1、Designation: D7968 14D7968 17Standard Test Method forDetermination of PerfluorinatedPolyfluorinated Compoundsin Soil by Liquid Chromatography Tandem MassSpectrometry (LC/MS/MS)1This standard is issued under the fixed designation D7968; the number immediately following the designation indicates the y
2、ear 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 determination of selected p
3、erfluorinatedpolyfluorinated compounds (PFCs) in a soil matrix usingsolvent extraction, filtration, followed by liquid chromatography (LC) and detection with tandem mass spectrometry (MS/MS).These analytes are qualitatively and quantitatively determined by this method.This method adheres to multiple
4、 reaction monitoring(MRM) mass spectrometry. This procedure utilizes a quick extraction and is not intended to generate an exhaustive accounting ofthe content of PFCs in difficult soil matrices. An exhaustive extraction procedure for polyfluoralkyl substances, such as publishedby Washington et al.al
5、.,2, for difficult matrices should be considered when analyzing PFCs.1.2 UnitsThe values stated in SI units are to be regarded as standard. No other units of measurement are included in thisstandard.1.3 The Method of Detection Limit3 and Reporting Range4 for the target analytes are listed in Table 1
6、.1.3.1 The reporting limit in this test method is the minimum value below which data are documented as non-detects. Analytedetections between the method detection limit and the reporting limit are estimated concentrations and are not reported followingthis test method. In most cases, the reporting l
7、imit is calculated from the concentration of the Level 1 calibration standard as shownin Table 2 for the perfluorinatedpolyfluorinated compounds after taking into account a 2 g 2-g sample weight and a final extractvolume of 10 mL, 50 % water/50 % MeOH with 0.1 % acetic acid.The final extract volume
8、is assumed to be 10 mL10 mLbecause10 mL of 50 % water/50 % MeOH with 0.1 % acetic acid was added to each soil sample and only the liquid layer after extractionis filtered, leaving the solid and any residual solvent behind. It is raised above the Level 1 calibration concentration for PFOS,PFHxA, FHEA
9、, and FOEA,FOEA; these compounds can be identified at the Level 1 concentration but the standard deviationamong replicates at this lower spike level resulted in a higher reporting limit.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is t
10、he responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.1.5 This international standard was developed in accordance with internationally recognized principles on standardizationestablishe
11、d in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:5D653 Terminology Relating to Soil, Rock, and Contained FluidsD1193 S
12、pecification for Reagent Water1 This test method is under the jurisdiction of ASTM Committee D34 on Waste Management and is the direct responsibility of Subcommittee D34.01.06 on AnalyticalMethods.Current edition approved Nov. 1, 2014May 1, 2017. Published December 2014May 2017. Originally approved
13、in 2014. Last previous edition approved in 2014 asD7968 14. DOI: 10.1520/D7968-14.10.1520/D7968-17.2 Washington, J. W., Naile, J. E., Jenkins, T. M., and Lynch, D. G., “Characterizing Fluorotelomer and Polyfluoroalkyl Substances in New and Aged Fluorotelomer-BasedPolymers for Degradation Studies wit
14、h GC/MS and LC/MS/MS,” Environmental Science and Technology, Vol.Vol 48, 2014, pp. 57625769.3 The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B utilizing solvent extraction of soil. Two gram Two-gram sample ofOttawa Sandsand was utilized. A detailed process
15、 determining the MDL is explained in the reference and is beyond the scope of this standard to be explained here.4 Reporting range concentration is calculated from Table 2 concentrations assuming a 30 L30-Linjection of the Level 1 calibration standard for the PFCs, and the highestlevel calibration s
16、tandard with a 10 mL 10-mL final extract volume of a 2 g 2-g soil sample. Volume variations will change the reporting limit and ranges.5 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume info
17、rmation, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately d
18、epict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA
19、19428-2959. United States1D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on WaterD3694 Practices for Preparation of Sample Containers and for Preservation of Organic ConstituentsD3740 Practice for Minimum Requirements for Agencies Engaged in Testin
20、g and/or Inspection of Soil and Rock as Used inEngineering Design and ConstructionD3856 Guide for Management Systems in Laboratories Engaged in Analysis of WaterD5681 Terminology for Waste and Waste ManagementD5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Wat
21、er AnalysisE2554 Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques2.2 Other Documents:6EPA SW-846 Test Methods for Evaluating Solid Waste, Physical/Chemical Methods40 CFR Part 136 Appendix B Definition and Procedure for the Determi
22、nation of the Method Detection Limit3. Terminology3.1 Definitions:3.1.1 reporting limit, RL, nthe minimum concentration below which data are documented as non-detects.3.1.2 perfluorinatedpolyfluorinated compounds, PFCs, nin this test method, eleven perfluoroalkyl carboxylic acids, threeperfluoroalky
23、lsulfonates, Decafluoro-4-(pentafluoroethyl)cyclohexanesulfonate, and six fluorotelomer acids listed in Table 1collectively (not including mass labeled surrogates).3.2 Abbreviations:3.2.1 CCCContinuing Calibration Check3.2.2 ICInitial Calibration3.2.3 pptparts per trillion, ng/kg or ng/L3.2.4 LCLiqu
24、id Chromatography3.2.5 LCS/LCSDLaboratory Control Sample/Laboratory Control Sample Duplicate3.2.6 MDLMethod Detection Limit3.2.7 MeOHMethanol3.2.8 mMmillimolar, 1 10-3 moles/L3.2.9 MRMMultiple Reaction Monitoring3.2.10 MS/MSDMatrix Spike/Matrix Spike Duplicate3.2.11 NANot available6 Available from N
25、ational Technical Information Service (NTIS), U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161, http:/www.epa.gov/epawaste/hazard/testmethods/index.htmTABLE 1 Method Detection Limit and Reporting RangeAAnalyte MDL(ng/kg) Reporting Limit(ng/kg)PFTreA 6.76 251000PFTriA 5.26 25
26、1000PFDoA 3.56 251000PFUnA 2.45 251000PFDA 5.54 251000PFOS 18.83 501000PFNA 2.82 251000PFecHS 2.41 251000PFOA 6.24 251000PFHxS 7.75 251000PFHpA 5.80 251000PFHxA 15.44 501000PFBS 6.49 251000PFPeA 20.93 1255000PFBA 22.01 1255000FHEA 199.04 60020 000FOEA 258.37 75020 000FDEA 137.46 50020 000FOUEA 4.85
27、251000FhpPa 5.09 251000FHUEA 3.50 251000AAbbreviations are defined in 3.2.D7968 1723.2.12 NDnon-detect3.2.13 P however, this test method is intended to be performance based and alternative operatingconditions can be used to perform this method provided data quality objectives are attained.4.2 For PF
28、C analysis, samples are shipped to the lab on ice and analyzed within 28 daysd of collection. A sample (2 g) istransferred to a polypropylene tube, spiked with surrogates (all samples) and target PFC compounds (laboratory control and matrixspike samples). The analytes are tumbled for an hour with 10
29、 mL of methanol:water (50:50) under basic condition (pH 9-10adjusted with 20 L ammonium hydroxide). The samples are centrifuged and the extract, leaving the solid behind, is filteredthrough a polypropylene filter unit.Acetic acid (50 L) is added to all the filtered samples to adjust the pH 3-4 and t
30、hen analyzedby LC/MS/MS.4.3 Most of the PFC target compounds are identified by comparing the single reaction monitoring (SRM) transition and itsconfirmatory SRM transition if correlated to the known standard SRM (Table 3) and quantitated utilizing an external calibration.The surrogates and some PFC
31、target analytes (PFPeA, PFBA, FOUEA, and FHUEA) only utilize one SRM transition due to a lesssensitive or non-existent secondary SRM transition. As an additional quality control measure, isotopically labeled PFC surrogates(listed in 12.4) recoveries are monitored. There is no correction to the data
32、based upon surrogate recoveries. The final report issuedfor each sample lists the concentration of PFCs, if detected, or RL, if not detected, in ng/kg (Dry Weight Basis)(dry weight basis)and the surrogate recoveries.5. Significance and Use5.1 This test method has been developed by the USU.S. EPA Reg
33、ion 5 Chicago Regional Laboratory (CRL).5.2 PFCs are widely used in various industrial and commercial products; they are persistent, bio-accumulative, and ubiquitousin the environment. PFCs have been reported to exhibit developmental toxicity, hepatotoxicity, immunotoxicity, and hormonedisturbance.
34、A draft Toxicological Profile for Perfluoroalkyls from the U.S. Department of Health and Human Services isavailable.7 PFCs have been detected in soils, sludges, and surface and drinking waters. Hence, there is a need for a quick, easy,and robust method to determine these compounds at trace levels in
35、 various soil matrices for understanding of the sources andpathways of exposure.5.3 This method has been used to determine selected perfluorinatedpolyfluorinated compounds in sand (Table 4) and fourASTMreference soils (Table 5).6. Interferences6.1 All glassware is washed in hot water with detergent
36、and rinsed in hot water followed by distilled water. The glassware isthen dried and heated in an oven at 250C250 C for 15 to 30 minutes. 30 min.All glassware is subsequently rinsed with methanolor acetonitrile.6.2 All reagents and solvents should be pesticide residue purity or higher to minimize int
37、erference problems. The use of PFCcontaining PFC-containing caps should be avoided.6.3 Matrix interferences may be caused by contaminants in the sample. The extent of matrix interferences can vary considerablydepending on variations in the sample matrices.6.4 Contaminants have been found in reagents
38、, glassware, tubing, glass disposable pipettes, filters, degassers, and otherapparatus that release perfluorinatedpolyfluorinated compounds. All of these materials and supplies are routinely demonstrated tobe free from interferences by analyzing laboratory reagent blanks under the same conditions as
39、 the samples. If found, measuresshould be taken to remove the contamination or data should be qualified; background subtraction of blank contamination is notallowed.6.5 The Liquid Chromatographyliquid chromatography system used should consist, as much as practical, of sample solution oreluent contac
40、ting components free of PFC target analytes of interest.6.6 Polyethylene LC vial caps or any other target analyte free analyte-free vial caps should be used.7 A draft Toxicological Profile for Perfluroalkyls can be found at http:/www.atsdr.cdc.gov/toxprofiles/tp.asp?id=1117 this should include asamp
41、le injection system, a solvent pumping system capable of mixing solvents, a sample compartment capable of maintainingrequired temperature, and a temperature controlled temperature-controlled column compartment. AAn LC system that is capableof performing at the flows, pressures, controlled temperatur
42、es, sample volumes, and requirements of the standard shall be used.7.1.2 Analytical Column9Areverse phase Charged Surface Hybrid Phenyl-Hexyl particle column was used to develop this testmethod. Any column that achieves adequate resolution may be used. The retention times and order of elution may ch
43、angedepending on the column used and need to be monitored.8 A Waters Acquity UPLC H-Class System, or equivalent, has been found suitable for use.9 AWatersAcquity UPLC CSH Phenyl-Hexyl, 2.1 100 mm and 1.7 m 1.7-m particle size column, or equivalent, has been found suitable for use. It was used to dev
44、elopthis test method and generate the precision and bias data presented in Section 16.TABLE 3 Retention Times, SRM Ions, and Analyte-Specific Mass Spectrometer ParametersChemical Primary/Confirmatory Retention Times(min) Cone (V) Collision (eV) MRM TransitionPrimary/Confirmatory SRMArea RatioPFTreA
45、Primary 10.63 20 13 712.9668.9 7.4Confirmatory 20 30 712.9169PFTriA Primary 10.17 25 12 662.9618.9 7.4Confirmatory 25 28 662.9169PFDoA Primary 9.61 10 12 612.9568.9 8.2Confirmatory 10 25 612.9169PFUnA Primary 9.05 15 10 562.9519 7.2Confirmatory 15 18 562.9269PFDA Primary 8.45 20 10 512.9468.9 6.5Con
46、firmatory 20 16 512.9219PFOS Primary 8.78 10 42 498.980.1 1.3Confirmatory 10 40 498.999.1PFNA Primary 7.78 20 10 462.9418.9 4.9Confirmatory 20 16 462.9219PFecHS Primary 8.1 10 25 460.9381 2.2Confirmatory 10 25 460.999.1PFOA Primary 7.11 20 10 412.9369 3.6Confirmatory 20 16 412.9169PFHxS Primary 7.39
47、 15 32 398.980.1 1Confirmatory 15 32 398.999.1PFHpA Primary 6.35 15 10 362.9319 4.1Confirmatory 15 15 362.9169PFHxA Primary 5.54 15 8 312.9269 24.1Confirmatory 15 18 312.9119.1PFBS Primary 5.66 10 30 298.980.1 1.6Confirmatory 10 25 298.999.1PFPeA Primary 4.68 10 8 263219 NAPFBA Primary 3.67 10 8 212
48、.9169 NAFHEA Primary 6.14 15 20 376.9293 3.6Confirmatory 15 6 376.9313FOEA Primary 7.54 15 18 476.9393 4.3Confirmatory 15 12 476.9413FDEA Primary 8.83 15 8 576.8493 3.2Confirmatory 15 15 576.8513FOUEA Primary 7.54 20 12 456.9392.9 NAFHpPA Primary 7.54 15 12 440.9337 1.1Confirmatory 15 20 440.9317FHU
49、EA Primary 6.08 10 12 357293 NAMPFBA Primary 3.67 10 7 217172.1 NAMPFHxA Primary 5.54 15 8 315270 NAMPFHxS Primary 7.39 15 34 402.984.1 NAMPFOA Primary 7.11 15 10 417372 NAMPFNA Primary 7.81 15 9 467.9423 NAMPFOS Primary 8.78 15 40 502.980.1 NAMPFDA Primary 8.45 15 10 514.9470 NAMPFUnA Primary 9.05 15 10 564.9519.9 NAMPFDoA Primary 9.61 15 12 614.9569.9 NAD7968 1757.1.3 Isolator Column10A reverse phase C18 column was used in this test method to separate the target analytes in
