1、Designation: D5316 98 (Reapproved 2017)Standard Test Method for1,2-Dibromoethane and 1,2-Dibromo-3-Chloropropane inWater by Microextraction and Gas Chromatography1This standard is issued under the fixed designation D5316; the number immediately following the designation indicates the year oforiginal
2、 adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of 1,2-dibromoethane (com
3、monly referred to as ethylene dibromideor EDB) and 1,2-dibromo-3-chloropropane (commonly re-ferred to as DBCP) in water at a minimum detection level of0.010 g/L by liquid-liquid extraction combined with gas-liquid chromatography. This test method is applicable to theanalysis of drinking waters and g
4、roundwaters. It is not recom-mended for wastewaters, due to the potential for interferencesfrom high concentrations of other extractable organics. Similarinformation can be found in EPA Method 504.1.2 This test method was used successfully with reagentwater and groundwater. It is the users responsib
5、ility to ensurethe validity of this test method for waters of untested matrices.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with
6、 its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.For specific hazard statements, see Sections 6 and 9.1.5 This international standard was develo
7、ped in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Docum
8、ents2.1 ASTM Standards:2D1066 Practice for Sampling SteamD1129 Terminology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits (Withdrawn 2003)3D1193 Specification for Reagent WaterD3370 Practices for Sampling Water from Closed ConduitsD3856 Guide for Management
9、 Systems in LaboratoriesEngaged in Analysis of WaterD4210 Practice for Intralaboratory Quality Control Proce-dures and a Discussion on Reporting Low-Level Data(Withdrawn 2002)3D5789 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Organic Constituents(Withdrawn 2002)3
10、2.2 U.S. EPA Standards:4Method 504 Methods for the Determination of OrganicCompounds in Drinking Water, Revision 2.0, 1989Method 524 Measurement of Purgeable Organic Com-pounds in Drinking Water by Gas Chromatography/MassSpectrometry3. Terminology3.1 Definitions:3.1.1 For definitions of terms used i
11、n this standard, refer toTerminology D1129.4. Summary of Test Method4.1 This test method consists of microextraction of thesample followed by gas chromatographic analysis of theextract.4.2 An aliquot of the sample is extracted with hexane. TwoL of the extract are then injected into a gas chromatogra
12、phequipped with a linearized electron capture detector for sepa-ration and analysis. Aqueous calibration standards are ex-tracted and analyzed in an identical manner as the samples inorder to compensate for possible extraction losses.1This test method is under the jurisdiction of ASTM Committee D19
13、on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Dec. 15, 2017. Published January 2018. Originallyapproved in 1992. Last previous edition approved in 2011 as D5316 98 (2011).DOI: 10.1520/D5316-98R17.2For re
14、ferenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced
15、 onwww.astm.org.4Available from United States Environmental ProtectionAgency (EPA),WilliamJefferson 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 StatesThis
16、international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT
17、) Committee.14.3 The extraction and analysis time is 30 to 50 min persample, depending upon the analytical conditions chosen.4.4 Confirmatory evidence can be obtained using a dissimi-lar column. When component concentrations are sufficientlyhigh, Gas Chromatography/Mass Spectrometric (GC/MS)methods
18、may be used for confirmation analysis. (See EPAMethod 524.2.)5. Significance and Use5.1 This test method is useful for the analysis of drinkingwater and groundwaters. Other waters may be analyzed by thistest method, see 1.2.5.2 EDB and DBCP have been widely used as soil fumi-gants. EDB is also used
19、as a lead scavenger in leaded gasolines.These compounds are very water soluble and are often found ingroundwater and drinking water. Since they are highly toxicand are suspected carcinogens, there is concern about thepotential health impact of even extremely low concentrationsin potable water.6. Int
20、erferences6.1 Impurities contained in the extracting solvent usuallyaccount for the majority of the analytical problems. Solventblanks should be analyzed on each new bottle of solvent beforeuse. Indirect daily checks on the extracting solvent are obtainedby monitoring the water blanks. Whenever an i
21、nterference isnoted in the water blank, the analyst should reanalyze theextracting solvent. Low-level interferences generally can beremoved by distillation or column chromatography.NOTE 1When a solvent is purified, stabilizers put into the solvent bythe manufacturer are removed, thus potentially mak
22、ing the solventhazardous. Also, when a solvent is purified, preservatives put into thesolvent by the manufacturer are removed, thus potentially making theshelf-life short. However, it is generally more economical to obtain a newsource of solvent. Interference-free solvent is defined as a solventcont
23、aining less than 0.1 g/L individual analyte interference. Protectinterference-free solvents by storing them in an area known to be free oforganochlorine solvents.6.2 This liquid-liquid extraction technique efficiently ex-tracts a wide boiling range of nonpolar organic compoundsand, in addition, extr
24、acts polar organic components of thesample with varying efficiencies.6.3 Current column technology suffers from the fact thatEDB at low concentrations may be masked by very high levelsof dibromochloromethane (DBCM), a common disinfectionby-product of chlorinated drinking waters.7. Apparatus and Equi
25、pment7.1 Gas Chromatography (GC) System:7.1.1 The GC system must be capable of temperatureprogramming and should be equipped with a linearized elec-tron capture detector and a capillary column splitless injector at200C. Separate heated zones for the injector and detectorcomponents are recommended.7.
26、1.2 Two gas chromatography columns are recommended.Column A (7.1.3) is a highly efficient column that providesseparations for EDB and DBCP without interferences fromtrihalomethanes. Column A should be used as the primaryanalytical column unless routinely occurring analytes are notadequately resolved
27、. Column B (7.1.4) is recommended for useas a confirmatory column when GC/MS confirmation is notviable.5Retention times for EDB and DBCP on these columnsare presented in Table 1.7.1.3 Column AA 0.32-mm ID by 30-m long fused silicacapillary with dimethyl silicone mixed phase.6The linearvelocity of th
28、e helium carrier gas should be about 25 cm/s at100C. The column temperature is programmed to hold at40C for 4 min, to increase to 190C at 8C/min, and hold at190C 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
29、 ID by30-m long fused silica capillary with methyl polysiloxanephase.7The linear velocity of the helium carrier gas should beabout 25 cm/s at 100C. The column temperature is pro-grammed to hold at 40C for 4 min, to increase to 270C at10C/min, and hold at 270C for 10 min or until all expectedcompound
30、s have eluted.7.1.5 Column C5(alternative column, wide bore)A0.53-mm ID by 30-m long fused silica capillary with dimethyldiphenyl polysiloxane, bonded phase with 2.0-m film.8Thehydrogen carrier gas flow is about 80 cm/s linear velocity,measured at 50C. The oven temperature is programmed tohold at 20
31、0C until all expected compounds have eluted.7.1.6 Other Heated ZonesInjector temperature: 250C.Detector temperature: 350C.97.2 Sample ContainersForty-mL screw cap vials, eachequipped with a size 24 cap, with a flat, disc-like PTFE-facedpolyethylene film/foam extrusion. Individual vials shown toconta
32、in at least 40.0 mL can be calibrated at the 35.0-mL markso that volumetric, rather than gravimetric, measurements ofsample volumes can be performed. Prior to use, wash vials andsepta with detergent and rinse with tap and reagent water.Allow the vials and septa to air dry at room temperature, placei
33、n a 105C oven for 1 h, then remove and allow to cool in anarea known to be free of organic solvent vapors.7.3 Vials, Auto Sampler, compatible with autosampler of gaschromatograph.5An alternative column has been recommended by the Restek Corporation andis described in 7.1.5 as Column C.6J each chemic
34、alshould be treated as a potential health hazard, and exposure tothese chemicals should be minimized. Each laboratory isresponsible for maintaining awareness of OSHA regulationsregarding safe handling of chemicals used in this test method.Additional references to laboratory safety need to be madeava
35、ilable to the analyst.9.2 EDB and DBCP have been tentatively classified asknown or suspected human or mammalian carcinogens. Purestandard 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
36、 theanalyst handles high concentrations of these toxic compounds.NOTE 2When a solvent is purified, stabilizers put into the solvent bythe manufacturer are removed, thus potentially making the solventhazardous.10Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Wa
37、shington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.FIG. 1
38、Extract of Reagent Water Spiked at 0.114 g/L with EDBand DBCPD5316 98 (2017)310. Sample Collection, Preservation, and Storage10.1 Sample Collection:10.1.1 Collect the sample in accordance with PracticeD1066, Guide D1192, and Practices D3370, as applicable.10.1.2 Collect all samples in 40-mL bottles
39、into which 3 mgof sodium thiosulfate crystals have been added to the emptybottles just prior to shipping to the sampling site. Alternately,add 75 Lof freshly-prepared sodium thiosulfate solution (0.04mg/L) added to empty 40-mL bottles just prior to samplecollection.10.1.3 When sampling from a water
40、tap, open the tap andallow the system to flush until the water temperature hasstabilized (usually about 10 min). Adjust the flow to about 500mL/min and collect samples from the flowing stream.10.1.4 When sampling from a well, fill a wide mouthedbottle or beaker with sample and carefully fill 40-mL s
41、amplebottles.10.2 Sample Preservation:10.2.1 Chill the samples to 4C on the day of collection andmaintain at that temperature until analysis. Field samples thatwill not be received at the laboratory on the day of collectionmust be packaged for shipment with sufficient ice to ensure thatthey will be
42、4C on arrival at the laboratory.10.2.2 The addition of sodium thiosulfate as a dechlorinat-ing agent or acidification, or both, to pH 2 with HCl (1 + 1),common preservative procedures for purgeable compounds,has been shown to have no effect on EDB or DBCP (see Table2). Nonetheless, sodium thiosulfat
43、e must be added to avoid thepossibility of reactions that may occur between residualchlorine and indeterminate contaminants present in somesolvents, yielding compounds which may subsequently inter-fere with the analysis. The presence of sodium thiosulfate willarrest the formation of DBCM (see 6.3).
44、Also, samples shouldbe acidified to avoid the possibility of microbial degradationthat may periodically affect these analytes contained in othergroundwater matrices.10.3 Sample Storage:10.3.1 Store samples and field reagent blanks together at4C until analysis. The sample storage area must be free of
45、organic solvent vapors.10.3.2 Analyze all samples within 28 days of collection.11. Preparation of Apparatus11.1 Set up the gas chromatograph in accordance with themanufacturers instructions. Install the capillary column(s) andtest for leaks using techniques recommended by the instru-ments or capilla
46、ry columns manufacturer.11.2 Instrument PerformanceCheck the performance ofthe entire analytical system daily using data gathered fromanalyses of water blanks and standards.11.2.1 Correct significant peak tailing in excess of thatshown for the target compounds in the method chromatogram(Fig. 1).11.2
47、.2 Check the precision between replicate analyses. Aproperly operating system will exhibit an average relativestandard deviation of less than 10 %.12. Calibration and Standardization12.1 Calibration:12.1.1 Use at least three calibration standards; five arerecommended. One should contain EDB and DBCP
48、 at aconcentration near to the reporting limit for each compound;the other two should be at concentrations that bracket the rangeexpected in samples.12.1.2 To prepare a calibration standard (CAL), add anappropriate volume of a primary dilution standard solution toan aliquot of water in a volumetric
49、flask. If less than 20 L ofan alcoholic standard is added to the reagent water, poorprecision may result. Use a 25-L microsyringe and rapidlyinject the alcoholic standard into the expanded area of the filledvolumetric flask. Remove the needle as quickly as possibleafter injection. Mix by inverting the flask several times.Aqueous standards should be prepared fresh and extractedimmediately after preparation unless sealed and stored withoutheadspace as described in 8.11.12.1.3 Each day, analyze each calibration standard accord-ing to Section 12
