-dibromoethane (commonly referred to as ethylene dibromide or EDB) and 1,2-dibromo-3-chloropropane (commonly referred to as DBCP) in water at a minimum detection level of 0.010 [mu]g/L by liquid-liquid extraction combined with gas-liquid chromatography. This test method is applicable to the analysis of drinking waters and groundwaters. It is not recommended for wastewaters, due to the potential for interferences from high concentrations of other extractable organics. Similar information can be found in EPA Method 504.
1.2 This test method was used successfully with reagent water and groundwater. It is the user's responsibility to ensure the validity of this test method for waters of untested matrices.
1.3 This standard does not purport to address all of the safety problems, 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 regulatory limitations prior to use. For specific hazard statements, see Sections 6 and 9.
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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An American National Standard
Designation: D 5316 – 98
Standard Test Method for
1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in
Water by Microextraction and Gas Chromatography
This standard is issued under the fixed designation D 5316; 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 for Standard Test Methods for Organic Constituents
D 5790 Test Method for Measurement of Purgeable Organic
1.1 This test method covers the determination of 1,2-
Compounds in Water by Capillary Column Gas
dibromoethane (commonly referred to as ethylene dibromide
Chromatography/Mass Spectrometry
or EDB) and 1,2-dibromo-3-chloropropane (commonly re-
2.2 U.S. Environmental Protection Agency Standards:
ferred to as DBCP) in water at a minimum detection level of
Winfield, T. W., “U.S. EPA Method 504, Revision 2.0,”
0.010 μg/L by liquid-liquid extraction combined with gas-
Methods for the Determination of Organic Compounds in
liquid chromatography. This test method is applicable to the
Drinking Water, 1989
analysis of drinking waters and groundwaters. It is not recom-
mended for wastewaters, due to the potential for interferences
3. Terminology
from high concentrations of other extractable organics. Similar
3.1 Definitions—For definitions of terms used in this test
information can be found in EPA Method 504.
method, refer to Terminology D 1129.
1.2 This test method was used successfully with reagent
water and groundwater. It is the user’s responsibility to ensure
4. Summary of Test Method
the validity of this test method for waters of untested matrices.
4.1 This test method consists of microextraction of the
1.3 This standard does not purport to address all of the
sample followed by gas chromatographic analysis of the
safety concerns, if any, associated with its use. It is the
extract.
responsibility of the user of this standard to establish appro-
4.2 An aliquot of the sample is extracted with hexane. Two
priate safety and health practices and determine the applica-
μL of the extract are then injected into a gas chromatograph
bility of regulatory limitations prior to use. For specific hazard
equipped with a linearized electron capture detector for sepa-
statements, see Sections 6 and 9.
ration and analysis. Aqueous calibration standards are ex-
2. Referenced Documents tracted and analyzed in an identical manner as the samples in
order to compensate for possible extraction losses.
2.1 ASTM Standards:
2 4.3 The extraction and analysis time is 30 to 50 min per
D 1066 Practice for Sampling Steam
2 sample, depending upon the analytical conditions chosen.
D 1129 Terminology Relating to Water
4.4 Confirmatory evidence can be obtained using a dissimi-
D 1192 Specification for Equipment for Sampling Water
2 lar column. When component concentrations are sufficiently
and Steam in Closed Conduits
2 high, Gas Chromatography/Mass Spectrometric (GC/MS)
D 1193 Specification for Reagent Water
methods may be used for confirmation analysis. (See EPA
D 3370 Practices for Sampling Water from Closed Con-
2 Method 524.2.)
duits
D 3896 Guide for Good Laboratory Practices in Laborato-
5. Significance and Use
ries Engaged in the Sampling and Analysis of Water
5.1 This test method is useful for the analysis of drinking
D 4210 Practice for Interlaboratory Quality Control Proce-
2 water and groundwaters. Other waters may be analyzed by this
dures and a Discussion on Reporting Low-Level Data
method, see 1.2.
D 5789 Practice for Writing Quality Control Specifications
5.2 EDB and DBCP have been widely used as soil fumi-
gants. EDB is also used as a lead scavenger in leaded gasolines.
1 These compounds are very water soluble and are often found in
This test method is under the jurisdiction of ASTM Committee D-19 on Water
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved July 10, 1998. Published March 1999. Originally
published as D 5316–92. Last previous edition D 5316–92. Available from U.S. Environmental Protection Agency, 26 W. Martin Luther
Annual Book of ASTM Standards, Vol 11.01. King Ave., Cincinnati, OH 45268.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D5316–98
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
Analyte Retention Time (min)
Column A Column B Column C
EDB 9.5 8.9 4.1
DBCP 17.3 15.0 12.8
groundwater and drinking water. Since they are highly toxic
and are suspected carcinogens, there is concern about the
potential health impact of even extremely low concentrations
in potable water.
6. Interferences
6.1 Impurities contained in the extracting solvent usually
account for the majority of the analytical problems. Solvent
blanks should be analyzed on each new bottle of solvent before
use. Indirect daily checks on the extracting solvent are obtained
by monitoring the water blanks. Whenever an interference is
noted in the water blank, the analyst should reanalyze the
extracting solvent. Low-level interferences generally can be
removed by distillation or column chromatography.
NOTE 1—Caution: When a solvent is purified, stabilizers put into the
solvent by the manufacturer are removed, thus potentially making the
solvent hazardous. Also, when a solvent is purified, preservatives put into
FIG. 1 Extract of Reagent Water Spiked at 0.114 μg/L with EDB
the solvent by the manufacturer are removed, thus potentially making the
and DBCP
shelf-life short. However, it is generally more economical to obtain a new
source of solvent. Interference-free solvent is defined as a solvent
containing less than 0.1 μg/L individual analyte interference. Protect
7.1.3 Column A—A 0.32-mm ID by 30-m long fused silica
interference-free solvents by storing them in an area known to be free of
capillary with dimethyl silicone mixed phase. The linear
organochlorine solvents.
velocity of the helium carrier gas should be about 25 cm/s at
6.2 This liquid-liquid extraction technique efficiently ex- 100°C. The column temperature is programmed to hold at
tracts a wide boiling range of nonpolar organic compounds
40°C for 4 min, to increase to 190°C at 8°C/min, and hold at
and, in addition, extracts polar organic components of the 190°C for 25 min or until all expected compounds have eluted.
sample with varying efficiencies. (See Fig. 1 for a sample chromatogram.)
6.3 Current column technology suffers from the fact that 7.1.4 Column B (alternative column)—A 0.32-mm ID by
EDB at low concentrations may be masked by very high levels 30-m long fused silica capillary with methyl polysiloxane
of dibromochloromethane (DBCM), a common disinfection phase. The linear velocity of the helium carrier gas should be
by-product of chlorinated drinking waters. about 25 cm/s at 100°C. The column temperature is pro-
grammed to hold at 40°C for 4 min, to increase to 270°C at
7. Apparatus and Equipment
10°C/min, and hold at 270°C for 10 min or until all expected
7.1 Gas Chromatography (GC) System: compounds have eluted.
7.1.5 Column C (alternative column, wide bore)—A 0.53-
7.1.1 The GC system must be capable of temperature
programming and should be equipped with a linearized elec- mm ID by 30-m long fused silica capillary with dimethyl
tron capture detector and a capillary column splitless injector at diphenyl polysiloxane, bonded phase with 2.0 μm film. The
200°C. Separate heated zones for the injector and detector hydrogen carrier gas flow is about 80 cm/s linear velocity,
components are recommended. measured at 50°C. The oven temperature is programmed to
7.1.2 Two gas chromatography columns are recommended. hold at 200°C until all expected compounds have eluted.
Column A (7.1.3) is a highly efficient column that provides 7.1.6 Other Heated Zones—Injector temperature: 250°C.
separations for EDB and DBCP without interferences from Detector temperature: 350°C.
trihalomethanes. Column A should be used as the primary
analytical column unless routinely occurring analytes are not
J & W Durawax DX-3, 0.25 μm, available from J & W Scientific, 91 Blue
adequately resolved. Column B (7.1.4) is recommended for use
Ravine Rd., Folsom, CA 95630, or its equivalent, has been found suitable for this
as a confirmatory column when GC/MS confirmation is not
purpose.
viable. Retention times for EDB and DBCP on these columns
J & W DB-1, 1.0 μm film, available from J & W Scientific, or its equivalent,
has been found suitable for this purpose.
are presented in Table 1.
Rt –Volatiles, 2.0 μm film thickness. Restek part #10902, available from Restek
x
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
suitable for this purpose.
4 8
An alternative column has been recommended by the Restek Corporation and These parameters were obtained by Restek Corporation during preliminary
is described in 7.1.5 as Column C. attempts to improve the separation of EDB and DBCM.
D5316–98
7.2 Sample Containers—Forty-mL screw cap vials, each 8.10.3 Reweigh, dilute to volume, stopper, then mix by
equipped with a size 24 cap, with a flat, disc-like PTFE-faced inverting the flask several times. Calculate the concentration in
polyethylene film/foam extrusion. Individual vials shown to μg/μL from the net gain in weight.
contain at least 40.0 mL can be calibrated at the 35.0 mL mark 8.10.4 Store stock standard solutions in 15-mL bottles
so that volumetric, rather than gravimetric, measurements of equipped with PTFE-lined screw caps. Methanol solutions
sample volumes can be performed. Prior to use, wash vials and prepared from liquid analytes are stable for at least four weeks
septa with detergent and rinse with tap and reagent water. when stored at 4°C.
Allow the vials and septa to air dry at room temperature, place 8.11 Standard Solutions, Primary Dilution—Use stock stan-
in a 105°C oven for 1 h, then remove and allow to cool in an dard solutions to prepare primary dilution standard solutions
area known to be free of organic solvent vapors. that contain both analytes in methanol. The primary dilution
7.3 Vials, Auto Sampler, compatible with autosampler of gas standards should be prepared at concentrations that can be
chromatograph. easily diluted to prepare aqueous calibration standards (see
7.4 Microsyringes, 10, 25, and 100-μL. 12.1.1) that will bracket the working concentration range. Store
7.5 Standard Solution Storage Containers—Fifteen-mL the primary dilution standard solutions with minimal head-
bottles with PTFE-lined screw caps. space, and check frequently for signs of deterioration or
evaporation, especially just before preparing calibration stan-
8. Reagents
dards. The storage time described for stock standard solutions
also applies to primary dilution standard solutions.
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
9. Hazards
all reagents shall conform to the specifications of the Commit-
9.1 The toxicity and carcinogenicity of chemicals used in
tee on Analytical Reagents of the American Chemical Society
9 this test method have not been precisely defined; each chemical
where such specifications are available. Other grades may be
should be treated as a potential health hazard, and exposure to
used, provided it is first ascertained that the reagent is of
these chemicals should be minimized. Each laboratory is
sufficiently high purity to permit its use without lessening the
responsible for maintaining awareness of OSHA regulations
accuracy of the determination.
regarding safe handling of chemicals used in this test method.
8.2 Purity of Water— Unless otherwise indicated, refer-
Additional references to laboratory safety need to be made
ences to water shall be understood to mean reagent water
available to the analyst.
conforming to Specification D 1193, Type III, which has been
9.2 EDB and DBCP have been tentatively classified as
shown to be free of the analytes of interest.
known or suspected human or mammalian carcinogens. Pure
8.3 1,2-dibromoethane,99%.
standard materials and stock standard solutions of these com-
8.4 1,2-dibromo-3-chloropropane,99%.
pounds should be handled in a hood or glovebox. A NIOSH/
8.5 Hexane Extraction Solvent, UV Grade.
MESA approved toxic gas respirator should be worn when the
8.6 Hydrochloric Acid (1 + 1)—Add one volume of concen-
analyst handles high concentrations of these toxic compounds.
trated HCl (sp. gr. 1.19) to one volume of water.
8.7 Methyl Alcohol— Demonstrated to be free of analytes.
NOTE 2—Caution: When a solvent is purified, stabilizers put into the
solvent by the manufacturer are removed, thus potentially making the
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
solvent hazardous.
pulverize a batch of NaCl and place in a muffle furnace at room
temperature. Increase the temperature to 400°C for 30 min.
10. Sample Collection, Preservation, and Storage
Place in a bottle and cap.
10.1 Sample Collection:
8.9 Sodium Thiosulfate Solution (40 g/L)—Dissolve 1.0 g
10.1.1 Collect the sample in accordance with Practice
of sodium thiosulfate (Na S O ) in 25 mL of water. Solid Na
2 2 3
D 1066, Specification D 1192, and Practices D 3370, as appli-
2S O may be used in place of the solution.
2 3
cable.
8.10 Solutions, Stock Standard—These solutions may be
10.1.2 Collect all samples in 40-mL bottles into which 3 mg
purchased as certified solutions or prepared from pure standard
of sodium thiosulfate crystals have been added to the empty
materials using the following procedures:
bottles just prior to shipping to the sampling site. Alternately,
8.10.1 Place approximately 9.8 mL of methanol into a
add 75 μL of freshly-prepared sodium thiosulfate solution (0.04
10-mL ground glass stoppered volumetric flask. Allow the flask
mg/μL) added to empty 40-mL bottles just prior to sample
to stand, unstoppered, for about 10 min and weigh to the
collection.
nearest 0.1 mg.
10.1.3 When sampling from a water tap, open the tap and
8.10.2 Use a 100-μL syringe and immediately add two or
allow the system to flush until the water temperature has
more drops of standard material to the flask. Be sure that the
stabilized (usually about 10 min). Adjust the flow to about 500
standard material falls directly into the alcohol without con-
mL/min and collect samples from the flowing stream.
tacting the neck of the flask.
10.1.4 When sampling from a well, fill a wide mouthed
bottle or beaker with sample an
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