ASTM D5316-98(2011)
(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
SIGNIFICANCE AND USE
This test method is useful for the analysis of drinking water and groundwaters. Other waters may be analyzed by this method, see 1.2.
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 and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements, see Sections 6 and 9.
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D5316 − 98 (Reapproved 2011)
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope D1193Specification for Reagent Water
D3370Practices for Sampling Water from Closed Conduits
1.1 This test method covers the determination of 1,2-
D3856Guide for Management Systems in Laboratories
dibromoethane (commonly referred to as ethylene dibromide
Engaged in Analysis of Water
or EDB) and 1,2-dibromo-3-chloropropane (commonly re-
D4210Practice for Intralaboratory Quality Control Proce-
ferred to as DBCP) in water at a minimum detection level of
dures and a Discussion on Reporting Low-Level Data
0.010 µg/L by liquid-liquid extraction combined with gas-
(Withdrawn 2002)
liquid chromatography. This test method is applicable to the
D5789Practice for Writing Quality Control Specifications
analysis of drinking waters and groundwaters. It is not recom-
for Standard Test Methods for Organic Constituents
mended for wastewaters, due to the potential for interferences
(Withdrawn 2002)
fromhighconcentrationsofotherextractableorganics.Similar
information can be found in EPA Method504. 2.2 U.S. Environmental Protection Agency Standards:
Winfield, T. W.,“U.S. EPA Method504, Revision 2.0,”
1.2 This test method was used successfully with reagent
Methods for the Determination of Organic Compounds in
water and groundwater. It is the user’s responsibility to ensure
Drinking Water, 1989
the validity of this test method for waters of untested matrices.
1.3 The values stated in SI units are to be regarded as
3. Terminology
standard. No other units of measurement are included in this
3.1 Definitions—For definitions of terms used in this test
standard.
method, refer to Terminology D1129.
1.4 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
4. Summary of Test Method
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4.1 This test method consists of microextraction of the
bility of regulatory limitations prior to use. For specific hazard
sample followed by gas chromatographic analysis of the
statements, see Sections 6 and 9.
extract.
4.2 An aliquot of the sample is extracted with hexane. Two
2. Referenced Documents
µL of the extract are then injected into a gas chromatograph
2.1 ASTM Standards:
equipped with a linearized electron capture detector for sepa-
D1066Practice for Sampling Steam
ration and analysis. Aqueous calibration standards are ex-
D1129Terminology Relating to Water
tracted and analyzed in an identical manner as the samples in
D1192Guide for Equipment for Sampling Water and Steam
order to compensate for possible extraction losses.
in Closed Conduits (Withdrawn 2003)
4.3 The extraction and analysis time is 30 to 50 min per
sample, depending upon the analytical conditions chosen.
This test method is under the jurisdiction ofASTM Committee D19 on Water
4.4 Confirmatory evidence can be obtained using a dissimi-
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
lar column. When component concentrations are sufficiently
Organic Substances in Water.
Current edition approved May 1, 2011. Published June 2011. Originally
high, Gas Chromatography/Mass Spectrometric (GC/MS)
approved in 1992. Last previous edition approved in 2004 as D5316 – 98 (2004).
methods may be used for confirmation analysis. (See EPA
DOI: 10.1520/D5316-98R11.
Method524.2.)
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
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.
3 4
The last approved version of this historical standard is referenced on Available from U.S. Environmental Protection Agency, 26 W. Martin Luther
www.astm.org. King Ave., Cincinnati, OH 45268.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5316 − 98 (2011)
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
5. Significance and Use
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
5.1 This test method is useful for the analysis of drinking
Analyte Retention Time (min)
waterandgroundwaters.Otherwatersmaybeanalyzedbythis
Column A Column B Column C
EDB 9.5 8.9 4.1
method, see 1.2.
DBCP 17.3 15.0 12.8
5.2 EDB and DBCP have been widely used as soil fumi-
gants.EDBisalsousedasaleadscavengerinleadedgasolines.
Thesecompoundsareverywatersolubleandareoftenfoundin
7.1.3 Column A—A 0.32-mm ID by 30-m long fused silica
groundwater and drinking water. Since they are highly toxic
capillary with dimethyl silicone mixed phase. The linear
and are suspected carcinogens, there is concern about the
velocity of the helium carrier gas should be about 25 cm/s at
potential health impact of even extremely low concentrations
100°C. The column temperature is programmed to hold at
in potable water.
40°C for 4 min, to increase to 190°C at 8°C/min, and hold at
190°Cfor25minoruntilallexpectedcompoundshaveeluted.
6. Interferences
(See Fig. 1 for a sample chromatogram.)
6.1 Impurities contained in the extracting solvent usually
7.1.4 Column B (alternative column)—A 0.32-mm ID by
account for the majority of the analytical problems. Solvent
30-m long fused silica capillary with methyl polysiloxane
blanksshouldbeanalyzedoneachnewbottleofsolventbefore
phase. The linear velocity of the helium carrier gas should be
use.Indirectdailychecksontheextractingsolventareobtained
about 25 cm/s at 100°C. The column temperature is pro-
by monitoring the water blanks. Whenever an interference is
grammed to hold at 40°C for 4 min, to increase to 270°C at
noted in the water blank, the analyst should reanalyze the
10°C/min, and hold at 270°C for 10 min or until all expected
extracting solvent. Low-level interferences generally can be
compounds have eluted.
removed by distillation or column chromatography.
7.1.5 Column C (alternative column, wide bore)—A 0.53-
mm ID by 30-m long fused silica capillary with dimethyl
NOTE 1—When a solvent is purified, stabilizers put into the solvent by
diphenyl polysiloxane, bonded phase with 2.0 µm film. The
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
J & W Durawax DX-3, 0.25 µm, available from J & W Scientific, 91 Blue
shelf-life short. However, it is generally more economical to obtain a new
Ravine Rd., Folsom, CA 95630, or its equivalent, has been found suitable for this
source of solvent. Interference-free solvent is defined as a solvent
purpose.
containing less than 0.1 µg/L individual analyte interference. Protect
J & W DB-1, 1.0 µm film, available from J & W Scientific, or its equivalent,
interference-free solvents by storing them in an area known to be free of
has been found suitable for this purpose.
organochlorine solvents.
Rt –Volatiles,2.0µmfilmthickness.Restekpart#10902,availablefromRestek
x
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
6.2 This liquid-liquid extraction technique efficiently ex-
suitable for this purpose.
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
EDBatlowconcentrationsmaybemaskedbyveryhighlevels
of dibromochloromethane (DBCM), a common disinfection
by-product of chlorinated drinking waters.
7. Apparatus and Equipment
7.1 Gas Chromatography (GC) System:
7.1.1 The GC system must be capable of temperature
programming and should be equipped with a linearized elec-
troncapturedetectorandacapillarycolumnsplitlessinjectorat
200°C. Separate heated zones for the injector and detector
components are recommended.
7.1.2 Two gas chromatography columns are recommended.
Column A (7.1.3) is a highly efficient column that provides
separations for EDB and DBCP without interferences from
trihalomethanes. Column A should be used as the primary
analytical column unless routinely occurring analytes are not
adequatelyresolved.ColumnB(7.1.4)isrecommendedforuse
as a confirmatory column when GC/MS confirmation is not
viable. Retention times for EDB and DBCPon these columns
are presented in Table 1.
An alternative column has been recommended by the Restek Corporation and FIG. 1 Extract of Reagent Water Spiked at 0.114 µg/L with EDB
is described in 7.1.5 as Column C. and DBCP
D5316 − 98 (2011)
hydrogen carrier gas flow is about 80 cm/s linear velocity, 8.10 Solutions, Stock Standard—These solutions may be
measured at 50°C. The oven temperature is programmed to purchasedascertifiedsolutionsorpreparedfrompurestandard
hold at 200°C until all expected compounds have eluted. materials using the following procedures:
7.1.6 Other Heated Zones—Injector temperature: 250°C. 8.10.1 Place approximately 9.8 mL of methanol into a
Detector temperature: 350°C.
10-mLgroundglassstopperedvolumetricflask.Allowtheflask
to stand, unstoppered, for about 10 min and weigh to the
7.2 Sample Containers—Forty-mL screw cap vials, each
nearest 0.1 mg.
equipped with a size 24 cap, with a flat, disc-like PTFE-faced
8.10.2 Use a 100-µL syringe and immediately add two or
polyethylene film/foam extrusion. Individual vials shown to
more drops of standard material to the flask. Be sure that the
contain at least 40.0 mLcan be calibrated at the 35.0 mLmark
standard material falls directly into the alcohol without con-
so that volumetric, rather than gravimetric, measurements of
tacting the neck of the flask.
samplevolumescanbeperformed.Priortouse,washvialsand
8.10.3 Reweigh, dilute to volume, stopper, then mix by
septa with detergent and rinse with tap and reagent water.
invertingtheflaskseveraltimes.Calculatetheconcentrationin
Allow the vials and septa to air dry at room temperature, place
µg/µL from the net gain in weight.
in a 105°C oven for 1 h, then remove and allow to cool in an
8.10.4 Store stock standard solutions in 15-mL bottles
area known to be free of organic solvent vapors.
equipped with PTFE-lined screw caps. Methanol solutions
7.3 Vials,Auto Sampler,compatiblewithautosamplerofgas
prepared from liquid analytes are stable for at least four weeks
chromatograph.
when stored at 4°C.
7.4 Microsyringes, 10, 25, and 100-µL.
8.11 Standard Solutions, Primary Dilution—Usestockstan-
7.5 Standard Solution Storage Containers—Fifteen-mL
dard solutions to prepare primary dilution standard solutions
bottles with PTFE-lined screw caps.
that contain both analytes in methanol. The primary dilution
standards should be prepared at concentrations that can be
8. Reagents
easily diluted to prepare aqueous calibration standards (see
12.1.1)thatwillbrackettheworkingconcentrationrange.Store
8.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that the primary dilution standard solutions with minimal
headspace, and check frequently for signs of deterioration or
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society evaporation, especially just before preparing calibration stan-
dards. The storage time described for stock standard solutions
wheresuchspecificationsareavailable. Othergradesmaybe
used, provided it is first ascertained that the reagent is of also applies to primary dilution standard solutions.
sufficiently high purity to permit its use without lessening the
accuracy of the determination. 9. Hazards
8.2 Purity of Water—Unless otherwise indicated, references 9.1 The toxicity and carcinogenicity of chemicals used in
towatershallbeunderstoodtomeanreagentwaterconforming thistestmethodhavenotbeenpreciselydefined;eachchemical
to Specification D1193, Type III, which has been shown to be should be treated as a potential health hazard, and exposure to
free of the analytes of interest. these chemicals should be minimized. Each laboratory is
responsible for maintaining awareness of OSHA regulations
8.3 1,2-dibromoethane, 99%.
regarding safe handling of chemicals used in this test method.
8.4 1,2-dibromo-3-chloropropane, 99%.
Additional references to laboratory safety need to be made
8.5 Hexane Extraction Solvent, UV Grade. available to the analyst.
8.6 Hydrochloric Acid(1+1)—Addonevolumeofconcen- 9.2 EDB and DBCP have been tentatively classified as
trated HCl (sp. gr. 1.19) to one volume of water. known or suspected human or mammalian carcinogens. Pure
standard materials and stock standard solutions of these com-
8.7 Methyl Alcohol— Demonstrated to be free of analytes.
pounds should be handled in a hood or glovebox. A NIOSH/
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
MESAapproved toxic gas respirator should be worn when the
pulverizeabatchofNaClandplaceinamufflefurnaceatroom
analyst handles high concentrations of these toxic compounds.
temperature. Increase the temperature to 400°C for 30 min.
NOTE 2—When a solvent is purified, stabilizers put into the solvent by
Place in a bottle and cap.
the manufacturer are removed, thus potentially making the solvent
8.9 Sodium Thiosulfate Solution(40g/L)—Dissolve1.0gof
hazardous.
sodium thiosulfate (Na S O ) in 25 mL of water. Solid
2 2 3
Na S O may be used in place of the solution.
10. Sample Collection, Preservation, and Storage
2 2 3
10.1 Sample Collection:
10.1.1 Collect the sample in accordance with Practice
These parameters were obtained by Restek Corporation during preliminary
D1066, Specification D1192, and Practices D3370, as appli-
attempts to improve the separation of EDB and DBCM.
“Reagent Chemicals, American Chemical Society Specifications,” American
cable.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
10.1.2 Collectallsamplesin40-mLbottlesintowhich3mg
listed by the American Chemical Society, see “Standards for Laboratory
of sodium thiosulfate crystals have been added to the empty
Chemicals,” BDH Limited, Poole, Dorset, UK, and the “United States Pharmaco-
peia.” bottles just prior to shipping to the sampling site. Alternately,
D5316 − 98 (20
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