1、Designation: D7968 14Standard Test Method forDetermination of Perfluorinated Compounds in Soil byLiquid Chromatography Tandem Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed designation D7968; the number immediately following the designation indicates the year oforiginal adoptio
2、n 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 selectedperfluorinated compounds
3、 (PFCs) in a soil matrix using solventextraction, filtration, followed by liquid chromatography (LC)and detection with tandem mass spectrometry (MS/MS). Theseanalytes are qualitatively and quantitatively determined by thismethod. This method adheres to multiple reaction monitoring(MRM) mass spectrom
4、etry. This procedure utilizes a quickextraction and is not intended to generate an exhaustiveaccounting of the content of PFCs in difficult soil matrices. Anexhaustive extraction procedure for polyfluoralkyl substances,such as published by Washington et al.2, for difficult matricesshould be consider
5、ed when analyzing PFCs.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 of Detection Limit3and Reporting Range4for the target analytes are listed in Table 1.1.3.1 The reporting limit in this test method is
6、 the minimumvalue below which data are documented as non-detects. Ana-lyte detections between the method detection limit and thereporting limit are estimated concentrations and are not re-ported following this test method. In most cases, the reportinglimit is calculated from the concentration of the
7、 Level 1calibration standard as shown in Table 2 for the perfluorinatedcompounds after taking into account a 2 g sample weight anda final extract volume of 10 mL, 50 % water/50 % MeOH with0.1 % acetic acid. The final extract volume is assumed to be 10mL because 10 mL of 50 % water/50 % MeOH with 0.1
8、 %acetic acid was added to each soil sample and only the liquidlayer after extraction is filtered leaving the solid and anyresidual solvent behind. It is raised above the Level 1 calibra-tion concentration for PFOS, PFHxA, FHEA, and FOEA, thesecompounds can be identified at the Level 1 concentration
9、 butthe standard deviation among replicates at this lower spikelevel resulted in a higher reporting limit.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 an
10、d health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:5D653 Terminology Relating to Soil, Rock, and ContainedFluidsD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable T
11、est Methods of Committee D19 on 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 and Rock asUsed in Engineering Design and ConstructionD3856 Guide for
12、Management Systems in LaboratoriesEngaged in Analysis of WaterD5681 Terminology for Waste and Waste ManagementD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test M
13、ethod Using ControlChart Techniques1This 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 Nov. 1, 2014. Published December 2014. DOI:10.1520/D7968-14.2Washington, J.
14、 W., Naile, J. E., Jenkins, T. M., and Lynch, D. G., “Character-izing Fluorotelomer and Polyfluoroalkyl Substances in New and AgedFluorotelomer-Based Polymers for Degradation Studies with GC/MS and LC/MS/MS,” Environmental Science and Technology, Vol. 48, 2014, pp. 57625769.3The MDL is determined fo
15、llowing the Code of Federal Regulations, 40 CFRPart 136, Appendix B utilizing solvent extraction of soil. Two gram sample ofOttawa Sand was utilized. A detailed process determining the MDL is explained inthe reference and is beyond the scope of this standard to be explained here.4Reporting range con
16、centration is calculated from Table 2 concentrationsassuming a 30 L injection of the Level 1 calibration standard for the PFCs, and thehighest level calibration standard with a 10 mL final extract volume ofa2gsoilsample. Volume variations will change the reporting limit and ranges.5For referenced AS
17、TM 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.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshoho
18、cken, PA 19428-2959. United States12.2 Other Documents:6EPA SW-846 Test Methods for Evaluating Solid Waste,Physical/Chemical Methods40 CFR Part 136 Appendix B Definition and Procedure forthe Determination of the Method Detection Limit3. Terminology3.1 Definitions:3.1.1 reporting limit, RL, nthe mini
19、mum concentrationbelow which data are documented as non-detects.3.1.2 perfluorinated compounds, PFCs, nin this testmethod, eleven perfluoroalkyl carboxylic acids, threeperfluoroalkylsulfonates, Decafluoro-4-(pentafluoroethyl)cyclohexanesulfonate, and six fluorotelomeracids listed in Table 1 collecti
20、vely (not including mass labeledsurrogates).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 LCLiquid Chromatography3.2.5 LCS/LCSDLaboratory Control Sample/LaboratoryControl Sample Duplicate3.2.6 MDLMethod Detection Lim
21、it3.2.7 MeOHMethanol3.2.8 mMmillimolar,110-3moles/L3.2.9 MRMMultiple Reaction Monitoring3.2.10 MS/MSDMatrix Spike/Matrix Spike Duplicate3.2.11 NANot available3.2.12 NDnon-detect3.2.13 P however, this test method is intendedto be performance based and alternative operating conditionscan be used to pe
22、rform this method provided data qualityobjectives are attained.4.2 For PFC analysis, samples are shipped to the lab on iceand analyzed within 28 days of collection. A sample (2 g) istransferred to a polypropylene tube, spiked with surrogates (allsamples) and target PFC compounds (laboratory control
23、andmatrix spike samples). The analytes are tumbled for an hourwith 10 mL of methanol:water (50:50) under basic condition(pH 9-10 adjusted with 20 L ammonium hydroxide). Thesamples are centrifuged and the extract, leaving the solidbehind, is filtered through a polypropylene filter unit. Aceticacid (5
24、0 L) is added to all the filtered samples to adjust thepH 3-4 and then analyzed by LC/MS/MS.4.3 Most of the PFC target compounds are identified bycomparing the single reaction monitoring (SRM) transition andits confirmatory SRM transition if correlated to the knownstandard SRM (Table 3) and quantita
25、ted utilizing an externalcalibration. The surrogates and some PFC target analytes(PFPeA, PFBA, FOUEA, and FHUEA) only utilize one SRMtransition due to a less sensitive or non-existent secondarySRM transition. As an additional quality control measure,isotopically labeled PFC surrogates (listed in 12.
26、4) recoveriesare monitored. There is no correction to the data based uponsurrogate recoveries. The final report issued for each samplelists the concentration of PFCs, if detected, or RL, if notdetected, in ng/kg (Dry Weight Basis) and the surrogaterecoveries.5. Significance and Use5.1 This test meth
27、od has been developed by the US EPARegion 5 Chicago Regional Laboratory (CRL).5.2 PFCs are widely used in various industrial and commer-cial products; they are persistent, bio-accumulative, and ubiq-uitous in the environment. PFCs have been reported to exhibitdevelopmental toxicity, hepatotoxicity,
28、immunotoxicity, andhormone disturbance.Adraft Toxicological Profile for Perfluo-roalkyls from the U.S. Department of Health and HumanServices is available.7PFCs have been detected in soils,sludges, surface and drinking waters. Hence, there is a need forquick, easy, and robust method to determine the
29、se compoundsat trace levels in various soil matrices for understanding of thesources and pathways of exposure.5.3 This method has been used to determine selected per-fluorinated compounds in sand (Table 4) and four ASTMreference soils (Table 5).6. Interferences6.1 All glassware is washed in hot wate
30、r with detergent andrinsed in hot water followed by distilled water. The glasswareis then dried and heated in an oven at 250C for 15 to 30minutes.All glassware is subsequently rinsed with methanol oracetonitrile.6.2 All reagents and solvents should be pesticide residuepurity or higher to minimize in
31、terference problems. The use ofPFC containing caps should be avoided.6.3 Matrix interferences may be caused by contaminants inthe sample. The extent of matrix interferences can varyconsiderably depending on variations in the sample matrices.6.4 Contaminants have been found in reagents, glassware,tub
32、ing, glass disposable pipettes, filters, degassers, and otherapparatus that release perfluorinated compounds. All of thesematerials and supplies are routinely demonstrated to be freefrom interferences by analyzing laboratory reagent blanksunder the same conditions as the samples. If found, measuress
33、hould be taken to remove the contamination or data should bequalified; background subtraction of blank contamination is notallowed.6.5 The Liquid Chromatography system used shouldconsist, as much as practical, of sample solution or eluentcontacting components free of PFC target analytes of interest.
34、6.6 Polyethylene LC vial caps or any other target analytefree vial caps should be used.6.7 Polyethylene disposable pipettes or target analyte freepipettes should be used. All disposable pipettes should bechecked for release of target analytes of interest.6.8 Degassers are important to continuous LC
35、operation andmost commonly are made of fluorinated polymers. To enableuse, an isolator column should be placed after the degasser andprior to the sample injection valve to separate the PFCs in thesample from the PFCs in the LC system.7. Apparatus7.1 LC/MS/MS System:7A draft Toxicological Profile for
36、 Perfluroalkyls can be found at http:/www.atsdr.cdc.gov/toxprofiles/tp.asp?id=1117 this shouldinclude a sample injection system, a solvent pumping systemcapable of mixing solvents, a sample compartment capable ofmaintaining required temperature, and a temperature controlledcolumn compartment.ALC sys
37、tem that is capable of perform-ing at the flows, pressures, controlled temperatures, samplevolumes, and requirements of the standard shall be used.7.1.2 Analytical Column9A reverse phase Charged Sur-face Hybrid Phenyl-Hexyl particle column was used to developthis test method.Any column that achieves
38、 adequate resolutionmay be used. The retention times and order of elution maychange depending on the column used and need to be moni-tored.7.1.3 Isolator Column10A reverse phase C18 column wasused in this test method to separate the target analytes in the LCsystem and solvents from the target analyt
39、es in the analyticalsample. This column was placed between the solvent mixingchamber and the injector sample loop.7.2 Tandem Mass Spectrometer System11A MS/MS sys-tem capable of multiple reaction monitoring (MRM) analysisor any system that is capable of meeting the requirements inthis test method sh
40、all be used.8A Waters Acquity UPLC H-Class System, or equivalent, has been foundsuitable for use.9A Waters Acquity UPLC CSH Phenyl-Hexyl, 2.1 100 mm and 1.7 m particlesize column, or equivalent, has been found suitable for use. It was used to developthis test method and generate the precision and bi
41、as data presented in Section 16.10A Waters Acquity UPLC BEH C18, 2.1 50 mm and 1.7 m particle sizecolumn, or equivalent, has been found suitable for use.11A Waters Xevo TQ-S triple quadrupole mass spectrometer, or equivalent, hasbeen found suitable for use.TABLE 3 Retention Times, SRM Ions, and Anal
42、yte-Specific Mass Spectrometer ParametersChemicalPrimary/ConfirmatoryRetention Times(min)Cone (V) Collision (eV) MRM TransitionPrimary/Confirmatory SRMArea RatioPFTreAPrimary10.6320 13 712.9668.97.4Confirmatory 20 30 712.9169PFTriAPrimary10.1725 12 662.9618.97.4Confirmatory 25 28 662.9169PFDoAPrimar
43、y9.6110 12 612.9568.98.2Confirmatory 10 25 612.9169PFUnAPrimary9.0515 10 562.95197.2Confirmatory 15 18 562.9269PFDAPrimary8.4520 10 512.9468.96.5Confirmatory 20 16 512.9219PFOSPrimary8.7810 42 498.980.11.3Confirmatory 10 40 498.999.1PFNAPrimary7.7820 10 462.9418.94.9Confirmatory 20 16 462.9219PFecHS
44、Primary8.110 25 460.93812.2Confirmatory 10 25 460.999.1PFOAPrimary7.1120 10 412.93693.6Confirmatory 20 16 412.9169PFHxSPrimary7.3915 32 398.980.11Confirmatory 15 32 398.999.1PFHpAPrimary6.3515 10 362.93194.1Confirmatory 15 15 362.9169PFHxAPrimary5.5415 8 312.926924.1Confirmatory 15 18 312.9119.1PFBS
45、Primary5.6610 30 298.980.11.6Confirmatory 10 25 298.999.1PFPeA Primary 4.68 10 8 263219 NAPFBA Primary 3.67 10 8 212.9169 NAFHEAPrimary6.1415 20 376.92933.6Confirmatory 15 6 376.9313FOEAPrimary7.5415 18 476.93934.3Confirmatory 15 12 476.9413FDEAPrimary8.8315 8 576.84933.2Confirmatory 15 15 576.8513F
46、OUEA Primary 7.54 20 12 456.9392.9 NAFHpPAPrimary7.5415 12 440.93371.1Confirmatory 15 20 440.9317FHUEA 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.
47、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 1447.3 CentrifugeA device to centrifuge the samples.7.4 Lab Rotator12A device to mix the samples by endover end rotation.7.5 Filtration
48、Device:7.5.1 Hypodermic SyringeA luer-lock tip glass syringecapable of holding a syringe driven filter unit.7.5.2 A10 mLLock Tip Glass Syringe size is recommendedsince a 10 mL sample size is used in this test method.12A Lab Rotator, or equivalent, has been found suitable to mix samples.TABLE 4 Singl
49、e-Laboratory Recovery Data in Ottawa SandSampleMeasured ng/kg from Ottawa Sand P some sources of PFC standards thathave been found suitable for use were fromAldrich Chemical Company, WellingtonLaboratories, Inc., and Wako Laboratory. Standards from other vendors may beused.16PFC surrogates from Wellington Laboratories Inc., or equivalent, have beenfound suitable for use.D7968 146caution that PFC containing products may be present insampling equipment. All sampling equipment and suppliesshall be PFC
