ASTM D5316-98(2017)
(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
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
Relations
Buy Standard
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 2017)
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 D1129Terminology Relating to Water
D1192Guide 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
D1193Specification for Reagent Water
or EDB) and 1,2-dibromo-3-chloropropane (commonly re-
D3370Practices for Sampling Water from Closed Conduits
ferred to as DBCP) in water at a minimum detection level of
D3856Guide for Management Systems in Laboratories
0.010 µg/L by liquid-liquid extraction combined with gas-
Engaged in Analysis of Water
liquid chromatography. This test method is applicable to the
D4210Practice for Intralaboratory Quality Control Proce-
analysis of drinking waters and groundwaters. It is not recom-
dures and a Discussion on Reporting Low-Level Data
mended for wastewaters, due to the potential for interferences
(Withdrawn 2002)
fromhighconcentrationsofotherextractableorganics.Similar
D5789Practice for Writing Quality Control Specifications
information can be found in EPA Method504.
for Standard Test Methods for Organic Constituents
1.2 This test method was used successfully with reagent 3
(Withdrawn 2002)
water and groundwater. It is the user’s responsibility to ensure
2.2 U.S. EPA Standards:
the validity of this test method for waters of untested matrices.
Method504Methods for the Determination of Organic
1.3 The values stated in SI units are to be regarded as
Compounds in Drinking Water, Revision 2.0, 1989
standard. No other units of measurement are included in this
Method 524 Measurement of Purgeable Organic Com-
standard.
pounds in Drinking Water by Gas Chromatography/Mass
1.4 This standard does not purport to address all of the
Spectrometry
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3. Terminology
priate safety, health, and environmental practices and deter-
3.1 Definitions:
mine the applicability of regulatory limitations prior to use.
3.1.1 For definitions of terms used in this standard, refer to
For specific hazard statements, see Sections 6 and 9.
Terminology D1129.
1.5 This international standard was developed in accor-
dance with internationally recognized principles on standard-
4. Summary of Test Method
ization established in the Decision on Principles for the
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.
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-
tracted and analyzed in an identical manner as the samples in
This test method is under the jurisdiction ofASTM Committee D19 on Water
order to compensate for possible extraction losses.
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water.
Current edition approved Dec. 15, 2017. Published January 2018. Originally
approved in 1992. Last previous edition approved in 2011 as D5316 – 98 (2011).
DOI: 10.1520/D5316-98R17. 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 service@astm.org. For Annual Book of ASTM AvailablefromUnitedStatesEnvironmentalProtectionAgency(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 (2017)
4.3 The extraction and analysis time is 30 to 50 min per analytical column unless routinely occurring analytes are not
sample, depending upon the analytical conditions chosen. adequatelyresolved.ColumnB(7.1.4)isrecommendedforuse
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 DBCPon these columns
lar column. When component concentrations are sufficiently
are presented in Table 1.
high, Gas Chromatography/Mass Spectrometric (GC/MS)
7.1.3 Column A—A 0.32-mm ID by 30-m long fused silica
methods may be used for confirmation analysis. (See EPA
capillary with dimethyl silicone mixed phase. The linear
Method524.2.)
velocity of the helium carrier gas should be about 25 cm/s at
100°C. The column temperature is programmed to hold at
5. Significance and Use
40°C for 4 min, to increase to 190°C at 8°C/min, and hold at
5.1 This test method is useful for the analysis of drinking
190°Cfor25minoruntilallexpectedcompoundshaveeluted.
waterandgroundwaters.Otherwatersmaybeanalyzedbythis
(See Fig. 1 for a sample chromatogram.)
test method, see 1.2.
7.1.4 Column B (alternative column)—A 0.32-mm ID by
5.2 EDB and DBCP have been widely used as soil fumi-
30-m long fused silica capillary with methyl polysiloxane
gants.EDBisalsousedasaleadscavengerinleadedgasolines.
phase. The linear velocity of the helium carrier gas should be
Thesecompoundsareverywatersolubleandareoftenfoundin
about 25 cm/s at 100°C. The column temperature is pro-
groundwater and drinking water. Since they are highly toxic
grammed to hold at 40°C for 4 min, to increase to 270°C at
and are suspected carcinogens, there is concern about the
10°C/min, and hold at 270°C for 10 min or until all expected
potential health impact of even extremely low concentrations
compounds have eluted.
in potable water.
7.1.5 Column C (alternative column, wide bore)—A
0.53-mm ID by 30-m long fused silica capillary with dimethyl
6. Interferences
diphenyl polysiloxane, bonded phase with 2.0-µm film. The
6.1 Impurities contained in the extracting solvent usually hydrogen carrier gas flow is about 80 cm/s linear velocity,
measured at 50°C. The oven temperature is programmed to
account for the majority of the analytical problems. Solvent
blanksshouldbeanalyzedoneachnewbottleofsolventbefore hold at 200°C until all expected compounds have eluted.
use.Indirectdailychecksontheextractingsolventareobtained 7.1.6 Other Heated Zones—Injector temperature: 250°C.
by monitoring the water blanks. Whenever an interference is Detector temperature: 350°C.
noted in the water blank, the analyst should reanalyze the
7.2 Sample Containers—Forty-mL screw cap vials, each
extracting solvent. Low-level interferences generally can be
equipped with a size 24 cap, with a flat, disc-like PTFE-faced
removed by distillation or column chromatography.
polyethylene film/foam extrusion. Individual vials shown to
containatleast40.0mLcanbecalibratedatthe35.0-mLmark
NOTE 1—When a solvent is purified, stabilizers put into the solvent by
the manufacturer are removed, thus potentially making the solvent
so that volumetric, rather than gravimetric, measurements of
hazardous. Also, when a solvent is purified, preservatives put into the
samplevolumescanbeperformed.Priortouse,washvialsand
solvent by the manufacturer are removed, thus potentially making the
septa with detergent and rinse with tap and reagent water.
shelf-life short. However, it is generally more economical to obtain a new
Allow the vials and septa to air dry at room temperature, place
source of solvent. Interference-free solvent is defined as a solvent
in a 105°C oven for 1 h, then remove and allow to cool in an
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
area known to be free of organic solvent vapors.
organochlorine solvents.
7.3 Vials,Auto Sampler,compatiblewithautosamplerofgas
6.2 This liquid-liquid extraction technique efficiently ex-
chromatograph.
tracts a wide boiling range of nonpolar organic compounds
and, in addition, extracts polar organic components of the
sample with varying efficiencies.
An alternative column has been recommended by the Restek Corporation and
6.3 Current column technology suffers from the fact that
is described in 7.1.5 as Column C.
EDBatlowconcentrationsmaybemaskedbyveryhighlevels
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
of dibromochloromethane (DBCM), a common disinfection
purpose.
by-product of chlorinated drinking waters.
J & W DB-1, 1.0 µm film, available from J & W Scientific, or its equivalent,
has been found suitable for this purpose.
7. Apparatus and Equipment 8
Rt –Volatiles,2.0µmfilmthickness.Restekpart#10902,availablefromRestek
x
Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found
7.1 Gas Chromatography (GC) System:
suitable for this purpose.
7.1.1 The GC system must be capable of temperature 9
These parameters were obtained by Restek Corporation during preliminary
programming and should be equipped with a linearized elec- attempts to improve the separation of EDB and DBCM.
troncapturedetectorandacapillarycolumnsplitlessinjectorat
200°C. Separate heated zones for the injector and detector TABLE 1 Chromatographic Conditions for 1,2-dibromethane
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
components are recommended.
7.1.2 Two gas chromatography columns are recommended. Retention Time (min)
Analyte
Column A Column B Column C
Column A (7.1.3) is a highly efficient column that provides
EDB 9.5 8.9 4.1
separations for EDB and DBCP without interferences from
DBCP 17.3 15.0 12.8
trihalomethanes. Column A should be used as the primary
D5316 − 98 (2017)
8.7 Methyl Alcohol—Demonstrated to be free of analytes.
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
pulverizeabatchofNaClandplaceinamufflefurnaceatroom
temperature. Increase the temperature to 400°C for 30 min.
Place in a bottle and cap.
8.9 Sodium Thiosulfate Solution(40g/L)—Dissolve1.0gof
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.
2 2 3
8.10 Solutions, Stock Standard—These solutions may be
purchasedascertifiedsolutionsorpreparedfrompurestandard
materials using the following procedures:
8.10.1 Place approximately 9.8 mL of methanol into a
10-mLgroundglassstopperedvolumetricflask.Allowtheflask
to stand, unstoppered, for about 10 min and weigh to the
nearest 0.1 mg.
8.10.2 Use a 100-µL syringe and immediately add two or
more drops of standard material to the flask. Be sure that the
standard material falls directly into the alcohol without con-
tacting the neck of the flask.
8.10.3 Reweigh, dilute to volume, stopper, then mix by
invertingtheflaskseveraltimes.Calculatetheconcentrationin
µg/µL from the net gain in weight.
8.10.4 Store stock standard solutions in 15-mL bottles
FIG. 1 Extract of Reagent Water Spiked at 0.114 µg/L with EDB equipped with PTFE-lined screw caps. Methanol solutions
and DBCP
prepared from liquid analytes are stable for at least four weeks
when stored at 4°C.
7.4 Microsyringes, 10, 25, and 100-µL.
8.11 Standard Solutions, Primary Dilution—Usestockstan-
dard solutions to prepare primary dilution standard solutions
7.5 Standard Solution Storage Containers—Fifteen-mL
that contain both analytes in methanol. The primary dilution
bottles with PTFE-lined screw caps.
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
the primary dilution standard solutions with minimal
used in all tests. Unless otherwise indicated, it is intended that
headspace, and check frequently for signs of deterioration or
all reagents shall conform to the specifications of the Commit-
evaporation, especially just before preparing calibration stan-
tee onAnalytical Reagents of theAmerican Chemical Society
dards. The storage time described for stock standard solutions
wheresuchspecificationsareavailable. Othergradesmaybe
also applies to primary dilution standard solutions.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
9. Hazards
accuracy of the determination.
9.1 The toxicity and carcinogenicity of chemicals used in
8.2 Purity of Water—Unless otherwise indicated, references
thistestmethodhavenotbeenpreciselydefined;eachchemical
towatershallbeunderstoodtomeanreagentwaterconforming
should be treated as a potential health hazard, and exposure to
to Specification D1193, Type III, which has been shown to be
these chemicals should be minimized. Each laboratory is
free of the analytes of interest.
responsible for maintaining awareness of OSHA regulations
8.3 1,2-dibromoethane, 99%. regarding safe handling of chemicals used in this test method.
Additional references to laboratory safety need to be made
8.4 1,2-dibromo-3-chloropropane, 99%.
available to the analyst.
8.5 Hexane Extraction Solvent, UV Grade.
9.2 EDB and DBCP have been tentatively classified as
8.6 Hydrochloric Acid(1+1)—Addonevolumeofconcen-
known or suspected human or mammalian carcinogens. Pure
trated HCl (sp. gr. 1.19) to one volume of water.
standard materials and stock standard solutions of these com-
pounds should be handled in a hood or glovebox. A NIOSH/
MESAapproved 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
...
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 2017)
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 Closed Conduits
ferred to as DBCP) in water at a minimum detection level of
D3856 Guide for Management Systems in Laboratories
0.010 µg/L by liquid-liquid extraction combined with gas-
Engaged in Analysis of Water
liquid chromatography. This test method is applicable to the
D4210 Practice for Intralaboratory Quality Control Proce-
analysis of drinking waters and groundwaters. It is not recom-
dures and a Discussion on Reporting Low-Level Data
mended for wastewaters, due to the potential for interferences
(Withdrawn 2002)
from high concentrations of other extractable organics. Similar
D5789 Practice for Writing Quality Control Specifications
information can be found in EPA Method 504.
for Standard Test Methods for Organic Constituents
1.2 This test method was used successfully with reagent
(Withdrawn 2002)
water and groundwater. It is the user’s responsibility to ensure
2.2 U.S. EPA Standards:
the validity of this test method for waters of untested matrices.
Method 504 Methods for the Determination of Organic
1.3 The values stated in SI units are to be regarded as
Compounds in Drinking Water, Revision 2.0, 1989
standard. No other units of measurement are included in this
Method 524 Measurement of Purgeable Organic Com-
standard.
pounds in Drinking Water by Gas Chromatography/Mass
1.4 This standard does not purport to address all of the
Spectrometry
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3. Terminology
priate safety, health, and environmental practices and deter-
3.1 Definitions:
mine the applicability of regulatory limitations prior to use.
3.1.1 For definitions of terms used in this standard, refer to
For specific hazard statements, see Sections 6 and 9.
Terminology D1129.
1.5 This international standard was developed in accor-
dance with internationally recognized principles on standard-
4. Summary of Test Method
ization established in the Decision on Principles for the
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.
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-
D1066 Practice for Sampling Steam
ration and analysis. Aqueous calibration standards are ex-
tracted and analyzed in an identical manner as the samples in
This test method is under the jurisdiction of ASTM Committee D19 on Water
order to compensate for possible extraction losses.
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved Dec. 15, 2017. Published January 2018. Originally
approved in 1992. Last previous edition approved in 2011 as D5316 – 98 (2011).
DOI: 10.1520/D5316-98R17. 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 service@astm.org. 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 (2017)
4.3 The extraction and analysis time is 30 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)
7.1.3 Column A—A 0.32-mm ID by 30-m long fused silica
methods may be used for confirmation analysis. (See EPA
capillary with dimethyl silicone mixed phase. The linear
Method 524.2.)
velocity of the helium carrier gas should be about 25 cm/s at
100°C. The column temperature is programmed to hold at
5. Significance and Use
40°C for 4 min, to increase to 190°C at 8°C/min, and hold at
5.1 This test method is useful for the analysis of drinking
190°C for 25 min or until all expected compounds have eluted.
water and groundwaters. Other waters may be analyzed by this
(See Fig. 1 for a sample chromatogram.)
test method, see 1.2.
7.1.4 Column B (alternative column)—A 0.32-mm ID by
5.2 EDB and DBCP have been widely used as soil fumi-
30-m long fused silica capillary with methyl polysiloxane
gants. EDB is also used as a lead scavenger in leaded gasolines.
phase. The linear velocity of the helium carrier gas should be
These compounds are very water soluble and are often found in
about 25 cm/s at 100°C. The column temperature is pro-
groundwater and drinking water. Since they are highly toxic
grammed to hold at 40°C for 4 min, to increase to 270°C at
and are suspected carcinogens, there is concern about the
10°C/min, and hold at 270°C for 10 min or until all expected
potential health impact of even extremely low concentrations
compounds have eluted.
in potable water.
7.1.5 Column C (alternative column, wide bore)—A
0.53-mm ID by 30-m long fused silica capillary with dimethyl
6. Interferences 8
diphenyl polysiloxane, bonded phase with 2.0-µm film. The
hydrogen carrier gas flow is about 80 cm/s linear velocity,
6.1 Impurities contained in the extracting solvent usually
account for the majority of the analytical problems. Solvent measured at 50°C. The oven temperature is programmed to
hold at 200°C until all expected compounds have eluted.
blanks should be analyzed on each new bottle of solvent before
use. Indirect daily checks on the extracting solvent are obtained 7.1.6 Other Heated Zones—Injector temperature: 250°C.
by monitoring the water blanks. Whenever an interference is Detector temperature: 350°C.
noted in the water blank, the analyst should reanalyze the
7.2 Sample Containers—Forty-mL screw cap vials, each
extracting solvent. Low-level interferences generally can be
equipped with a size 24 cap, with a flat, disc-like PTFE-faced
removed by distillation or column chromatography.
polyethylene film/foam extrusion. Individual vials shown to
contain at least 40.0 mL can be calibrated at the 35.0-mL mark
NOTE 1—When a solvent is purified, stabilizers put into the solvent by
the manufacturer are removed, thus potentially making the solvent
so that volumetric, rather than gravimetric, measurements of
hazardous. Also, when a solvent is purified, preservatives put into the
sample volumes can be performed. Prior to use, wash vials and
solvent by the manufacturer are removed, thus potentially making the
septa with detergent and rinse with tap and reagent water.
shelf-life short. However, it is generally more economical to obtain a new
Allow the vials and septa to air dry at room temperature, place
source of solvent. Interference-free solvent is defined as a solvent
in a 105°C oven for 1 h, then remove and allow to cool in an
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
area known to be free of organic solvent vapors.
organochlorine solvents.
7.3 Vials, Auto Sampler, compatible with autosampler of gas
6.2 This liquid-liquid extraction technique efficiently ex-
chromatograph.
tracts a wide boiling range of nonpolar organic compounds
and, in addition, extracts polar organic components of the
sample with varying efficiencies.
An alternative column has been recommended by the Restek Corporation and
6.3 Current column technology suffers from the fact that
is described in 7.1.5 as Column C.
EDB at low concentrations may be masked by very high levels
J & W Durawax DX-3, 0.25 µm, available from J & W Scientific, 91 Blue
of dibromochloromethane (DBCM), a common disinfection Ravine Rd., Folsom, CA 95630, or its equivalent, has been found suitable for this
purpose.
by-product of chlorinated drinking waters.
J & W DB-1, 1.0 µm film, available from J & W Scientific, or its equivalent,
has been found suitable for this purpose.
7. Apparatus and Equipment 8
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
7.1 Gas Chromatography (GC) System:
suitable for this purpose.
7.1.1 The GC system must be capable of temperature 9
These parameters were obtained by Restek Corporation during preliminary
programming and should be equipped with a linearized elec-
attempts to improve the separation of EDB and DBCM.
tron capture detector and a capillary column splitless injector at
200°C. Separate heated zones for the injector and detector
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
components are recommended.
7.1.2 Two gas chromatography columns are recommended. Retention Time (min)
Analyte
Column A Column B Column C
Column A (7.1.3) is a highly efficient column that provides
EDB 9.5 8.9 4.1
separations for EDB and DBCP without interferences from
DBCP 17.3 15.0 12.8
trihalomethanes. Column A should be used as the primary
D5316 − 98 (2017)
8.7 Methyl Alcohol—Demonstrated to be free of analytes.
8.8 Sodium Chloride (NaCl)—For pretreatment before use,
pulverize a batch of NaCl and place in a muffle furnace at room
temperature. Increase the temperature to 400°C for 30 min.
Place in a bottle and cap.
8.9 Sodium Thiosulfate Solution (40 g/L)—Dissolve 1.0 g of
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.
2 2 3
8.10 Solutions, Stock Standard—These solutions may be
purchased as certified solutions or prepared from pure standard
materials using the following procedures:
8.10.1 Place approximately 9.8 mL of methanol into a
10-mL ground glass stoppered volumetric flask. Allow the flask
to stand, unstoppered, for about 10 min and weigh to the
nearest 0.1 mg.
8.10.2 Use a 100-µL syringe and immediately add two or
more drops of standard material to the flask. Be sure that the
standard material falls directly into the alcohol without con-
tacting the neck of the flask.
8.10.3 Reweigh, dilute to volume, stopper, then mix by
inverting the flask several times. Calculate the concentration in
µg/µL from the net gain in weight.
8.10.4 Store stock standard solutions in 15-mL bottles
FIG. 1 Extract of Reagent Water Spiked at 0.114 µg/L with EDB equipped with PTFE-lined screw caps. Methanol solutions
and DBCP
prepared from liquid analytes are stable for at least four weeks
when stored at 4°C.
7.4 Microsyringes, 10, 25, and 100-µL.
8.11 Standard Solutions, Primary Dilution—Use stock stan-
dard solutions to prepare primary dilution standard solutions
7.5 Standard Solution Storage Containers—Fifteen-mL
that contain both analytes in methanol. The primary dilution
bottles with PTFE-lined screw caps.
standards should be prepared at concentrations that can be
8. Reagents
easily diluted to prepare aqueous calibration standards (see
12.1.1) that will bracket the working concentration range. Store
8.1 Purity of Reagents—Reagent grade chemicals shall be
the primary dilution standard solutions with minimal
used in all tests. Unless otherwise indicated, it is intended that
headspace, and check frequently for signs of deterioration or
all reagents shall conform to the specifications of the Commit-
evaporation, especially just before preparing calibration stan-
tee on Analytical Reagents of the American Chemical Society
dards. The storage time described for stock standard solutions
where such specifications are available. Other grades may be
also applies to primary dilution standard solutions.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
9. Hazards
accuracy of the determination.
9.1 The toxicity and carcinogenicity of chemicals used in
8.2 Purity of Water—Unless otherwise indicated, references
this test method have not been precisely defined; each chemical
to water shall be understood to mean reagent water conforming
should be treated as a potential health hazard, and exposure to
to Specification D1193, Type III, which has been shown to be
these chemicals should be minimized. Each laboratory is
free of the analytes of interest.
responsible for maintaining awareness of OSHA regulations
8.3 1,2-dibromoethane, 99 %. regarding safe handling of chemicals used in this test method.
Additional references to laboratory safety need to be made
8.4 1,2-dibromo-3-chloropropane, 99 %.
available to the analyst.
8.5 Hexane Extraction Solvent, UV Grade.
9.2 EDB and DBCP have been tentatively classified as
8.6 Hydrochloric Acid (1 + 1)—Add one volume of concen-
known or suspected human or mammalian carcinogens. Pure
trated HCl (sp. gr. 1.19) to one volume of water.
standard materials and stock standard solutions of these com-
pounds should be handled in a hood or glovebox. A NIOSH/
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 compo
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D5316 − 98 (Reapproved 2011) D5316 − 98 (Reapproved 2017)
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
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 safety, health, and healthenvironmental 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.
2. Referenced Documents
2.1 ASTM Standards:
D1066 Practice for Sampling Steam
D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
D3370 Practices for Sampling Water from Closed Conduits
D3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water
D4210 Practice for Intralaboratory Quality Control Procedures and a Discussion on Reporting Low-Level Data (Withdrawn
2002)
D5789 Practice for Writing Quality Control Specifications for Standard Test Methods for Organic Constituents (Withdrawn
2002)
2.2 U.S. Environmental Protection Agency EPA Standards:
Winfield, T. W.,Method 504 “U.S. EPA Method 504, Revision 2.0,” Methods for the Determination of Organic Compounds in
Drinking Water, Revision 2.0, 1989
Method 524 Measurement of Purgeable Organic Compounds in Drinking Water by Gas Chromatography/Mass Spectrometry
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved May 1, 2011Dec. 15, 2017. Published June 2011January 2018. Originally approved in 1992. Last previous edition approved in 20042011 as
D5316 – 98 (2004).(2011). DOI: 10.1520/D5316-98R11.10.1520/D5316-98R17.
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.
The last approved version of this historical standard is referenced on www.astm.org.
Available from U.S. Environmental Protection Agency, 26 W. Martin Luther King Ave., Cincinnati, OH 45268.United States Environmental Protection Agency (EPA),
William Jefferson Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460, http://www.epa.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D5316 − 98 (2017)
3. Terminology
3.1 Definitions—Definitions: For definitions of terms used in this test method, refer to Terminology D1129.
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
4. Summary of Test Method
4.1 This test method consists of microextraction of the sample followed by gas chromatographic analysis of the extract.
4.2 An aliquot of the sample is extracted with hexane. Two μL of the extract are then injected into a gas chromatograph equipped
with a linearized electron capture detector for separation and analysis. Aqueous calibration standards are extracted and analyzed
in an identical manner as the samples in order to compensate for possible extraction losses.
4.3 The extraction and analysis time is 30 to 50 min per sample, depending upon the analytical conditions chosen.
4.4 Confirmatory evidence can be obtained using a dissimilar column. When component concentrations are sufficiently high,
Gas Chromatography/Mass Spectrometric (GC/MS) methods may be used for confirmation analysis. (See EPA Method 524.2.)
5. 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.
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 extracts 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.
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 electron capture
detector and a capillary column splitless injector at 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 adequately resolved. Column B (7.1.4) is recommended for use as a
confirmatory column when GC/MS confirmation is not viable. Retention times for EDB and DBCP on these columns are
presented in Table 1.
7.1.3 Column A—A 0.32-mm ID by 30-m long fused silica capillary with dimethyl silicone mixed phase. The linear velocity
of the helium carrier gas should be about 25 cm/s at 100°C. The column temperature is programmed to hold at 40°C for 4 min,
to increase to 190°C at 8°C/min, and hold at 190°C for 25 min or until all expected compounds have eluted. (See Fig. 1 for a
sample chromatogram.)
7.1.4 Column B (alternative column)—A 0.32-mm ID by 30-m long fused silica capillary with methyl polysiloxane phase. The
linear velocity of the helium carrier gas should be about 25 cm/s at 100°C. The column temperature is programmed to hold at 40°C
for 4 min, to increase to 270°C at 10°C/min, and hold at 270°C for 10 min or until all expected compounds have eluted.
An alternative column has been recommended by the Restek Corporation and is described in 7.1.5 as Column C.
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 purpose.
J & W DB-1, 1.0 μm film, available from J & W Scientific, or its equivalent, has been found suitable for this purpose.
D5316 − 98 (2017)
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
Retention Time (min)
Analyte
Column A Column B Column C
EDB 9.5 8.9 4.1
DBCP 17.3 15.0 12.8
TABLE 1 Chromatographic Conditions for 1,2-dibromethane
(EDB) and 1,2-dibromo-3-chloropropane (DBCP)
Retention Time (min)
Analyte
Column A Column B Column C
EDB 9.5 8.9 4.1
DBCP 17.3 15.0 12.8
FIG. 1 Extract of Reagent Water Spiked at 0.114 μg/L with EDB and DBCP
7.1.5 Column C (alternative column, wide bore)—A 0.53- mm 0.53-mm ID by 30-m long fused silica capillary with dimethyl
diphenyl polysiloxane, bonded phase with 2.0 μm 2.0-μm film. The hydrogen carrier gas flow is about 80 cm/s linear velocity,
measured at 50°C. The oven temperature is programmed to hold at 200°C until all expected compounds have eluted.
7.1.6 Other Heated Zones—Injector temperature: 250°C. Detector temperature: 350°C.
7.2 Sample Containers—Forty-mL screw cap vials, each equipped with a size 24 cap, with a flat, disc-like PTFE-faced
polyethylene film/foam extrusion. Individual vials shown to contain at least 40.0 mL can be calibrated at the 35.0 mL 35.0-mL
mark so that volumetric, rather than gravimetric, measurements of sample volumes can be performed. Prior to use, wash vials and
septa with detergent and rinse with tap and reagent water. Allow the vials and septa to air dry at room temperature, place in a 105°C
oven for 1 h, then remove and allow to cool in an area known to be free of organic solvent vapors.
7.3 Vials, Auto Sampler, compatible with autosampler of gas chromatograph.
7.4 Microsyringes, 10, 25, and 100-μL.
7.5 Standard Solution Storage Containers—Fifteen-mL bottles with PTFE-lined screw caps.
Rt –Volatiles, 2.0 μm film thickness. Restek part #10902, available from Restek Corp., 110 Benner Circle, Bellefonte, PA 16823, or its equivalent has been found suitable
x
for this purpose.
These parameters were obtained by Restek Corporation during preliminary attempts to improve the separation of EDB and DBCM.
D5316 − 98 (2017)
8. Reagents
8.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Specification D1193, Type III, which has been shown to be free of the analytes of interest.
8.3 1,2-dibromoethane, 99 %.
8.4 1,2-dibromo-3-chloropropane, 99 %.
8.5 Hexane Extraction Solvent, UV Grade.
8.6 Hydrochloric Acid (1 + 1)—Add one volume of concentrated HCl (sp. gr. 1.19) to one volume of water.
8.7 Methyl Alcohol—Demonstrated to be free of analytes.
8.8 Sodium Chloride (NaCl)—For pretreatment before use, pulverize a batch of NaCl and place in a muffle furnace at room
temperature. Increase the temperature to 400°C for 30 min. Place in a bottle and cap.
8.9 Sodium Thiosulfate Solution (40 g/L)—Dissolve 1.0 g of sodium thiosulfate (Na S O ) in 25 mL of water. Solid Na S O
2 2 3 2 2 3
may be used in place of the solution.
8.10 Solutions, Stock Standard—These solutions may be purchased as certified solutions or prepared from pure standard
materials using the following procedures:
8.10.1 Place approximately 9.8 mL of methanol into a 10-mL ground glass stoppered volumetric flask. Allow the flask to stand,
unstoppered, for about 10 min and weigh to the nearest 0.1 mg.
8.10.2 Use a 100-μL syringe and immediately add two or more drops of standard material to the flask. Be sure that the standard
material falls directly into the alcohol without contacting the neck of the flask.
8.10.3 Reweigh, dilute to volume, stopper, then mix by inverting the flask several times. Calculate the concentration in μg/μL
from the net gain in weight.
8.10.4 Store stock standard solutions in 15-mL bottles equipped with PTFE-lined screw caps. Methanol solutions prepared from
liquid analytes are stable for at least four weeks when stored at 4°C.
8.11 Standard Solutions, Primary Dilution—Use stock standard solutions to prepare primary dilution standard solutions that
contain both analytes in methanol. The primary dilution standards should be prepared at concentrations that can be easily diluted
to prepare aqueous calibration standards (see 12.1.1) that will bracket the working concentration range. Store the primary dilution
standard solutions with minimal headspace, and check frequently for signs of deterioration or evaporation, especially just before
preparing calibration standards. The storage time described for stock standard solutions also applies to primary dilution standard
solutions.
9. Hazards
9.1 The toxicity and carcinogenicity of chemicals used in this test method have not been pr
...
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