1、Designation: D7858 13Standard Test Method forDetermination of Bisphenol A in Soil, Sludge and Biosolidsby Pressurized Fluid Extraction and Analyzed by LiquidChromatography/Tandem Mass Spectrometry1This standard is issued under the fixed designation D7858; the number immediately following the designa
2、tion 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.1. Scope1.1 This procedure covers the determi
3、nation of BisphenolA(BPA) in soil, sludge, and biosolids. This test method is basedupon solvent extraction of a soil matrix by pressurized fluidextraction (PFE). The extract is filtered and analyzed by liquidchromatography/tandem mass spectrometry (LC/MS/MS).BPA is qualitatively and quantitatively d
4、etermined by this testmethod.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 BPA arelisted in Table 1.1.4 This standard do
5、es 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 Documents2.1 ASTM Sta
6、ndards: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 Inspection of Soil an
7、d Rock asUsed in Engineering Design and ConstructionD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD5681 Terminology for Waste and Waste ManagementE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniqu
8、es2.2 Other Documents:EPA Publication SW-846 Test Methods for Evaluating SolidWaste, Physical/Chemical Methods5The Code of Federal Regulations 40 CFR Part 136, Appen-dix B63. Terminology3.1 Definitions:3.1.1 Bisphenol A (BPA), n2,2-bis(4-hydroxyphenyl) pro-pane.3.1.2 Bisphenol A (propane-D6) (BPA-D6
9、), ndeuteriumlabeled BisphenolAwhere the two methyl moieties contain all2H and is used as a surrogate in this method.3.1.3 filter unit, nin this test method, a filter that issupported with a housing that is inert to the solvents used asdescribed in 7.4 of this test method.3.1.4 filtration device, na
10、 device used to remove particlesfrom the extract that may clog the liquid chromatographysystem as described in 7.4 of this test method.3.1.5 glass fiber filter, na porous glass fiber material ontowhich solid particles present in the extraction fluid, whichflows through it, are largely caught and ret
11、ained, thus removingthem from the extract.1This test method is under the jurisdiction of ASTM Committee D34 on WasteManagement and is the direct responsibility of Subcommittee D34.01.06 onAnalytical Methods.Current edition approved April 1, 2013. Published May 2013. DOI: 10.1520/D7858-13.2The MDL is
12、 determined following the Code of Federal Regulations, 40 CFRPart 136, Appendix B utilizing solvent extraction of soil by PFE. 10 gram sampleof Ottawa Sand was utilized. A detailed process determining the MDL is explainedin the reference and is beyond the scope of this test method to be explained he
13、re.3Reporting range concentration is calculated from Table 4 concentrationsassuming a 25 L injection of the Level 1 calibration standard for BPA, and thehighest level calibration standard witha5mLfinal extract volume of a 10 gram soilsample. Volume variations will change the reporting limit and rang
14、es.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 onthe ASTM website.5Available from National Technical Information Service (NT
15、IS), U.S. Depart-ment of Commerce, 5285 Port Royal 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.
16、gov.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.6 hypodermic syringe, nin this test method, a luer-lock-tipped glass syringe capable of holding a syringe-drivenfilter unit as described in 7.4 of this test method.3.1.7 pressuri
17、zed 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.3.1.8 reporting range, nthe quantitative concentrationrange for an analyte in this test method.3.2 Abbreviations:3.2.1 BPABis
18、phenol A3.2.2 LCLiquid Chromatography3.2.3 LCS/LCSDLaboratory Control Spike/LaboratoryControl Spike Duplicate3.2.4 mMmillimolar,110-3moles/L3.2.5 MRMMultiple Reaction Monitoring3.2.6 MSMatrix Spike3.2.7 NAnot available3.2.8 NDnon-detect3.2.9 PFEPressurized Fluid Extraction3.2.10 PPBParts Per Billion
19、3.2.11 QCQuality Control3.2.12 RLReporting Limit3.2.13 SDStandard Deviation3.2.14 SRMSingle Reaction Monitoring3.2.15 VOAVolatile Organic Analysis4. Summary of Test Method4.1 For BPA analysis in soil, sludge and biosolid, samplesare shipped to the lab between 0C and 6C. The samples areto be extracte
20、d and filtered within 14 days of collection, andanalyzed by LC/MS/MS within 14 days of extraction.4.2 BPA and the surrogate (BPA-D6) are identified byretention time and one SRM transition. The target analytes andsurrogates are quantitated using the SRM transitions utilizingan external calibration. T
21、he final report issued for each samplelists the concentration of BPA and surrogate recovery.5. Significance and Use5.1 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
22、to the analysis describedin this test method are allowed as long as better or equivalentperformance data result. Any modifications shall be docu-mented and performance data generated. The user of the datagenerated by this test method shall be made aware of thesechanges and given the performance data
23、 demonstrating betteror equivalent performance.5.2 The first reported synthesis of BPA was by the reactionof phenol with acetone by Zincke.7BPA has become animportant high volume industrial chemical used in the manu-facture of polycarbonate plastic and epoxy resins. Polycarbon-ate plastic and resins
24、 are used in numerous products includingelectrical and electronic equipment, automobiles, sports andsafety equipment, reusable food and drink containers, electricallaminates for printed circuit boards, composites, paints,adhesives, dental sealants, protective coatings and many otherproducts.85.3 The
25、 environmental source of BPA is predominantlyfrom the decomposition of polycarbonate plastics and resins.BPAis not classified as bio-accumulative by the U.S. Environ-mental Protection Agency and will biodegrade. BPA has beenreported to have adverse effects in aquatic organisms and maybe released int
26、o environmental waters directly at trace levelsthrough landfill leachate and sewage treatment plant effluents.This method has been investigated for use with soil, sludge,and biosolids.5.4 The land application of biosolids has raised concernsover the fate of BPAin the environment and a standard metho
27、dis needed to monitor concentrations. This method has beeninvestigated for use with various soils.6. Interferences6.1 Method interferences may be caused by contaminants insolvents, reagents, glassware, and other apparatus producingdiscrete artifacts or elevated baselines. All of these materialsare d
28、emonstrated 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 or higher to minimize interference problems.6.3 Matrix interferences may be caused by contaminantsthat are co-extracte
29、d 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 Liquid Chromatography (LC) System9A completeLC system is required in order to analyze samples. A LCsystem that is capable
30、of performing at the flows, pressures,controlled temperatures, sample volumes, and requirements ofthe standard shall be used.7Zincke, T., 1905, “Mittheilungen aus dem chemischen Laboratorium derUniversitat Marburg,” Justus Leibigs Annals Chemie, Vol 343, pp. 7579.8Additional information about BPA is
31、 available on the Internet at http:/www.bisphenol-a.org (2008).9A Waters Acquity UPLC H-Class System was used to develop this testmethod and generate the precision and bias data presented in Section 16. WatersCorporation, Milford, MA 01757. Instrumentation from other vendors may also beable to gener
32、ate similar method performance.TABLE 1 Method Detection Limit and Reporting RangeAnalyte ESI Mode MDL (PPB)Reporting Range(PPB)Bisphenol A Negative 2.8 10-250D7858 1327.1.2 Analytical Column10A column that achieves ad-equate resolution shall be used. The retention times and orderof elution may chang
33、e 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 develop this test method.7.1.3 Tandem Mass Spectrometer (MS/MS) System11AMS/MS s
34、ystem capable of multiple reaction monitoring(MRM) analysis or any system that is capable of performing atthe requirements in this test method shall be used.7.2 Pressurized Fluid Extraction Device (PFE):127.2.1 A PFE system was used for this test method withappropriately-sized extraction cells. Cell
35、s 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 extractiondevice shall be used that can meet the n
36、ecessary requirementsin this test method.7.2.2 Glass Fiber Filters.137.2.3 Amber VOAvials-60 mL for sample extracts for PFE.7.3 Organic Solvent Evaporation Device.147.4 Filtration Device:7.4.1 Hypodermic SyringeA luer-lock tip glass syringecapable of holding a syringe driven filter unit.7.4.1.1 A 10
37、 mL Lock Tip Glass Syringe size is recom-mended sincea3mLsample extract results after blow-down.7.4.2 Filter Unit15Filter units of polyvinylidene fluoride(PVDF) with a glass fiber prefilter were used to filter the PFEextracts.7.4.3 DiscussionA filter unit shall be used that meets therequirements of
38、the test 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 Ana
39、lytical Reagents 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 re
40、agent water 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 Ethyl
41、Acetate (CH3COOC2H5, CAS # 141-78-6).8.6 2-Propanol (C3H8O, CAS # 67-63-0).8.7 Methanol (CH3OH, CAS # 67-56-1).8.8 Ammonium Acetate (CH3CO2NH4, CAS # 631-61-8).8.9 Bisphenol A (C15H16O2, 2,2-Bis(4-hydroxyphenyl)propane, CAS # 80-05-7).8.10 Bisphenol A (Propane-D6) represents deuterium la-beled Bisph
42、enol A where the two methyl moieties contain all2H.8.10.1 DiscussionBPA-D6is used as a surrogate in thistest method.8.11 Ottawa Sand (CAS # 14808-60-7) or equivalent.8.12 Drying Agent.178.13 Sodium sulfate (Na2SO4, CAS # 7757-82-6).8.14 Sodium Chloride (NaCl, CAS # 7647-14-5).9. Hazards9.1 Normal la
43、boratory safety applies to this method. Ana-lysts shall wear safety glasses, gloves, and lab coats whenworking in the lab. Analysts shall review the Material SafetyData Sheets (MSDS) for all reagents used in this test methodand shall be fully trained to perform this test method.10. Glassware Washing
44、, Sampling, and Preservation10.1 Glassware WashingAll glassware is washed in hottap water with a detergent and rinsed in hot water, then ASTM10A Waters-UPLC T3, 100 mm x 2.1 mm, 1.8 m particle size, was used todevelop this test method and generate the precision and bias data presented inSection 16.
45、Waters Corporation, Milford, MA 01757. Columns from other vendorsthat are able to generate similar method performance and that achieve adequateresolution may be used. A guard column was also used, VanGuard Pre-Column,2.1 5 mm, 1.8 m particle size.11AWaters Quattro microAPI mass spectrometer was used
46、 to develop this testmethod and generate the precision and bias data presented in Section 16. WatersCorporation, Milford, MA 01757. Instrumentation from other vendors may also beable to generate similar method performance.12A Dionex Accelerated Solvent Extraction (ASE 200) system withappropriately-s
47、ized extraction cells was used to develop this test method andgenerate the precision and bias data presented in Section 16. Dionex Corporation,Sunnyvale, CA 94088. Instrumentation from other vendors may also be able togenerate similar method performance.13Whatman Glass Fiber Filters 19.8 mm, Dionex
48、Corporation, Part # 047017specially designed for the PFE system11were used to develop this test method andgenerate the precision and bias data presented in Section 16. Filters from othervendors may also be able to generate similar method performance.14A TurboVap LV was used in this test method from
49、Caliper Life Sciences,Hopkinton, MA01748 and an N-Evap 24-port nitrogen evaporation device was usedin this test method from Organomation Associates Inc., West Berlin, MA 01503.In-house built or devices from other vendors may also be able to generate similarmethod performance.15Pall-Acrodisc Premium 25 mm Syringe Filter with GxF/0.2 m PVDFMembrane(Pall Corporation, Catalog # AP-4793, were used to develop this testmethod and generate the precision and bias data presented in Section 16. Filtersfrom other vendors may also be able
