ASTM D5316-98(2004)
(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 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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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 2004)
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 D4210 Practice for Intralaboratory Quality Control Proce-
dures and a Discussion on Reporting Low-Level Data
1.1 This test method covers the determination of 1,2-
D5789 Practice for Writing Quality Control Specifications
dibromoethane (commonly referred to as ethylene dibromide
for Standard Test Methods for Organic Constituents
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 D1129.
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
2 order to compensate for possible extraction losses.
2.1 ASTM Standards:
4.3 The extraction and analysis time is 30 to 50 min per
D1066 Practice for Sampling Steam
sample, depending upon the analytical conditions chosen.
D1129 Terminology Relating to Water
4.4 Confirmatory evidence can be obtained using a dissimi-
D1192 Guide for Equipment for SamplingWater and Steam
3 lar column. When component concentrations are sufficiently
in Closed Conduits
high, Gas Chromatography/Mass Spectrometric (GC/MS)
D1193 Specification for Reagent Water
methods may be used for confirmation analysis. (See EPA
D3370 Practices for Sampling Water from Closed Conduits
Method 524.2.)
D3856 Guide for Good Laboratory Practices in Laborato-
ries Engaged in Sampling and Analysis of Water
5. Significance and Use
5.1 This test method is useful for the analysis of drinking
This test method is under the jurisdiction of ASTM Committee D19 on Water
water and groundwaters. Other waters may be analyzed by this
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
method, see 1.2.
Organic Substances in Water.
5.2 EDB and DBCP have been widely used as soil fumi-
Current edition approved June 1, 2004. Published June 2004. Originally
approved in 1992. Last previous edition approved in 1998 as D5316–98. DOI: gants.EDBisalsousedasaleadscavengerinleadedgasolines.
10.1520/D5316-98R04.
Thesecompoundsareverywatersolubleandareoftenfoundin
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
groundwater and drinking water. Since they are highly toxic
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
Withdrawn. The last approved version of this historical standard is referenced Available from U.S. Environmental Protection Agency, 26 W. Martin Luther
on 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 (2004)
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
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
blanksshouldbeanalyzedoneachnewbottleofsolventbefore
use.Indirectdailychecksontheextractingsolventareobtained
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
FIG. 1 Extract of Reagent Water Spiked at 0.114 µg/L with EDB
shelf-life short. However, it is generally more economical to obtain a new and DBCP
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.
7.1.1 The GC system must be capable of temperature
7.1.5 Column C (alternative column, wide bore)—A 0.53-
programming and should be equipped with a linearized elec-
mm ID by 30-m long fused silica capillary with dimethyl
troncapturedetectorandacapillarycolumnsplitlessinjectorat
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 9
Detector temperature: 350°C.
trihalomethanes. Column A should be used as the primary
analytical column unless routinely occurring analytes are not
adequatelyresolved.ColumnB(7.1.4)isrecommendedforuse J & W Durawax DX-3, 0.25 µm, available from J & W Scientific, 91 Blue
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 DBCPon these columns
J & W DB-1, 1.0 µm film, available from J & W Scientific, or its equivalent,
are presented in Table 1.
has been found suitable for this purpose.
Rt –Volatiles,2.0µmfilmthickness.Restekpart#10902,availablefromRestek
x
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
suitable for this purpose.
5 9
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 (2004)
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 mLcan be calibrated at the 35.0 mLmark 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—Usestockstan-
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,AutoSampler,compatiblewithautosamplerofgas 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)thatwillbrackettheworkingconcentrationrange.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
thistestmethodhavenotbeenpreciselydefined;eachchemical
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, references
Additional references to laboratory safety need to be made
towatershallbeunderstoodtomeanreagentwaterconforming
available to the analyst.
to Specification D1193, Type III, which has been shown to be
9.2 EDB and DBCP have been tentatively classified as
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.
MESAapproved toxic gas respirator should be worn when the
8.6 HydrochloricAcid(1 + 1)—Addonevolumeofconcen-
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—When a solvent is purified, stabilizers put into the solvent by
the manufacturer are removed, thus potentially making the solvent
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
hazardous.
pulverizeabatchofNaClandplaceinamufflefurnaceatroom
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 SodiumThiosulfateSolution(40g/L)—Dissolve1.0gof
10.1.1 Collect the sample in accordance with Practice
sodium thiosulfate (Na S O ) in 25 mL of water. Solid Na
2 2 3
D1066, Specification D1192, and Practices D3370, 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-mLbottles 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
add75µLoffreshly-preparedsodiumthiosulfatesolution(0.04
10-mLgroundglassstopperedvolumetricflask.Allowtheflask
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 and carefully fill 4
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