1、Designation: E2866 12 (Reapproved 2016)Standard 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 Chromatogr
2、aphy/Tandem Mass Spectrometry1This 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. Asup
3、erscript epsilon () 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 Met
4、hylphosphonicAcid(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). OP
5、s are qualitativelyand 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 are
6、listed in Table 1.1.4 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 u
7、se.2. Referenced Documents2.1 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 i
8、n Testing and/or Inspection 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 Using ControlChart Techniques2.2 Othe
9、r Documents:EPA publication SW-846 Test Methods 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 tub
10、e (column)that the mobile phase passes through using the pressuregenerated by the liquid chromatography system.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
11、approved June 1, 2016. Published July 2016. Originally approvedin 2012. Last previous edition approved in 2012 as E2866 12. DOI: 10.1520/E2866-12R16.2The MDL is determined following the Code of Federal Regulations, 40 CFRPart 136,Appendix B utilizing solvent extraction of soil by PFE.Adetailed proce
12、ssdetermining 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 concentrationsassuming a 100 L injection of the lowest and highest level calibration standardswith a 40 mL final extract volume
13、 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 from the concentration of the Level 1calibration standard as shown in Table 4.4For referenced ASTM standards, visit the ASTM w
14、ebsite, 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.5Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal
15、Road, Springfield, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/testmethods/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.Copyright ASTM International, 100 Barr Harbor D
16、rive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.2 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, nA porous glass fiber material ontowhich solid particles present in the extraction fluid, whichflows through it, are largely caught and retained, thus removingthem 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 thisstandard, a separation system using liquid as the mobile phaseand a stationary phase packed into a
19、 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, nth
21、e 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 methylphosp
22、honic acid3.2.3 IMPAisopropyl methylphosphonic acid3.2.4 LCliquid chromatography3.2.5 LCS/LCSDlaboratory control spike/laboratory con-trol spike duplicate3.2.6 mMmillimolar,110-3moles/L3.2.7 MPAmethylphosphonic acid3.2.8 MRMmultiple reaction monitoring3.2.9 MSmatrix spike3.2.10 NAnot applicable3.2.1
23、1 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, sampl
24、es 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 retentiontim
25、e 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 Use5.1 T
26、his 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 modifi
27、cations 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 enzym
28、e 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 are usu
29、ally not persistent in theenvironment.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 insolvents, rea
30、gents, glassware, and other apparatus producing7Additional information about organophosphate pesticides is available on theInternet at http:/www.epa.gov (2011).8Additional information about chemical weapon agents is available on theInternet at http:/www.opcw.org (2011).TABLE 1 Method Detection Limit
31、 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 methylphosphonicacidNegative 5.7 40-2000Isopropyl methylphosphonicacidPositive 2.8
32、 40-2000Methylphosphonic acid Positive 8.7 40-2000Pinacolyl methylphosphonicacidNegative 5.3 40-2000E2866 12 (2016)2discrete artifacts or elevated baselines. All of these materialsare demonstrated to be free from interferences by analyzinglaboratory reagent blanks under the same conditions assamples
33、.6.2 All reagents and solvents shall be of pesticide residuepurity 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 variati
34、ons of the sample matrix.7. Apparatus7.1 LC/MS/MS System:7.1.1 Liquid 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 sh
35、all be used.7.1.2 Analytical Column11,10A column that achieves ad-equate 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-phase
36、HPLC column with the ability to separate polar compoundswas used to 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 Ta
37、ndem Mass Spectrometer (MS/MS) System12,10AMS/MS system capable of 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 met
38、hod withappropriately-sized extraction cells. Cells are available thatwill 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
39、extractiondevice shall be used that can meet the necessary requirementsin 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 fil
40、ter unit.7.3.1.1 A 50 mL Lock Tip Glass Syringe size is recom-mended 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
41、method.8. Reagents and Materials8.1 Purity of ReagentsHigh Performance 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 R
42、eagents of theAmerican Chemical Society.16Other reagent grades may 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 wat
43、er conforming to ASTM TypeI of Specification D1193. It must be demonstrated that thiswater does not contain contaminants at concentrations suffi-cient to interfere with the analysis.8.3 GasesNitrogen (purity 97%) and Argon (purity99.999%).8.4 Acetonitrile (CH3CN, CAS # 75-05-8).8.5 2-Propanol (C3H8O
44、, CAS # 67-63-0).8.6 Methanol (CH3OH, CAS # 67-56-1).8.7 Formic 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.
45、11 Methylphosphonic Acid (CH5O3P, MPA, CAS # 993-13-5).9AWaters Acquity UPLC H-Class System was used to develop this test methodand generate the precision and bias data presented in Section 16. The sole source ofsupply known to the committee at this time is Waters Corporation, Milford, MA01757.10If
46、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 committee,1which you may attend.11AWaters-Atlantis dC18, 150 mm 2.1 mm, 3 m particle size, was used t
47、odevelop 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 Quattro microAPI mass spectrometer was used to develop this testmethod and generate the precision
48、 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 (ASE 200) system with appropri-ately sized extraction cells was used to develop this test method and generate theprec
49、ision 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 94088.15Millex-GV Syringe Driven Filter Units PVDF 0.22 m (Catalog #SLGV033NS) were use
