1、Designation: E2866 12Standard Test Method forDetermination of Diisopropyl Methylphosphonate, EthylMethylphosphonic Acid, Isopropyl Methylphosphonic Acid,Methylphosphonic Acid and Pinacolyl MethylphosphonicAcid in Soil by Pressurized Fluid Extraction and Analyzedby Liquid Chromatography/Tandem Mass S
2、pectrometry1This standard is issued under the fixed designation E2866; the number immediately following the designation 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 (
3、) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This procedure covers the determination of DiisopropylMethylphosphonate (DIMP), Ethyl Methylphosphonic Acid(EMPA), Isopropyl Methylphosphonic Acid (IMPA), Methyl-phosphonicAcid (MPA) and Pinacolyl MethylphosphonicAcid(
4、PMPA), referred to collectively as organophosphonates (OPs)in this test method, in soil. This method is based upon solventextraction of a soil by pressurized fluid extraction (PFE). Theextract is filtered and analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). OPs are qualitativel
5、yand quantitatively determined by this method.1.2 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.3 The Method Detection Limit2(MDL), electrosprayionization (ESI) mode and Reporting Range3for the OPs arelisted in Table 1.
6、1.4 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 practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced D
7、ocuments2.1 ASTM Standards:4D653 Terminology Relating to Soil, Rock, and ContainedFluidsD1193 Specification for Reagent WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD3740 Practice for Minimum Requirements for AgenciesEngaged in Testing and/or I
8、nspection of Soil and Rock asUsed in Engineering Design and ConstructionD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method in a SingleLaboratory Using a Control Sample Program2.2
9、 Other Documents:1This test method is under the jurisdiction of ASTM Committee E54 onHomeland Security Applications and is the direct responsibility of SubcommitteeE54.03 on Decontamination.Current edition approved Feb. 1, 2012. Published March 2012. DOI: 10.1520/E2866-12.2The MDL is determined foll
10、owing the Code of Federal Regulations, 40 CFRPart 136, Appendix B utilizing solvent extraction of soil by PFE. A detailed processdetermining the MDL is explained in the reference and is beyond the scope of thisStandard to be explained here.3Reporting range concentrations are calculated from Table 4
11、concentrationsassuming a 100 L injection of the lowest and highest level calibration standardswith a 40 mL final extract volume of a 10 gram soil sample. Volume variations willchange the reporting limit and ranges. The reporting limit (RL), lowest concentra-tion of the reporting range, is calculated
12、 from the concentration of the Level 1calibration standard as shown in Table 4.4For 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 o
13、nthe ASTM website.TABLE 1 Method Detection Limit and Reporting RangeAnalyteESIModeMDL(PPB)Reporting Range(PPB)Diisopropyl methylphosphonate Positive 2.7 40-2000Ethyl methylphosphonic acid Negative 2.3 40-2000Ethyl methylphosphonic acid Positive 1.3 40-2000Isopropyl methylphosphonic acid Negative 5.7
14、 40-2000Isopropyl methylphosphonic acid Positive 2.8 40-2000Methylphosphonic acid Positive 8.7 40-2000Pinacolyl methylphosphonic acid Negative 5.3 40-20001Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.EPApublication SW-846 Test Meth
15、ods for Evaluating SolidWaste, Physical/Chemical Methods540 CFR Part 136 The Code of Federal Regulations, Appen-dix B63. Terminology3.1 Definitions:3.1.1 analytical column, nthe particles of the solid sta-tionary phase fill the whole inside volume of a tube (column)that the mobile phase passes throu
16、gh using the pressuregenerated by the liquid chromatography system.3.1.2 filter unit, nin this standard, a filter that is supportedwith an inert housing to the solvents as described in Section 7of this standard.3.1.3 filtration device, na device used to remove particlesfrom the extract that may clog
17、 the liquid chromatographysystem. Described in section 7.3 of this standard.3.1.4 glass fiber filter, nAporous glass fiber material ontowhich solid particles present in the extraction fluid, whichflows through it, are largely caught and retained , thusremoving them from the extract.3.1.5 hypodermic
18、syringe, nin this standard, a luer-lock-tipped glass syringe capable of holding a syringe-driven filterunit as described in section 7.3 of this standard.3.1.6 liquid chromatography (LC) system, nin this stan-dard, a separation system using liquid as the mobile phase anda stationary phase packed into
19、 a column. The use of smallparticles packed inside a column and a high inlet pressureenables the separation of components in a mixture.3.1.7 organophosphonates (OPs), nin this test method,Diisopropyl Methylphosphonate (DIMP), Ethyl Methylphos-phonic Acid (EMPA), Isopropyl Methylphosphonic Acid(IMPA)
20、, Methylphosphonic Acid (MPA) and Pinacolyl Meth-ylphosphonic Acid (PMPA) collectively.3.1.8 pressurized fluid extraction, nthe process of trans-ferring the analytes of interest from the solid matrix, a soil, intothe extraction solvent using pressure and elevated temperature.3.1.9 reporting range, n
21、the quantitative concentrationrange for an analyte in this standard.3.1.10 tandem mass spectrometer, nan arrangement inwhich ions are subjected to two sequential stages of analysisaccording to the quotient mass/charge.3.2 Abbreviations:3.2.1 DIMPdiisopropyl methylphosphonate3.2.2 EMPAethyl methylpho
22、sphonic acid3.2.3 IMPAisopropyl methylphosphonic acid3.2.4 LCliquid chromatography3.2.5 LCS/LCSDlaboratory control spike/laboratory con-trol spike duplicate3.2.6 mMmillimolar, 1 3 10-3moles/L3.2.7 MPAmethylphosphonic acid3.2.8 MRMmultiple reaction monitoring3.2.9 MSmatrix spike3.2.10 NAnot applicabl
23、e3.2.11 NDnon-detect3.2.12 PFEpressurized fluid extraction3.2.13 PMPApinacolyl methylphosphonic acid3.2.14 PPBparts per billion3.2.15 QCquality control3.2.16 SDstandard deviation3.2.17 SRMsingle reaction monitoring3.2.18 VOAvolatile organic analysis4. Summary of Test Method4.1 For OPs soil analysis,
24、 samples are shipped to the labbetween 0C and 6C. The samples are to be extracted, filteredand analyzed by LC/MS/MS within 7 days of collection.4.2 The OPs and the surrogates (diisopropylmethylphosphonate-D14, pinacolyl methylphosphonic acid-13C6and methylphosphonic acid-D3) are identified by retent
25、iontime and one SRM transition. The target analytes and surro-gates are quantitated using the SRM transitions utilizing anexternal calibration. The final report issued for each samplelists the concentration of each organophosphonate target com-pound and each surrogate recovery.5. Significance and Us
26、e5.1 This is a performance based method, and modificationsare allowed to improve performance.5.1.1 Due to the rapid development of newer instrumenta-tion and column chemistries, changes to the analysis describedin this standard are allowed as long as better or equivalentperformance data result. Any
27、modifications shall be docu-mented and performance data generated. The user of the datagenerated by this Standard shall be made aware of thesechanges and given the performance data demonstrating betteror equivalent performance.5.2 Organophosphate pesticides affect the nervous systemby disrupting the
28、 enzyme that regulates acetylcholine, a neu-rotransmitter. They were developed during the early 19thcentury, but their effects on insects, which were similar to theireffects on humans, were discovered in 1932. Some are poison-ous and were used as chemical weapon agents. Organophos-phate pesticides a
29、re usually not persistent in the environ-ment.7,85.3 This test method is for the analysis of selected organo-phosphorous based pesticide degradation products.5.4 This method has been investigated for use with varioussoils.6. Interferences6.1 Method interferences may be caused by contaminants insolve
30、nts, reagents, glassware, and other apparatus producingdiscrete artifacts or elevated baselines. All of these materials5Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/tes
31、tmethods/index.htm6Available from U.S. Government Printing Office Superintendent of Documents,732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:/www.access.gpo.gov.7Additional information about organophosphate pesticides is available on theInternet at http:/www.epa.gov (2011).8Addit
32、ional information about chemical weapon agents is available on theInternet at http:/www.opcw.org (2011).E2866 122are demonstrated to be free from interferences by analyzinglaboratory reagent blanks under the same conditions assamples.6.2 All reagents and solvents shall be of pesticide residuepurity
33、or higher to minimize interference problems.6.3 Matrix interferences may be caused by contaminantsthat are co-extracted from the sample. The extent of matrixinterferences can vary considerably from sample source de-pending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System:7.1.1 Liqu
34、id Chromatography (LC) System9,10AcompleteLC system is required in order to analyze samples. A LCsystem that is capable of performing at the flows, pressures,controlled temperatures, sample volumes, and requirements ofthe standard shall be used.7.1.2 Analytical Column11,10A column that achieves ad-e
35、quate resolution shall be used. The retention times and orderof elution may change depending on the column used and needto be monitored. A reverse-phase analytical column thatcombines the desirable characteristics of a reversed-phaseHPLC column with the ability to separate polar compoundswas used to
36、 develop this test method. MPA elutes early in thechromatograph, at approximately 2 minutes, which is justbeyond the instrument void volume of 1.5 minutes. A columnis required that elutes MPA after the instrument void volume.7.1.3 Tandem Mass Spectrometer (MS/MS) System12,10AMS/MS system capable of
37、multiple reaction monitoring(MRM) analysis or any system that is capable of performing atthe requirements in this standard shall be used.7.2 Pressurized Fluid Extraction Device (PFE)13,10:7.2.1 A PFE system was used for this test method withappropriately-sized extraction cells. Cells are available t
38、hatwill accommodate the 10 g sample sizes used in this testmethod. Cells shall be made of stainless steel or other materialcapable of withstanding the pressure requirements ($2000 psi)necessary for this procedure. A pressurized fluid extractiondevice shall be used that can meet the necessary require
39、mentsin this test method.7.2.2 Glass Fiber Filters.14,107.2.3 Amber VOA Vials40 mL for sample extracts and 60mL for PFE.7.3 Filtration Device:7.3.1 Hypodermic SyringeA luer-lock tip glass syringecapable of holding a syringe driven filter unit.7.3.1.1 A 50 mL Lock Tip Glass Syringe size is recom-mend
40、ed since a 40 mL sample extract may result.7.3.2 Filter Unit15,10Filter units of polyvinylidene fluo-ride (PVDF) were used to filter the PFE extracts.7.3.2.1 DiscussionAfilter unit shall be used that meets therequirements of the test method.8. Reagents and Materials8.1 Purity of ReagentsHigh Perform
41、ance Liquid Chroma-tography (HPLC) pesticide residue analysis and spectropho-tometry grade chemicals shall be used in all tests. Unlessindicated otherwise, it is intended that all reagents shallconform to the Committee on Analytical Reagents of theAmerican Chemical Society.16Other reagent grades may
42、 beused provided they are first determined to be of sufficientlyhigh purity to permit their use without affecting the accuracy ofthe measurements.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall mean reagent water conforming to ASTM TypeI of Specification D1193. It must be dem
43、onstrated that thiswater does not contain contaminants at concentrations suffi-cient to interfere with the analysis.8.3 GasesNitrogen (purity $97%) and Argon (purity$99.999%).8.4 Acetonitrile (CH3CN, CAS # 75-05-8).8.5 2-Propanol (C3H8O, CAS # 67-63-0).8.6 Methanol (CH3OH, CAS # 67-56-1).8.7 Formic
44、Acid (HCO2H, $95%, CAS # 64-18-6).8.8 Diisopropyl Methylphosphonate (C7H17O3P, DIMP,CAS # 1445-75-6).8.9 Ethyl Methylphosphonic Acid (C3H9O3P, EMPA, CAS# 1832-53-7).8.10 Isopropyl Methylphosphonic Acid (C4H11O3P, IMPA,CAS # 1832-54-8).8.11 Methylphosphonic Acid (CH5O3P, MPA, CAS # 993-13-5).8.12 Pin
45、acolyl Methylphosphonic Acid (C7H17O3P, PMPA,CAS # 616-52-4).8.13 Diisopropyl Methylphosphonate-D14(C7H3D14O3P,DIMP-D14, Unlabeled CAS # 1445-75-6).9A Waters Acquity UPLC H-Class System was used to develop this test methodand generate the precision and bias data presented in Section 16. The sole sou
46、rce ofsupply known to the committee at this time is Waters Corporation, Milford, MA01757.10If you are aware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committ
47、ee,1which you may attend.11A Waters-Atlantist dC18, 150 mm 3 2.1 mm, 3 m particle size, was used todevelop this test method and generate the precision and bias data presented inSection 16. The sole source of supply known to the committee at this time is WatersCorporation, Milford, MA 01757.12AWaters
48、 Quattro microy API mass spectrometer was used to develop this testmethod and generate the precision and bias data presented in Section 16. The solesource of supply known to the committee at this time is Waters Corporation,Milford, MA 01757.13A Dionex Accelerated Solvent Extraction (ASEt 200) system
49、 with appropri-ately sized extraction cells was used to develop this test method and generate theprecision and bias data presented in Section 16. The sole source of supply known tothe committee at this time is Dionex Corporation, Sunnyvale, CA 94088.14Whatman Glass Fiber Filters 19.8 mm, Part # 047017, specially designed forthe PFE system,13were used to develop this test method and generate the precisionand bias data presented in Section 16. The sole source of supply known to thecommittee at this time is Dionex Corporation, Sunnyvale, CA
