1、Designation: D7979 151D7979 16Standard 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 t
2、he 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. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1 NOTEEditorial corrections were ma
3、de throughout in November 2015.1. Scope1.1 This procedure covers the determination of selected perfluorinated compounds (PFCs) in a water matrix using liquidchromatography (LC) and detection with tandem mass spectrometry (MS/MS). These analytes are qualitatively and quantitativelydetermined by this
4、method. This method adheres to multiple reaction monitoring (MRM) mass spectrometry.1.2 The Method Detection Limit (MDL)2 and Reporting Range3 for the target analytes are listed in Table 1.1.2.1 The reporting limit in this test method is the minimum value below which data are documented as non-detec
5、ts. 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 limit is the concentration of the Level 1 calibration standard as shown in Table 4 forthe perfluorinated compound
6、s after taking into account the 50 % dilution with methanol. It is above the Level 1 calibration1 This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis forOrganic Substances in Water.Current edition a
7、pproved Jan. 1, 2015June 1, 2016. Published February 2015June 2016. Originally approved in 2004. Last previous edition approved in 2015 asD7979 151. DOI: 10.1520/D7979-15E01.10.1520/D7979-16.2 The MDL is determined following the Code of Federal Regulations, 40 CFR Part 136, Appendix B utilizing dilu
8、tion and filtration. 5 mL sample of water was utilized.A detailed process determining the MDL is explained in the reference and is beyond the scope of this test method to be explained here.3 Reporting range concentration is calculated from Table 4 concentrations assuming a 30 L injection of the Leve
9、l 1 calibration standard for PFCs, and the highest levelcalibration standard with a 10 mL final extract volume of a 5 mL water sample. Volume variations will change the reporting limit and ranges.TABLE 1 Method Detection Limit and Reporting RangeAnalyteA MDL(ng/L) Reporting Ranges(ng/L)PFTreA 1.74 1
10、0 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 400PFOA 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 47.17 200 800
11、0FOUEA 2.31 10 400FHpPA 3.25 10 400FHUEA 1.53 10 400A Acronyms are defined in 3.3.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 adeq
12、uately depict 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 Conshohoc
13、ken, PA 19428-2959. United States1concentration for PFOS, PFBS, FHEAand FOEA, these compounds can be identified at the Level 1 concentration but the standarddeviation among replicates at this lower spike level resulted in a higher reporting limit.1.3 UnitsThe values stated in SI units are to be rega
14、rded as standard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determ
15、ine the applicability of regulatorylimitations 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 of Applicable Test Methods of Committee D19 on WaterD3856 Guide for Ma
16、nagement Systems in Laboratories Engaged in Analysis of WaterD3694 Practices for Preparation of Sample Containers and for Preservation of Organic ConstituentsD4841 Practice for Estimation of Holding Time for Water Samples Containing Organic and Inorganic ConstituentsD5847 Practice for Writing Qualit
17、y Control Specifications for Standard Test Methods for Water AnalysisE2554 Practice for Estimating and Monitoring the Uncertainty of Test Results of a Test Method Using Control Chart Techniques2.2 Other Standards:5EPA Publication SW-846, Test Methods for Evaluating Solid Waste, Physical/Chemical Met
18、hodsThe Code of Federal Regulations 40 CFR Part 136, Appendix B3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.4 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For A
19、nnual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.5 Available from National Technical Information Service (NTIS), U.S. Department of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/testmetho
20、ds/index.htmD7979 1623.2 Definitions of Terms Specific to This Standard:3.2.1 perfluorinated compounds, nin this test method, 11 perfluoroalkyl carboxylic acids, 3 perfluoroalkylsulfonates,Decafluoro-4-(pentafluoroethyl)cyclohexanesulfonate and 6 fluorotelomer acids listed in Table 1 collectively (n
21、ot including masslabeled surrogates).3.2.2 reporting limit, nthe minimum concentration below which data are documented as non-detects.3.3 Acronyms:3.3.1 CCC, nContinuing Calibration Check3.3.2 FTAs and FTUAs, nFluorotelomer and Unsaturated Fluorotelomer Acids3.3.2.1 FDEA, n2-perfluorodecyl ethanoic
22、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 Calibration3.3.4 LC, nLiquid Chromatography3.3.5 LC
23、S/LCSD, nLaboratory Control Sample/Laboratory Control Sample Duplicate3.3.6 MDL, nMethod Detection Limit3.3.7 MeOH, nMethanol3.3.8 mM, nmillimolar, 1 10-3 moles/L3.3.9 MRM, nMultiple Reaction Monitoring3.3.10 MPFAS, nIsotopically labeled Perfluoroalkylsulfonates3.3.10.1 MPFHxS, n18O2-Perfluorohexyls
24、ulfonate3.3.10.2 MPFOS, n13C4-Perfluorooctylsulfonate3.3.11 MPFCA, nIsotopically labeled Perfluoroalkylcarboxylates3.3.11.1 MPFBA, n13C4-Perfluorobutanoate3.3.11.2 MPFDA, n13C2-Perfluorodecanoate3.3.11.3 MPFDoA, n13C2-Perfluorododecanoate3.3.11.4 MPFHxA, n13C2-Perfluorohexanoate3.3.11.5 MPFNA, n13C5
25、-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 is intended to be performance based and alternative operating c
26、onditions can beused to perform this method provided data quality objectives are attained.4.2 For PFC analysis, samples are shipped to the lab at a temperature between 0C and 6C and analyzed within 28 days ofcollection. A sample (5 mL) is transferred to a polypropylene tube (or a 5 mL sample is coll
27、ected in a polypropylene tube in thefield to limit target analyte loss due to sample manipulation), spiked with surrogates (all samples) and target PFC compounds(laboratory control and matrix spike samples) and hand shaken for 2 minutes after adding 5 mL of methanol. The samples are thenfiltered thr
28、ough a polypropylene filter unit. Acetic acid (10 L) is added to all the samples to adjust to pH 3 and analyzed byLC/MS/MS. For 5 mL sludge samples; 5 mL methanol is added, adjusted to pH 9 (adding 20 l of ammonium hydroxide), handshaken, filtered, acidified to pH 3 (50 L acetic acid) and then analy
29、zed by LC/MS/MS.NOTE 1Sludge in this method is defined as sewage sample containing approximately 0.2 % solids based upon a sample by weight.4.3 Most of the PFC target compounds are identified by comparing the single reaction monitoring (SRM) transition and itsconfirmatory SRM transition if correlate
30、d to the known standard SRM transition (Table 3) and quantitated utilizing an externalcalibration. The surrogates and some PFC target analytes (PFPeA, PFBA, FOUEA and FHUEA) only utilize one SRM transitiondue to a less sensitive or non-existent secondary SRM transition. As an additional quality-cont
31、rol measure, isotopically labeledPFC surrogates (listed in 12.4) recoveries are monitored. There is no correction to the data based upon surrogate recoveries. Thefinal report issued for each sample lists the concentration of PFCs, if detected, or RL, if not detected, in ng/L and the surrogaterecover
32、ies.5. Significance and Use5.1 This test method has been developed by the US EPA Region 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 exhi
33、bit developmental toxicity, hepatotoxicity, immunotoxicity, and hormonedisturbance. A draft Toxicological Profile for Perfluoroalkyls from the U.S. Department of Health and Human Services isavailable.6 PFCs have been detected in soils, sludges, surface, and drinking waters. Hence, there is a need fo
34、r quick, easy, androbust method to determine these compounds at trace levels in water matrices for understanding of the sources and pathways ofexposure.5.3 This method has been investigated for use with reagent, surface, sludge and wastewaters for selected perfluorinatedcompounds.6 A Draft Toxicolog
35、ical Profile for Perfluoroalkyls can be found at: http:/www.atsdr.cdc.gov/toxprofiles/tp.asp?id=1117 Sample compartment, 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 per SRM chann
36、el while maintaining adequate sensitivity, the tuneparameters may be optimized according to your instrument. Each peak requires at least 10 scans per peak for adequate quantitation.This test method contains nine surrogates, which are isotopically labeled PFCs, and 21 PFCs which were split up into ei
37、ghteenMRM acquisition functions to optimize sensitivity. Variable parameters regarding retention times, SRM transitions, and cone andcollision energies are shown in Table 3. Mass spectrometer parameters used in the development of this method are listed below:The instrument is set in the Electrospray
38、 negative source setting.Capillary Voltage: 0.75 kVCone: Variable depending on analyteExtractor: 2 Volts15 Guides to help determine holding times can be found at: http:/www.epa.gov/esd/cmb/research/bs_033cmb06.pdf (2014) and Practice D4841.TABLE 2 Gradient Conditions for Liquid ChromatographyTime (m
39、in) Flow(mL/min)95 % Water:5 %Acetonitrile%Acetonitrile%95 % Water:5 %Acetonitrile,400 mMAmmoniumAcetate%0 0.3 95 0 51 0.3 75 20 56 0.3 50 45 513 0.3 15 80 514 0.4 0 95 517 0.4 0 95 518 0.4 95 0 521 0.4 95 0 5D7979 167Source Temperature: 150CSource Temperature: 150CDesolvation Gas Temperature: 450CD
40、esolvation 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 Resolution 2: 2.5High Mass resolution 2: 14Ion Energy 2: 3Gain
41、: 1.0Multiplier: 511.1Inter-Scan Delay: 0.004 secondsTABLE 3 Retention Times, SRM Ions, and Analyte-Specific Mass Spectrometer ParametersChemical Primary/Confirmatory RetentionTimes (min) Cone (V) Collision (eV) MRMTransitionPrimary/ConfirmatorySRM AreaRatioPFTreA Primary 10.63 20 13 712.9668.9 7.4C
42、onfirmatory 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 6.5Confirmatory 20 16 512.9219PFOS Primar
43、y 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 15 32 398.980.1 1Confirmatory 15 3
44、2 398.999.1PFHpA 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 8 212.9169 NAFHEA Primary 6.14 15 20 376
45、.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 20 440.9317FHUEA Primary 6.08 10 12 357293 NAMPFB
46、A 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
47、.61 15 12 614.9569.9 NAD7979 16812. Calibration and Standardization12.1 The mass spectrometer shall be calibrated as in accordance with manufacturers specifications before analysis. Analyticalvalues satisfying test method criteria have been achieved using the following procedures. Prepare all soluti
48、ons in the lab usingClass A volumetric glassware.12.2 Calibration and StandardizationTo calibrate the instrument, analyze nine calibration standards containing theperfluorinated compounds prior to analysis as shown in Table 4. Calibration stock standard solution is prepared from the target andsurrog
49、ate spike solutions directly to ensure consistency. Stock standard Solution A containing the perfluorinated compounds andsurrogates is prepared at Level 9 concentration and aliquots of that solution are diluted to prepare Levels 1 through 8. Thefollowing steps will produce standards with the concentration values shown in Table 4. The analyst is responsible for recordinginitial component weights carefully when working with pure m
