1、Designation: D7979 15Standard Test Method forDetermination of Perfluorinated Compounds in Water,Sludge, Influent, Effluent and Wastewater by LiquidChromatography Tandem Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed designation D7979; the number immediately following the design
2、ation 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 determ
3、ination of selectedperfluorinated compounds (PFCs) in a water matrix usingliquid chromatography (LC) and detection with tandem massspectrometry (MS/MS). These analytes are qualitatively andquantitatively determined by this method. This method adheresto multiple reaction monitoring (MRM) mass spectro
4、metry.1.2 The Method Detection Limit (MDL)2and ReportingRange3for the target analytes are listed in Table 1.1.2.1 The reporting limit in this test method is the minimumvalue below which data are documented as non-detects. Ana-lyte detections between the method detection limit and thereporting limit
5、are estimated concentrations and are not re-ported following this test method. In most cases, the reportinglimit is the concentration of the Level 1 calibration standard asshown in Table 4 for the perfluorinated compounds after takinginto account the 50 % dilution with methanol. It is above theLevel
6、 1 calibration concentration for PFOS, PFBS, FHEA andFOEA, these compounds can be identified at the Level 1concentration but the standard deviation among replicates atthis lower spike level resulted in a higher reporting limit.1.3 UnitsThe values stated in SI units are to be regardedas standard. No
7、other units of measurement are included in thisstandard.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-bilit
8、y of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:4D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3856 Guide for Management Systems in
9、LaboratoriesEngaged in Analysis of WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD5847 Practice for Writing Quality Control Specification
10、sfor Standard Test Methods for Water AnalysisE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniques2.2 Other Standards:5EPAPublication SW-846, Test Methods for Evaluating SolidWaste, Physical/Chemical MethodsThe Code of Federal Re
11、gulations 40 CFR Part 136, Appen-dix B3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this standard, refer toTerminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 perfluorinated compounds, nin this test method, 11perfluoroalkyl carboxylic acids, 3 perfluoroa
12、lkylsulfonates,Decafluoro-4-(pentafluoroethyl)cyclohexanesulfonate and 61This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Jan. 1, 2015. Publi
13、shed February 2015. DOI: 10.1520/D7979-15.2The MDL is determined following the Code of Federal Regulations, 40 CFRPart 136, Appendix B utilizing dilution and filtration. 5 mL sample of water wasutilized. A detailed process determining the MDL is explained in the reference andis beyond the scope of t
14、his test method to be explained here.3Reporting range concentration is calculated from Table 4 concentrationsassuming a 30 L injection of the Level 1 calibration standard for PFCs, and thehighest level calibration standard with a 10 mLfinal extract volume ofa5mLwatersample. Volume variations will ch
15、ange the reporting limit and ranges.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
16、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/testmethods/index.htmCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1fluorotelome
17、r acids listed in Table 1 collectively (not includingmass labeled surrogates).3.2.2 reporting limit, nthe minimum concentration belowwhich data are documented as non-detects.3.3 Acronyms:3.3.1 CCC, nContinuing Calibration Check3.3.2 FTAs and FTUAs, nFluorotelomer and UnsaturatedFluorotelomer Acids3.
18、3.2.1 FDEA, n2-perfluorodecyl ethanoic acid3.3.2.2 FHEA, n2-perfluorohexyl ethanoic acid3.3.2.3 FHpPA, n3-perfluoroheptyl propanoic acid3.3.2.4 FHUEA, n2H-perfluoro-2-octenoic acid3.3.2.5 FOEA, n2-perfluorooctyl ethanoic acid3.3.2.6 FOUEA, n2H-perfluoro-2-decenoic acid3.3.3 IC, nInitial Calibration3
19、.3.4 LC, nLiquid Chromatography3.3.5 LCS/LCSD, nLaboratory Control Sample/Laboratory Control Sample Duplicate3.3.6 MDL, nMethod Detection Limit3.3.7 MeOH, nMethanol3.3.8 mM, nmillimolar,110-3moles/L3.3.9 MRM, nMultiple Reaction Monitoring3.3.10 MPFAS, nIsotopically labeled Perfluoroalkylsul-fonates3
20、.3.10.1 MPFHxS, n18O2-Perfluorohexylsulfonate3.3.10.2 MPFOS, n13C4-Perfluorooctylsulfonate3.3.11 MPFCA, nIsotopically labeled Perfluoroalkylcar-boxylates3.3.11.1 MPFBA, n13C4-Perfluorobutanoate3.3.11.2 MPFDA, n13C2-Perfluorodecanoate3.3.11.3 MPFDoA, n13C2-Perfluorododecanoate3.3.11.4 MPFHxA, n13C2-P
21、erfluorohexanoate3.3.11.5 MPFNA, n13C5-Perfluorononanoate3.3.11.6 MPFOA, n13C4-Perfluorooctanoate3.3.11.7 MPFUnA, n13C2-Perfluoroundecanoate3.3.12 MS/MSD, nMatrix Spike/Matrix Spike Duplicate3.3.13 NA, adjNot Available3.3.14 ND, nnon-detect3.3.15 P however, this test method isintended to be performa
22、nce based and alternative operatingconditions can be used to perform this method provided dataquality objectives are attained.4.2 For PFC analysis, samples are shipped to the lab at atemperature between 0C and 6C and analyzed within 28 daysof collection. A sample (5 mL) is transferred to a polypropy
23、l-ene tube (ora5mLsample is collected in a polypropylene tubeTABLE 1 Method Detection Limit and Reporting RangeAnalyteMDL(ng/L)Reporting Ranges(ng/L)PFTreA 1.74 10 - 400PFTriA 2.65 10 - 400PFDoA 2.42 10 - 400PFUnA 1.08 10 - 400PFDA 3.03 10 - 400PFOS 4.19 15 - 400PFNA 1.76 10 - 400PFecHS 1.93 10 - 40
24、0PFOA 3.04 10 - 400PFHxS 2.51 10 - 400PFHpA 2.32 10 - 400PFHxA 1.31 10 - 400PFBS 7.60 30 - 400PFPeA 11.59 50 - 2000PFBA 13.85 50 - 2000FHEA 92.93 300 - 8000FOEA 106.75 300 - 8000FDEA 47.17 200 - 8000FOUEA 2.31 10 - 400FHpPA 3.25 10 - 400FHUEA 1.53 10 - 400AAcronyms are defined in 3.3.D7979 152in the
25、 field to limit target analyte loss due to samplemanipulation), spiked with surrogates (all samples) and targetPFC compounds (laboratory control and matrix spike samples)and hand shaken for 2 minutes after adding 5 mL of methanol.The samples are then filtered through a polypropylene filterunit. Acet
26、ic acid (10 L) is added to all the samples to adjustto pH 3 and analyzed by LC/MS/MS. For 5 mL sludgesamples; 5 mL methanol is added, adjusted to pH 9 (adding20 l of ammonium hydroxide), hand shaken, filtered, acidi-fied to pH 3 (50 L acetic acid) and then analyzed byLC/MS/MS.NOTE 1Sludge in this me
27、thod is defined as sewage sample containingapproximately 0.2 % solids based upon a sample by weight.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 transition (Ta
28、ble 3) and quantitated utilizing anexternal calibration. The surrogates and some PFC targetanalytes (PFPeA, PFBA, FOUEA and FHUEA) only utilizeone SRM transition due to a less sensitive or non-existentsecondary SRM transition. As an additional quality-controlmeasure, isotopically labeled PFC surroga
29、tes (listed in 12.4)recoveries are monitored. There is no correction to the databased upon surrogate recoveries. The final report issued foreach sample lists the concentration of PFCs, if detected, or RL,if not detected, in ng/L and the surrogate recoveries.5. Significance and Use5.1 This test metho
30、d 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, i
31、mmunotoxicity, andhormone disturbance.Adraft Toxicological Profile for Perfluo-roalkyls from the U.S. Department of Health and HumanServices is available.6PFCs have been detected in soils,sludges, surface, and drinking waters. Hence, there is a needfor quick, easy, and robust method to determine the
32、se com-pounds at trace levels in water matrices for understanding ofthe sources and pathways of exposure.5.3 This method has been investigated for use with reagent,surface, sludge and wastewaters for selected perfluorinatedcompounds.6. Interferences6.1 All glassware is washed in hot water with deter
33、gent 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 interference p
34、roblems. The use ofPFC containing caps shall be avoided.6.3 Matrix interferences may be caused by contaminants inthe sample. The extent of matrix interferences can varyconsiderably depending on variations of the sample matrices.6.4 Contaminants have been found in reagents, glassware,tubing, glass di
35、sposable 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, measuresshould be taken
36、 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.6.6 Polyethyle
37、ne 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 operation andm
38、ost 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:7.1.1 Liquid Chromatography System7A complete LC
39、system is required in order to analyze samples, 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 system that is capable of perform-ing a
40、t the flows, pressures, controlled temperatures, samplevolumes, and requirements of the standard shall be used.7.1.2 Analytical Column8A reverse phase Charged Sur-face Hybrid Phenyl-Hexyl particle column was used to developthis test method.Any column that achieves adequate resolutionmay be used. The
41、 retention times and order of elution maychange depending on the column used and needs to bemonitored.7.1.3 Isolator Column9A reverse phase C18 column wasused in this test method to separate the target analytes in the LCsystem and solvents from the target analytes in the analyticalsample. This colum
42、n was placed between the solvent mixingchamber and the injector sample loop.7.2 Tandem Mass Spectrometer System10A MS/MS sys-tem capable of multiple reaction monitoring (MRM) analysis6A Draft Toxicological Profile for Perfluoroalkyls can be found at: http:/www.atsdr.cdc.gov/toxprofiles/tp.asp?id=111
43、7 Samplecompartment, 15C.11.2.3 Seal WashSolvent: 60 % acetonitrile/40 %2-propanol; Time: 5 minutes.11.3 Mass Spectrometer Parameters:11.3.1 To acquire the maximum number of data points perSRM channel while maintaining adequate sensitivity, the tuneparameters may be optimized according to your instr
44、ument.Each peak requires at least 10 scans per peak for adequatequantitation. This test method contains nine surrogates, whichare isotopically labeled PFCs, and 21 PFCs which were split upinto eighteen MRM acquisition functions to optimize sensitiv-ity. Variable parameters regarding retention times,
45、 SRMtransitions, and cone and collision energies are shown in Table3. Mass spectrometer parameters used in the development ofthis method are listed below:The instrument is set in the Electrospray negative source setting.Capillary Voltage: 0.75 kVCone: Variable depending on analyteExtractor: 2 VoltsS
46、ource Temperature: 150CDesolvation Gas Temperature: 450CDesolvation Gas Flow: 800 L/hrCone Gas Flow: 200 L/hrCollision Gas Flow: 0.15 mL/minLow Mass Resolution 1: 2.6High Mass Resolution 1: 14Ion Energy 1: 1Entrance Energy: 1Collision Energy: Variable depending on analyteExit Energy: 1Low Mass Resol
47、ution 2: 2.5High Mass resolution 2: 14Ion Energy 2: 3Gain: 1.0Multiplier: 511.1Inter-Scan Delay: 0.004 seconds12. Calibration and Standardization12.1 The mass spectrometer shall be calibrated as in accor-dance with manufacturers specifications before analysis. Ana-lytical values satisfying test meth
48、od criteria have beenachieved using the following procedures. Prepare all solutionsin the lab using Class A volumetric glassware.12.2 Calibration and StandardizationTo calibrate theinstrument, analyze nine calibration standards containing theperfluorinated compounds prior to analysis as shown in Tab
49、le4. Calibration stock standard solution is prepared from thetarget and surrogate spike solutions directly to ensure consis-tency. Stock standard Solution A containing the perfluorinatedcompounds and surrogates is prepared at Level 9 concentrationand aliquots of that solution are diluted to prepare Levels 1through 8. The following steps will produce standards with theconcentration values shown in Table 4. The analyst is respon-sible for recording initial component weights carefully whenworking with pure materials and correctl
