ASTM D5316-98(2024)

Standard Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and Gas Chromatography

SIGNIFICANCE AND USE
5.1 This test method is useful for the analysis of drinking water and groundwaters. Other waters may be analyzed by this test method, see 1.2.  
5.2 EDB and DBCP have been widely used as soil fumigants. EDB is also used as a lead scavenger in leaded gasolines. These compounds are very water soluble and are often found in 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.
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 μg/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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Sections 6 and 9.  
1.5 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.

General Information

• Status: Published
• Publication Date: 31-Mar-2024
• ICS: 71.080.20 - Halogenated hydrocarbons
• Technical Committee: D19 - Water
• Drafting Committee: D19.06 - Methods for Analysis for Organic Substances in Water

Relations

• Replaces: ASTM D5316-98(2017) - Standard Test Method for 1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane in Water by Microextraction and Gas Chromatography
• Effective Date: 01-Apr-2024
• Referred By: ASTM D4128-18 - Standard Guide for Identification and Quantitation of Organic Compounds in Water by Combined Gas Chromatography and Electron Impact Mass Spectrometry
• Effective Date: 01-Apr-2024
• Referred By: ASTM D3694-96(2024) - Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents
• Effective Date: 01-Apr-2024

Overview

ASTM D5316-98(2024) is the Standard Test Method for determining the presence of 1,2-dibromoethane (EDB) and 1,2-dibromo-3-chloropropane (DBCP) in water, utilizing microextraction and gas chromatography techniques. Developed by ASTM International, this method provides laboratories and environmental professionals with a reliable procedure for detecting extremely low concentrations (as low as 0.010 μg/L) of these compounds in drinking water and groundwater. Both EDB and DBCP are highly toxic, water-soluble chemicals, historically used as soil fumigants and in leaded gasoline, and are classified as suspected carcinogens. Their frequent detection in water sources raises significant public health concerns.

Key Topics

• Test Method Scope and Applicability
  • Designed for drinking water and groundwater analyses.
  • Employs liquid-liquid extraction followed by gas chromatography for detection.
  • Not recommended for wastewater due to potential interferences from high levels of organics.
  • Minimum detection level: 0.010 μg/L.
• Relevance of EDB and DBCP
  • Both are persistent, toxic, and potentially carcinogenic chemicals often found in potable water.
  • Monitoring is essential due to health risks associated with chronic exposure, even at trace levels.
• Microextraction and Gas Chromatography
  • Technique involves extracting analytes from water using hexane, followed by chromatographic separation and quantification.
  • Use of specific columns and daily calibration ensures accurate and reproducible results.
• Quality Control and Assurance
  • Includes ongoing system calibration, precision and bias evaluations, and frequent quality control checks.
  • Prescribes standard protocols for sample collection, preservation, storage, and handling to minimize contamination or analyte loss.

Applications

• Drinking Water and Groundwater Quality Monitoring
  • Routine testing by water utilities, government agencies, and environmental laboratories to ensure regulatory compliance and public safety.
  • Detection of EDB and DBCP supports risk assessment and remediation efforts, particularly in areas impacted by previous fumigant use or where legacy contamination is suspected.
• Environmental Site Assessment
  • Used in evaluating contamination at sites with historical pesticide, fumigant application, or petroleum storage.
  • Supports cleanup operations and long-term environmental monitoring.
• Regulatory and Compliance Testing
  • Valuable for compliance with national and local standards for toxic compounds in potable water.
  • Provides standardized data for reporting to health authorities and stakeholders.
• Laboratory Accreditation and Proficiency
  • Accredited laboratories are often required to verify technical competence and demonstrate ongoing proficiency using recognized methods such as ASTM D5316.

Related Standards

• EPA Method 504 - Similar methodology for determining EDB and DBCP in drinking water.
• ASTM D1129 - Terminology Relating to Water.
• ASTM D1192 - Guide for Equipment for Sampling Water and Steam.
• ASTM D1193 - Specification for Reagent Water.
• ASTM D3370 - Practices for Sampling Water from Flowing Process Streams.
• Additional standards for laboratory quality management and quality control, including withdrawn standards referenced in the document.

Keywords: ASTM D5316, 1,2-dibromoethane, EDB, 1,2-dibromo-3-chloropropane, DBCP, drinking water analysis, microextraction, gas chromatography, water quality, groundwater testing, carcinogenic compounds in water, EPA Method 504, laboratory standards, environmental monitoring.

Standards Content (Sample)

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: D5316 − 98 (Reapproved 2024)
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 D5316; 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 D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam
1.1 This test method covers the determination of 1,2-
in Closed Conduits (Withdrawn 2003)
dibromoethane (commonly referred to as ethylene dibromide
D1193 Specification for Reagent Water
or EDB) and 1,2-dibromo-3-chloropropane (commonly re-
D3370 Practices for Sampling Water from Flowing Process
ferred to as DBCP) in water at a minimum detection level of
Streams
0.010 μg/L by liquid-liquid extraction combined with gas-
D3856 Guide for Management Systems in Laboratories
liquid chromatography. This test method is applicable to the
Engaged in Analysis of Water (Withdrawn 2024)
analysis of drinking waters and groundwaters. It is not recom-
D4210 Practice for Intralaboratory Quality Control Proce-
mended for wastewaters, due to the potential for interferences
dures and a Discussion on Reporting Low-Level Data
from high concentrations of other extractable organics. Similar
(Withdrawn 2002)
information can be found in EPA Method 504.
D5789 Practice for Writing Quality Control Specifications
1.2 This test method was used successfully with reagent
for Standard Test Methods for Organic Constituents
water and groundwater. It is the user’s responsibility to ensure
(Withdrawn 2002)
the validity of this test method for waters of untested matrices.
2.2 U.S. EPA Standards:
1.3 The values stated in SI units are to be regarded as
Method 504 Methods for the Determination of Organic
standard. No other units of measurement are included in this
Compounds in Drinking Water, Revision 2.0, 1989
standard.
Method 524 Measurement of Purgeable Organic Com-
1.4 This standard does not purport to address all of the pounds in Drinking Water by Gas Chromatography/Mass
safety concerns, if any, associated with its use. It is the
Spectrometry
responsibility of the user of this standard to establish appro-
3. Terminology
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
3.1 Definitions:
For specific hazard statements, see Sections 6 and 9.
3.1.1 For definitions of terms used in this standard, refer to
1.5 This international standard was developed in accor-
Terminology D1129.
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 This test method consists of microextraction of the
mendations issued by the World Trade Organization Technical
sample followed by gas chromatographic analysis of the
Barriers to Trade (TBT) Committee.
extract.
2. Referenced Documents
4.2 An aliquot of the sample is extracted with hexane. Two
2.1 ASTM Standards: μL of the extract are then injected into a gas chromatograph
D1066 Practice for Sampling Steam
equipped with a linearized electron capture detector for sepa-
ration and analysis. Aqueous calibration standards are ex-
This test method is under the jurisdiction of ASTM Committee D19 on Water
tracted and analyzed in an identical manner as the samples in
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
order to compensate for possible extraction losses.
Organic Substances in Water.
Current edition approved April 1, 2024. Published April 2024. Originally
approved in 1992. Last previous edition approved in 2017 as D5316 – 98 (2017).
DOI: 10.1520/D5316-98R24. The last approved version of this historical standard is referenced on
For referenced ASTM standards, visit the ASTM website, www.astm.org, or www.astm.org.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Available from United States Environmental Protection Agency (EPA), William
Standards volume information, refer to the standard’s Document Summary page on Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,
the ASTM website. http://www.epa.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5316 − 98 (2024)
4.3 The extraction and analysis time is 30 min to 50 min per analytical column unless routinely occurring analytes are not
sample, depending upon the analytical conditions chosen. adequately resolved. Column B (7.1.4) is recommended for use
as a confirmatory column when GC/MS confirmation is not
4.4 Confirmatory evidence can be obtained using a dissimi-
viable. Retention times for EDB and DBCP on these columns
lar column. When component concentrations are sufficiently
are presented in Table 1.
high, Gas Chromatography/Mass Spectrometric (GC/MS)
methods may be used for confirmation analysis. (See EPA
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
Method 524.2.)
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
Retention Time (min)
5. Significance and Use
Analyte
Column A Column B Column C
5.1 This test method is useful for the analysis of drinking
EDB 9.5 8.9 4.1
DBCP 17.3 15.0 12.8
water and groundwaters. Other waters may be analyzed by this
test method, see 1.2.
5.2 EDB and DBCP have been widely used as soil fumi-
7.1.3 Column A—A 0.32 mm ID by 30 m long fused silica
gants. EDB is also used as a lead scavenger in leaded gasolines.
capillary with dimethyl silicone mixed phase. The linear
These compounds are very water soluble and are often found in
velocity of the helium carrier gas should be about 25 cm/s at
groundwater and drinking water. Since they are highly toxic
100 °C. The column temperature is programmed to hold at
and are suspected carcinogens, there is concern about the
40 °C for 4 min, to increase to 190 °C at 8 °C ⁄min, and hold at
potential health impact of even extremely low concentrations
190 °C for 25 min or until all expected compounds have eluted.
in potable water.
(See Fig. 1 for a sample chromatogram.)
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—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 the
solvent by the manufacturer are removed, thus potentially making the
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
interference-free solvents by storing them in an area known to be free of
organochlorine solvents.
6.2 This liquid-liquid extraction technique efficiently ex-
tracts a wide boiling range of nonpolar organic compounds
and, in addition, extracts polar organic components of the
sample with varying efficiencies.
6.3 Current column technology suffers from the fact that
EDB at low concentrations may be masked by very high levels
of dibromochloromethane (DBCM), a common disinfection
by-product of chlorinated drinking waters. FIG. 1 Extract of Reagent Water Spiked at 0.114 μg/L with EDB
and DBCP
7. Apparatus and Equipment
7.1.4 Column B (alternative column)—A 0.32 mm ID by
7.1 Gas Chromatography (GC) System:
30 m long fused silica capillary with methyl polysiloxane
7.1.1 The GC system must be capable of temperature
phase. The linear velocity of the helium carrier gas should be
programming and should be equipped with a linearized elec-
tron capture detector and a capillary column splitless injector at
200 °C. Separate heated zones for the injector and detector 5
An alternative column has been recommended by the Restek Corporation and
components are recommended.
is described in 7.1.5 as Column C.
J & W Durawax DX-3, 0.25 μm, available from J & W Scientific, 91 Blue
7.1.2 Two gas chromatography columns are recommended.
Ravine Rd., Folsom, CA 95630, or its equivalent, has been found suitable for this
Column A (7.1.3) is a highly efficient column that provides
purpose.
separations for EDB and DBCP without interferences from
J & W DB-1, 1.0 μm film, available from J & W Scientific, or its equivalent,
trihalomethanes. Column A should be used as the primary has been found suitable for this purpose.
D5316 − 98 (2024)
about 25 cm/s at 100 °C. The column temperature is pro- 8.7 Methyl Alcohol—Demonstrated to be free of analytes.
grammed to hold at 40 °C for 4 min, to increase to 270 °C at
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
10 °C ⁄min, and hold at 270 °C for 10 min or until all expected
pulverize a batch of NaCl and place in a muffle furnace at room
compounds have eluted.
temperature. Increase the temperature to 400 °C for 30 min.
7.1.5 Column C (alternative column, wide bore)—A
Place in a bottle and cap.
0.53 mm ID by 30 m long fused silica capillary with dimethyl
8.9 Sodium Thiosulfate Solution (40 g/L)—Dissolve 1.0 g of
diphenyl polysiloxane, bonded phase with 2.0 μm film. The
sodium thiosulfate (Na S O ) in 25 mL of water. Solid
hydrogen carrier gas flow is about 80 cm/s linear velocity, 2 2 3
Na S O may be used in place of the solution.
measured at 50 °C. The oven temperature is programmed to 2 2 3
hold at 200 °C until all expected compounds have eluted.
8.10 Solutions, Stock Standard—These solutions may be
7.1.6 Other Heated Zones—Injector temperature: 250 °C.
purchased as certified solutions or prepared from pure standard
Detector temperature: 350 °C.
materials using the following procedures:
8.10.1 Place approximately 9.8 mL of methanol into a
7.2 Sample Containers—Forty-mL screw cap vials, each
10 mL ground glass stoppered volumetric flask. Allow the flask
equipped with a size 24 cap, with a flat, disc-like PTFE-faced
to stand, unstoppered, for about 10 min and weigh to the
polyethylene film/foam extrusion. Individual vials shown to
nearest 0.1 mg.
contain at least 40.0 mL can be calibrated at the 35.0 mL mark
so that volumetric, rather than gravimetric, measurements of 8.10.2 Use a 100 μL syringe and immediately add two or
sample volumes can be performed. Prior to use, wash vials and more drops of standard material to the flask. Be sure that the
standard material falls directly into the alcohol without con-
septa with detergent and rinse with tap and reagent water.
Allow the vials and septa to air dry at room temperature, place tacting the neck of the flask.
in a 105 °C oven for 1 h, then remove and allow to cool in an 8.10.3 Reweigh, dilute to volume, stopper, then mix by
area known to be free of organic solvent vapors.
inverting the flask several times. Calculate the concentration in
μg/μL from the net gain in weight.
7.3 Vials, Auto Sampler, compatible with autosampler of gas
8.10.4 Store stock standard solutions in 15 mL bottles
chromatograph.
equipped with PTFE-lined screw caps. Methanol solutions
7.4 Microsyringes, 10 μL, 25 μL, and 100 μL.
prepared from liquid analytes are stable for at least four weeks
7.5 Standard Solution Storage Containers—Fifteen-mL
when stored at 4 °C.
bottles with PTFE-lined screw caps.
8.11 Standard Solutions, Primary Dilution—Use stock stan-
dard solutions to prepare primary dilution standard solutions
8. Reagents
that contain both analytes in methanol. The primary dilution
8.1 Purity of Reagents—Reagent grade chemicals shall be
standards should be prepared at concentrations that can be
used in all tests. Unless otherwise indicated, it is intended that
easily diluted to prepare aqueous calibration standards (see
all reagents shall conform to the specifications of the Commit-
12.1.1) that will bracket the working concentration range. Store
tee on Analytical Reagents of the American Chemical Society
10 the primary dilution standard solutions with minimal
where such specifications are available. Other grades may be
headspace, and check frequently for signs of deterioration or
used, provided it is first ascertained that the reagent is of
evaporation, especially just before preparing calibration stan-
sufficiently high purity to permit its use without lessening the
dards. The storage time described for stock standard solutions
accuracy of the determination.
also applies to primary dilution standard solutions.
8.2 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water conforming
9. Hazards
to Specification D1193, Type III, which has been shown to be
9.1 The toxicity and carcinogenicity of chemicals used in
free of the analytes of interest.
this test method have not been precisely defined; each chemical
8.3 1,2-dibromoethane, 99 %.
should be treated as a potential health hazard, and exposure to
8.4 1,2-dibromo-3-chloropropane, 99 %. these chemicals should be minimized. Each laboratory is
responsible for maintaining awareness of OSHA regulations
8.5 Hexane Extraction Solvent, UV Grade.
regarding safe handling of chemicals used in this test method.
8.6 Hydrochloric Acid (1 + 1)—Add one volume of concen-
Additional references to laboratory safety need to be made
trated HCl (sp. gr. 1.19) to one volume of water.
available to the analyst.
9.2 EDB and DBCP have been tentatively classified as
Rt –Volatiles, 2.0 μm film thickness. Restek part #10902, available from Restek
x
known or suspected human or mammalian carcinogens. Pure
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
suitable for this purpose.
standard materials and stock standard solutions of these com-
These parameters were obtained by Restek Corporation during preliminary
pounds should be handled in a hood or glovebox. A NIOSH/
attempts to improve the separation of EDB and DBCM.
10 MESA approved toxic gas respirator should be worn when the
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not analyst handles high concentrations of these toxic compounds.
listed by the American Chemical Society, see Analar Standards for Laboratory
NOTE 2—When a solvent is purified, stabilizers put into the solvent by
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, the manufacturer are removed, thus potentially making the solvent
MD. hazardous.
D5316 − 98 (2024)
10. Sample Collection, Preservation, and Storage 10.3.2 Analyze all samples within 28 days of collection.
10.1 Sample Collection:
11. Preparation of Apparatus
10.1.1 Collect the sample in accordance with Practice
11.1 Set up the gas chromatograph in accordance with the
D1066, Guide D1192, and Practices D3370, as applicable.
manufacturer’s instructions. Install the capillary column
...