1、Designation: D5315 04 (Reapproved 2017)1Standard Test Method forDetermination of N-Methyl-Carbamoyloximes andN-Methylcarbamates in Water by Direct Aqueous InjectionHPLC with Post-Column Derivatization1This standard is issued under the fixed designation D5315; the number immediately following the des
2、ignation indicates the year oforiginal 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.1NOTEWarning notes were editorially updat
3、ed throughout in December 2017.1. Scope1.1 This is a high-performance liquid chromatographic(HPLC) test method applicable to the determination of certainn-methylcarbamoyloximes and n-methylcarbamates in groundwater and finished drinking water (1).2This test method isapplicable to any carbamate analy
4、te that can be hydrolyzed toa primary amine. The following compounds have been vali-dated using this test method:AnalyteChemical Abstract ServicesRegistry NumberAAldicarb 116-06-3Aldicarb sulfone 1646-88-4Aldicarb sulfoxide 1646-87-3Baygon 114-26-1Carbaryl 63-25-2Carbofuran 1563-66-23-Hydroxycarbofu
5、ran 16655-82-6Methiocarb 2032-65-7Methomyl 16752-77-5Oxamyl 23135-22-0ANumbering system of Chemical Abstracts, Inc.1.2 This test method has been validated in a collaborativeround-robin study (2) and estimated detection limits (EDLs)have been determined for the analytes listed in 1.1 (Table 1).Observ
6、ed detection limits may vary between ground waters,depending on the nature of interferences in the sample matrixand the specific instrumentation used.1.3 This test method is restricted to use by, or under thesupervision of, analysts experienced in both the use of liquidchromatography and the interpr
7、etation of liquid chromato-grams. Each analyst should demonstrate an ability to generateacceptable results with this test method using the proceduredescribed in 12.3.1.4 When this test method is used to analyze unfamiliarsamples for any or all of the analytes listed in 1.1, analyteidentifications sh
8、ould be confirmed by at least one additionalqualitative technique.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It i
9、s 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.Additional guidance on laboratory safety is available andsuitable references for the information are provided
10、 (3-5).1.7 This international standard was developed 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 TechnicalBarr
11、iers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:3D1129 Terminology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits (Withdrawn 2003)4D1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicab
12、le Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Closed ConduitsD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic Constituents1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility o
13、f 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 D5315 04 (2011).DOI: 10.1520/D5315-04R17E01.2The boldface numbers in parentheses refer to
14、the references at the end of thistest method.3For referenced 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.4The last approv
15、ed version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization e
16、stablished in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1E682 Practice for Liquid Chromatography Terms and Rela-tionships2.2 U.S. Environmental Protection Age
17、ncy Standard:5EPAMethod 531.1 Revision 3.0, USEPA, EMSL-Cincinnati,1989EPAMethod 531.2 Revision 1.0, USEPA, EMSL-Cincinnati,20013. Terminology3.1 Definitions:3.1.1 For definitions of water terms used in this standard,refer to Terminology D1129.3.1.2 For definitions of other terms used in this standa
18、rd,refer to Practice E682.3.2 Definitions of Terms Specific to This Standard:3.2.1 calibration standard (CAL),na solution preparedfrom the primary dilution standard solution and stock standardsolutions of the internal standards and surrogate analytes. CALsolutions are used to calibrate the instrumen
19、t response withrespect to analyte concentration.3.2.2 field duplicates (FD1 and FD2),ntwo separatesamples collected at the same time, placed under identicalcircumstances, and treated exactly the same throughout fieldand laboratory procedures. Analyses of FD1 and FD2 providea measure of the precision
20、 associated with sample collection,preservation, and storage, as well as with laboratory proce-dures.3.2.3 field reagent blank (FRB),nreagent water placed ina sample container in the laboratory and treated in all respectsas a sample, including being exposed to sampling siteconditions, storage, prese
21、rvation, and all analytical procedures.The purpose of the FRB is to determine whether methodanalytes or other interferences are present in the field environ-ment.3.2.4 internal standard, na pure analyte(s) added to asolution in known amount(s) and used to measure the relativeresponses of other analy
22、tes and surrogates that are componentsof the same solution. The internal standard must be an analytethat is not a sample component.3.2.5 laboratory duplicates (LD1 and LD2),ntwo samplealiquots taken in the analytical laboratory and analyzed sepa-rately with identical procedures. Analyses of LD1 and
23、LD2provide a measure of the precision associated with laboratoryprocedures, but not with sample collection, preservation, orstorage procedures.3.2.6 laboratory-fortified blank (LFB),nan aliquot ofreagent water to which known quantities of the test methodanalytes are added in the laboratory. The LFB
24、is analyzedexactly as a sample is; its purpose is to determine whether themethodology is in control and whether the laboratory iscapable of making accurate and precise methods at the requiredtest method detection limit.3.2.7 laboratory-fortified sample matrix (LFM),nan ali-quot of an environmental s
25、ample to which known quantities ofthe test method analytes are added in the laboratory. The LFMis analyzed exactly as a sample is; its purpose is to determinewhether the sample matrix contributes bias to the analyticalresults. The background concentrations of the analytes in thesample matrix must be
26、 determined in a separate aliquot and themeasured values in the LFM corrected for background concen-trations.3.2.8 laboratory performance check solution (LPC),nasolution of method analytes, surrogate compounds, and internalstandards used to evaluate the performance of the instrumentsystem with respe
27、ct to a defined set of method criteria.3.2.9 laboratory reagent blank (LRB),nan aliquot ofreagent water treated exactly the same as a sample, includingbeing exposed to all glassware, equipment, solvents, reagents,internal standards, and surrogates that are used with othersamples. The LRB is used to
28、determine whether methodanalytes or other interferences are present in the laboratoryenvironment, the reagents, or the apparatus.3.2.10 primary dilution standard solution, na solution ofseveral analytes prepared in the laboratory from stock standardsolutions and diluted as necessary to prepare calib
29、rationsolutions and other necessary analyte solutions.3.2.11 quality control sample (QCS),na sample matrixcontaining test method analytes or a solution of test methodanalytes in a water miscible solvent that is used to fortify wateror environmental samples. The QCS is obtained from a sourceexternal
30、to the laboratory and is used to check the laboratoryperformance with externally prepared test materials.3.2.12 stock standard solution, na concentrated solutioncontaining a single certified standard that is a method analyte,or a concentrated solution of a single analyte prepared in thelaboratory wi
31、th an assayed reference compound. Stock stan-dard solutions are used to prepare primary dilution standards.3.2.13 surrogate analyte, na pure analyte(s), which isextremely unlikely to be found in any sample, and which is5Available from United States Environmental ProtectionAgency (EPA),WilliamJeffers
32、on Clinton Bldg., 1200 Pennsylvania Ave., NW, Washington, DC 20460,http:/www.epa.gov.TABLE 1 Relative Retention Times for the Primary andConfirmation Columns and EDLs for the 10 CarbamatePesticidesAnalyteRetention Time (minutes)PrimaryAConfirmationBEDLCAldicarb 27.0 21.4 1.0Aldicarb sulfone 15.2 12.
33、2 2.0Aldicarb sulfoxide 15.0 17.5 2.0Baygon (Propoxur) 29.6 23.4 1.0Carbaryl 30.8 25.4 2.0Carbofuran 29.3 24.4 1.53-Hydroxycarbofuran 23.3 19.0 2.0Methiocarb 34.9 28.6 4.0Methomyl 18.4 14.8 0.50Oxamyl 17.4 14.6 2.0APrimary column250 by 4.6 mm inside diameter Altex Ultrasphere ODS, 5 m.BConfirmation
34、column250 by 4.6 mm inside diameter Supelco LC-1, 5 m.CEstimated method detection limit in micrograms per litre.D5315 04 (2017)12added to a sample aliquot in known amount(s) before extrac-tion. It is measured with the same procedures used to measureother sample components. The purpose of a surrogate
35、 analyteis to monitor the method performance with each sample.4. Summary of Test Method4.1 The water sample is filtered, and a 200 to 400-Laliquotis injected onto a reverse phase HPLC column. Separation ofthe analytes is achieved using gradient elution chromatogra-phy. After elution from the HPLC co
36、lumn, the analytes arehydrolyzed with sodium hydroxide (2.0 g/L NaOH) at 95C.The methylamine formed during hydrolysis is reacted witho-phthalaldehyde (OPA) and 2-mercaptoethanol to form ahighly fluorescent derivative that is detected by a fluorescencedetector (5).4.2 This test method is applicable t
37、o any carbamte analytethat can be hydrolyzed to a primary amine, not necessarilymethylamine.5. Significance and Use5.1 N-methylcarbamates and n-methylcarbomoyloximes areused in agriculture as insecticides and herbicides. They aresometimes found in both surface and ground waters and can betoxic to an
38、imals and plants at moderate to high concentrations.The manufacturing precursors and degradation products maybe equally as hazardous to the environment.6. Interferences6.1 Test method interferences may be caused by contami-nants in solvents, reagents, glassware, and other sample pro-cessing apparatu
39、ses that lead to discrete artifacts or elevatedbaselines in liquid chromatograms. Specific sources of con-tamination have not been identified.All reagents and apparatusmust be routinely demonstrated to be free of interferencesunder the analysis conditions by running laboratory reagentblanks in accor
40、dance with 12.2.6.1.1 Glassware must be cleaned scrupulously. Clean allglassware as soon as possible after use by rinsing thoroughlywith the last solvent used in it.6.1.2 After drying, store glassware in a clean environmentto prevent any accumulation of dust or other contaminants.Store the glassware
41、 inverted or capped with aluminum foil.6.1.3 The use of high-purity reagents and solvents helps tominimize interference problems.6.2 Interfering contamination may occur when a samplecontaining low concentrations of analytes is analyzed imme-diately after a sample containing relatively high concentra
42、tionsof analytes. A preventive technique is between-sample rinsingof the sample syringe and filter holder with two portions ofwater. Analyze one or more laboratory method blanks afteranalysis of a sample containing high concentrations of ana-lytes.6.3 Matrix interference may be caused by contaminant
43、spresent in the sample. The extent of matrix interference willvary considerably from source to source, depending upon thewater sampled. Positive analyte identifications must be con-firmed using the alternative conformational columns, or LC/MS.6.4 The quality of the reagent water used to prepare stan
44、-dards and samples must conform to Specification D1193,especially in TOC content. High reagent water TOC causes adeterioration of column selectivity, baseline stability, andanalyte sensitivity.6.5 Eliminate all sources of airborne primary amines, espe-cially ammonia, which are absorbed into the mobi
45、le phases andeffect sensitivity.7. Apparatus7.1 Sampling Equipment:7.1.1 Sample Bottle, 60-mLscrew cap glass vials6and caps7equipped with a PTFE-faced silicone septa. Prior to use, washthe vials and septa as described in 6.1.1.7.2 Filtration Apparatus:7.2.1 Macrofiltration Device, to filter derivati
46、zation solu-tions and mobile phases used in HPLC. It is recommended that47-mm, 0.45-m pore size filters be used.87.2.2 Microfiltration Device, to filter samples prior to HPLCanalysis. Use a 13-mm filter holder9and 13-mm diameter,0.2-m polyester filters.107.3 Syringes and Valves:7.3.1 Hypodermic Syri
47、nge, 10 mL, glass, with Luer-Lok11tip.7.3.2 Syringe Valve, three-way.127.3.3 Syringe Needle, 7 to 10 cm long, 17-gage, blunt tip.7.3.4 Micro Syringes, various sizes.7.4 Miscellaneous:7.4.1 Solution Storage Bottles, amber glass, 10 to 15-mLcapacity with TFE-fluorocarbon-lined screw cap.7.5 High-Perfo
48、rmance Liquid Chromatograph (HPLC):7.5.1 HPLC System,13capable of injecting 200 to 1000-Laliquots and performing ternary linear gradients at a constantflow rate. A data system is recommended for measuring peakareas. Table 2 lists the retention times observed for test methodanalytes using the columns
49、 and analytical conditions describedbelow.7.5.2 Column 1 (Primary Column), 250-mm long by4.6-mm inside diameter, stainless steel, packed with 5-m C-18material.14Mobile phase is established at 1.0 mL/min as a6Sample bottle vial, Pierce No. 13075, available from Pierce Chemical Co., 3747N. Meridian Rd., Rockford, IL61101, or equivalent, has been found suitable for use.7Sample bottle cap, Pierce No. 12722, available from Pierce Chemical Co., 3747N. Meridian Rd., Rockford, IL61101, or equivalent, has been found suitable for use.8Millipore Type HA, 0.45 m for
