1、Designation: D 5175 91 (Reapproved 2003)Standard Test Method forOrganohalide Pesticides and Polychlorinated Biphenyls inWater by Microextraction and Gas Chromatography1This standard is issued under the fixed designation D 5175; the number immediately following the designation indicates the year ofor
2、iginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method (1,2,3)2is applicable to the determi-nation
3、 of the following analytes in finished drinking water,drinking water during intermediate stages of treatment, and theraw source water:AnalyteChemical Abstract ServiceRegistry NumberAAlachlor 5972-60-8Aldrin 309-00-2Chlordane 57-74-9Dieldrin 60-57-1Endrin 72-20-8Heptachlor 76-44-8Heptachlor Epoxide 1
4、024-57-3Hexachlorobenzene 118-74-1Lindane 58-89-9Methoxychlor 72-43-5Toxaphene 8001-35-2AroclorB1016 12674-11-2AroclorB1221 11104-28-2AroclorB1232 11141-16-5AroclorB1242 53469-21-9AroclorB1248 12672-29-6AroclorB1254 11097-69-1AroclorB1260 11096-82-5ANumbering system of CAS Registry Services, P.O. Bo
5、x 3343, Columbus, OH43210-0334.BAroclor is a registered trademark of Monsanto Co.1.2 Detection limits for most test method analytes are lessthan 1 g/L. Actual detection limits are highly dependent onthe characteristics of the sample matrix and the gas chroma-tography system. Table 1 contains the app
6、licable concentrationrange for the precision and bias statements. Only Aroclor 1016and 1254 were included in the interlaboratory test used toderive the precision and bias statements. Data for other PCBproducts are likely to be similar.1.3 Chlordane, toxaphene, and Aroclor products (polychlo-rinated
7、biphenyls) are multicomponent materials. Precision andbias statements reflect recovery of these materials dosed intowater samples. The precision and bias statements may notapply to environmentally altered materials or to samplescontaining complex mixtures of polychlorinated biphenyls(PCBs) and organ
8、ochlorine pesticides.1.4 For compounds other than those listed in 1.1 or for othersample sources, the analyst must demonstrate the applicabilityof this test method by collecting precision and bias data onspiked samples (groundwater, tap water) (4) and providequalitative confirmation of results by ga
9、s chromatography/mass spectrometry (GC/MS) (5) or by GC analysis usingdissimilar columns.1.5 This test method is restricted to use by or under thesupervision of analysts experienced in the use of GC and in theinterpretation of gas chromatograms. Each analyst must dem-onstrate the ability to generate
10、 acceptable results using theprocedure described in Section 13.1.6 Analytes that are not separated chromatographically,(analytes that have very similar retention times) cannot beindividually identified and measured in the same calibrationmixture or water sample unless an alternative technique foride
11、ntification and quantitation exists (see section 13.4).1.7 When this test method is used to analyze unfamiliarsamples for any or all of the analytes listed in 1.1, analyteidentifications and concentrations should be confirmed by atleast one additional technique.1.8 The values stated in SI units are
12、to be regarded as thestandard. The inch-pound units given in parentheses are forinformation only.1.9 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health
13、practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardstatements, see Section 9.2. Referenced Documents2.1 ASTM Standards:D 1129 Terminology Relating to Water31This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct r
14、esponsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Jan. 10, 2003. Published January 2003. Originallyapproved in 1991. Last previous edition approved in 1996 as D 5175 91 (1996)e1.2The boldface numbers in parentheses refer to a list of
15、references at the end ofthis test method.3Annual Book of ASTM Standards, Vol 11.01.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.D 1193 Specification for Reagent Water3D 3534 Test Method for Polychlorinated Biphenyls (PCBs)in Water
16、4D 3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of Water3D 4128 Practice for Identification of Organic Compounds inWater by Combined Gas Chromatography and ElectronImpact Mass Spectrometry4D 4210 Practice for Intralaboratory Quality Control Proce-dures a
17、nd a Discussion on Reporting Low-Level Data34Annual Book of ASTM Standards, Vol 11.02.TABLE 1 Test Method Precision and BiasAas Functions of ConcentrationCompound Applicable Concentration Range, g/LWater TypeBCDEReagent water Ground waterAlachlor 0.50 to 37.50 So= 0.077X + 0.09 So= 0.075X + 0.05St=
18、0.107X + 0.15 St= 0.086X + 0.29X = 1.004C 0.08 X = 1.059C + 0.03Aldrin 0.04 to 1.42 So= 0.030X + 0.02 So=0.115X + 0.00St= 0.251X + 0.00 St= 0.189X + 0.01X = 1.066C + 0.00 X = 0.945C 0.00Chlordane 0.51 to 50.90 So= 0.083X + 0.06St= 0.125X + 0.19X = 1.037C + 0.06So= 0.062X + 0.09St= 0.147X + 0.24X = 0
19、.941C + 0.09Dieldrin 0.10 to 7.53 So= 0.091X + 0.01St= 0.199X + 0.02X = 1.027C + 0.00So= 0.089X + 0.04St= 0.221X + 0.04X = 0.961C + 0.01Endrin 0.10 to 7.50 So=0.116X + 0.01St= 0.134X + 0.02X = 0.958C + 0.01So= 0.045X + 0.15St= 0.196X + 0.07X = 0.958C + 0.05Heptachlor 0.04 to 1.41 So= 0.104X + 0.01St
20、= 0.206X + 0.02X = 1.002C + 0.02So= 0.058X + 0.02St= 0.153X + 0.02X = 0.964C + 0.02Heptachlor Epoxide 0.04 to 1.42 So= 0.031X + 0.02St= 0.127X + 0.02X = 0.952C + 0.00So= 0.032X + 0.00St= 0.103X + 0.02X = 0.932C + 0.01Hexachlorobenzene 0.01 to 0.37 So= 0.104X + 0.00St= 0.231X + 0.00X = 1.028C 0.00So=
21、 0.148X + 0.00St= 0.301X + 0.00X = 0.901C 0.00Lindane 0.04 to 1.39 So= 0.056X + 0.01St= 0.141X + 0.00X = 1.009C 0.00So= 0.095X + 0.00St= 0.134X 0.00X = 0.909C + 0.00Methoxychlor 0.20 to 15.00 So=0.115X + 0.12St= 0.122X + 0.21X = 0.950C + 0.15So= 0.179X + 0.02St= 0.210X + 0.08X = 1.014C + 0.07Toxaphe
22、ne 5.63 to 70.40 So= 0.132X 0.32St= 0.273X 0.72X = 1.087C + 0.24So= 0.067X + 0.28St= 0.181X + 1.52X = 0.903C + 0.50PCB-1016 0.50 to 49.80 So= 0.106X + 0.31St= 0.144X + 0.46X = 0.856C + 0.31So= 0.141X + 0.13St= 0.218X + 0.06X = 0.958C + 0.07PCB-1254 0.50 to 50.40 So= 0.122X + 0.12St= 0.282X + 0.05X =
23、 0.872C 0.01So= 0.126X + 0.17St= 0.396X + 0.02X = 0.938C 0.02ABias = CX.BX = Mean recovery.CC = True concentration value.DSt= Overall standard deviation.ESo= Single analyst standard deviation.D 5175 91 (2003)2E 355 Practice for Gas Chromatography Terms and Rela-tionships52.2 EPA Standards:Method 505
24、, Analysis of Organohalide Pesticides and Aro-clors in Water by Microextraction and Gas Chromatogra-phy6Method 680, Determination of Pesticides and PCBs inWater and Soil/Sediment by Gas Chromatography/MassSpectrometry63. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, ref
25、er to Terminology D 1129 and Practice E 355.3.2 Definitions of Terms Specific to This Standard:3.2.1 field duplicates (FD 1 and FD 2), ntwo separatesamples collected at the same time and placed under identicalcircumstances and treated exactly the same throughout fieldand laboratory procedures. Analy
26、ses of FD 1 and FD 2 give ameasure of the precision associated with sample collection,preservation and storage, as well as with laboratory procedures.3.2.2 field reagent blank (FRB), nreagent water placed ina sample container in the laboratory and treated as a sample inall respects, including exposu
27、re to sampling site conditions,storage, preservation, and all analytical procedures. The re-agent water must be transferred to an empty, clean samplecontainer in the field. The purpose of the FRB is to determineif analytes or other interferences are present in the fieldenvironment.3.2.3 instrument p
28、erformance check solution (IPC), nasolution of analytes used to evaluate the performance of theinstrument system with respect to test method criteria.3.2.4 laboratory duplicates (LD 1 and LD 2), ntwosample aliquots taken in the analytical laboratory and analyzedseparately with identical procedures.
29、Analyses of LD 1 and LD2 give a measure of the precision associated with laboratoryprocedures but not with sample collection, preservation, orstorage procedures.3.2.5 laboratory fortified blank (LFB), nan aliquot ofreagent water to which known quantities of the analytes areadded in the laboratory. T
30、he LFB is analyzed exactly like asample, and its purpose is to determine whether the method-ology is in control, and whether the laboratory is capable ofmaking accurate and precise measurements.3.2.6 laboratory fortified sample matrix (LFM), nanaliquot of an environmental sample to which known quant
31、itiesof the analytes are added in the laboratory. The LFM isanalyzed as a sample, and its purpose is to determine whetherthe sample matrix contributes bias to the analytical results. Thebackground concentrations of the analytes in the sample matrixmust be determined in a separate aliquot and the mea
32、suredvalues in the LFM corrected for background concentrations.3.2.7 laboratory reagent blank (LRB), nan aliquot ofreagent water that is treated as a sample including exposure toall glassware, equipment, solvents, and reagents used withother samples. The LRB is used to determine if methodanalytes or
33、 other interferences are present in the laboratoryenvironment, the reagents, or the apparatus.3.2.8 standard solution, secondary dilution, na solutionof several analytes prepared in the laboratory from stockstandard solutions and diluted as needed to prepare calibrationsolutions and other needed ana
34、lyte solutions.3.2.9 standard solution, stock, na concentrated solutioncontaining a single certified standard that is an analyte or aconcentrated solution of a single analyte prepared in thelaboratory with an assayed reference compound. Stock stan-dard solutions are used to prepare secondary dilutio
35、n standards.3.2.10 quality control sample (QCS), na sample contain-ing analytes or a solution of analytes in a water-misciblesolvent used to fortify reagent water or environmental samples.The QCS must be independent of solutions used to preparestandards and should be obtained from a source external
36、to thelaboratory. The QCS is used to check laboratory performancewith externally prepared test materials.4. Summary of Test Method4.1 This is a microextraction method in which 35 mL ofsample are extracted with 2 mL of hexane. Two L of theextract are injected into a gas chromatograph equipped with al
37、inearized electron capture detector for separation and analysis.Aqueous calibration standards are extracted and analyzed in anidentical manner to compensate for possible extraction losses.4.2 The extraction and analysis time is 30 to 50 min persample depending upon the analytes and the analytical co
38、ndi-tions chosen.4.3 This test method is based largely on EPA Method 505.5. Significance and Use5.1 The extensive and widespread use of organochlorinepesticides and PCBs has resulted in their presence in all partsof the environment. These compounds are persistent and mayhave adverse effects on the e
39、nvironment. Thus, there is a needto identify and quantitate these compounds in water samples.6. Interferences6.1 Interferences may be caused by contaminants in sol-vents, reagents, glassware, and other sample processing appa-ratus that lead to discrete artifacts or elevated baselines in gaschromatog
40、rams. All reagents and apparatus must be routinelydemonstrated to be free from interferences under the conditionsof the analysis by running laboratory reagent blanks asdescribed in 12.2.6.1.1 Glassware must be scrupulously cleaned (2). Clean allglassware as soon as possible after use by thoroughly r
41、insingwith the last solvent used in it. Follow by washing with hot tapwater and detergent and thoroughly rinsing with tap andreagent water. Drain dry and heat in an oven or muffle furnaceat 400C for 1 h. Do not heat volumetric ware. Thermallystable materials might not be eliminated by this treatment
42、.Thorough rinsing with acetone may be substituted for theheating. After drying and cooling, seal and store glassware ina clean environment to prevent any accumulation of dust orother contaminants. Store inverted or capped with aluminumfoil.5Annual Book of ASTM Standards, Vol 14.02.6Available from US
43、 EPA, Environmental Monitoring Systems Laboratory,Cincinnati, OH 45268.D 5175 91 (2003)36.1.2 The use of high purity reagents and solvents helps tominimize interference problems. Purification of solvents bydistillation in all-glass systems may be required.6.2 Phthalate esters, frequently found in pl
44、astics, paints, andother common laboratory items, produce a positive response onan electron capture detector. Therefore, samples and solventsshould come in contact only with those materials specified inthis test method.6.3 Interfering contamination may occur when a samplecontaining low concentration
45、s of analytes is analyzed imme-diately following a sample containing relatively high concen-trations of analytes. Between-sample rinsing of the samplesyringe and associated equipment with hexane can minimizesample cross contamination. After analysis of a sample con-taining high concentrations of ana
46、lytes, one or more injectionsof hexane should be made to ensure that accurate values areobtained for the next sample.6.4 Matrix interferences may be caused by contaminantsthat are coextracted from the sample. Also, note that all theanalytes listed in the scope are not resolved from each other onany
47、one column; one analyte of interest may be an interferentfor another analyte of interest. The extent of matrix interfer-ences will vary considerably from source to source dependingupon the water sampled. Cleanup of sample extracts may benecessary. Positive identifications should be confirmed (seesec
48、tion 13.4).6.5 It is important that samples and working standards becontained in the same solvent. The solvent for workingstandards must be the same as the final solvent used in samplepreparation. If this is not the case, chromatographic compara-bility of standards to sample may be affected.6.6 Caut
49、ion must be taken in the determination of endrinsince it has been reported that the splitless injector may causeendrin degradation (6). The analyst should be alerted to thispossible interference resulting in an erratic response for endrin.6.7 Variable amounts of pesticides and PCBs from aqueoussolutions adhere to glass surfaces. It is recommended thatsample transfers and glass surface contacts be minimized.6.8 Aldrin and methoxychlor are rapidly oxidized by chlo-rine. Dechlorination with sodium thiosulfate at time of collec-tion will reta
