ASTM_D_7485_-_09.pdf

Designation:D748509Standard Test Method forDetermination of Nonylphenol,p-tert-Octylphenol,Nonylphenol Monoethoxylate and Nonylphenol Diethoxylatein Environmental Waters by Liquid Chromatography/TandemMass Spectrometry1This standard is issued under the fixed designation D7485;the number immediately following the 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.Scope1.1 This test method covers the determination of nonylphe-nol(NP),nonylphenol ethoxylate(NP1EO),nonylphenol di-ethoxylate(NP2EO),and octylphenol(OP),extracted fromwater utilizing solid phase extraction(SPE),separated usingliquid chromatography(LC)and detected with tandem massspectrometry(MS/MS).These compounds are qualitativelyand quantitatively determined by this method.This methodadheres to single reaction monitoring(SRM)mass spectrom-etry.1.2 The method detection limit(MDL)and reporting limit(RL)for NP,NP1EO,NP2EO,and OP are listed in Table 1.1.3 The values stated in SI units are to be regarded asstandard.No 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-bility of regulatory limitations prior to use.2.Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water AnalysisD5905 Practice for the Preparation of Substitute Wastewater2.2 Other DocumentsThe Code of Federal Regulations 40 CFR Part 136,Appen-dix B33.Terminology3.1 Nonylphenol(NP)isamixtureofbranchedp-nonylphenol isomers.Commercial NP is produced by thereaction of phenol with commercial nonene.Commercialnonene is not simply a linear C9H18alpha olefin;it is acomplex mixture of predominantly nine-carbon olefins,calledpropylene trimer,containing no linear isomers.This synthesisresults in a mixture of various branched nonylphenol isomersrather than a discrete chemical structure.The branched nonylgroup is positioned predominantly in the para position on thephenol ring.3.2 OP represents octylphenol.Commercial octylphenol isproduced by the reaction of phenol and diisobutylene toproduce predominantly the 4-(1,1,3,3-tetramethylbutyl)phenolisomer.3.3 NP1EO represents branched nonylphenol monoethoxy-late.3.4 NP2EO represents branched nonylphenol diethoxylate.3.5 n-NP2EO represents normal straight chain nonylphenoldiethoxylate.n-NP2EO is used in this method as a surrogate.Itis not produced commercially and is not expected to be foundin environmental waters.3.6 2-Bromo-4-(1,1,3,3-tetramethylbutyl)phenol(Br-OP)isused in this method as a surrogate.It is not producedcommercially and is not expected to be found in environmental1This 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 March 1,2009.Published March 2009.DOI:10.1520/D7485-09.2For 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.3Available from U.S.Government Printing Office Superintendent of Documents,732 N.Capitol St.,NW,Mail Stop:SDE,Washington,DC 20401,http:/www.access.gpo.gov.Copyright ASTM International,100 Barr Harbor Drive,PO Box C700,West Conshohocken,PA 19428-2959.United States1 waters.It was reported that compounds in highly chlorinatedbromide rich wastewaters could potentially interfere with theBr-OPsurrogate.Ifthisinterferenceisencounteredn-nonylphenol is suggested as an alternative surrogate.3.7 Unitsparts per trillion(ng/L,ppt),parts per billion(g/L,ppb),parts per million(mg/L,ppm)3.8 Environmental water shall refer to water tested usingthis method.See Section 5.4.Summary of Test Method4.1 This is a performance-based method and modificationsare allowed to improve performance.4.2 For NP,NP1EO,NP2EO,and OP analysis,solid phaseextraction is used to extract water samples.4.2.1 Solid Phase Extraction250 milliliter volume ofsample adjusted to pH 2 is extracted using a solid phaseextraction cartridge.The acetonitrile/water extract is concen-trated to a volume of 1.0 mL,and then analyzed by LC/MS/MSoperated in the multiple reaction monitoring(MRM)mod