气相色谱分析农药残留的基质效应及其解决方法

20081January2008ChineseJournalofChromatographyVol.26No.198～104:2007-07-18:,.E-mail:[e-mail].:.Tel:[phone],E-mail:[e-mail].:(070106-69)(2007B003).贺利民,　刘祥国,　曾振灵((),510642):,。,,。;;,。。:;;;:O658　　:A　　:1000-8713(2008)01-0098-07　　:Solutionstomatrix-inducedresponseenhancementinpesticideresidueanalysisbygaschromatographyHELimin,LIUXiangguo,ZENGZhenling(TestingCenterofAnimalandPoultryProductsQualityControlInspection(Guangzhou)ofMinistryofAgriculture,CollegeofVeterinaryMedicine,SouthChinaAgriculturalUniversity,Guangzhou510642,China)Abstract:Thesamplematrixcancauseanenhancementintheobservedchromatographicre-sponseforpesticideresiduesinamatrixextractcomparedwiththesameconcentrationinama-trix-freesolution.Thematrixincreasesthetransferofpesticidesfromthehotvaporizinginjec-torsbyreducingthethermalstressforlabilecompoundsandbymaskingtheactivesitesintheinjectorresponsiblefortheadsorptionordecompositionofpolarpesticides.Theuseofdiffer-entinjectortypesandmatrixsimplificationprocedurescanreducematrix-inducedenhancementbutdonoteliminateit.Themosteffectivestrategyistousematrix-matchedcalibrationstand-ardsoranalyteprotectantswhichequalizetheresponseenhancementforcalibrationstandardsandsampleextracts.Fromapracticalpointofview,itisimportantthatthemethodusedtocorrectformatrix-inducedenhancementiscompatiblewithlowsystemmaintenance.Thedif-ferentapproachesforcorrectingmatrix-inducedenhancementforcalibrationinpesticideresi-dueanalysisarediscussedandcomparedinthisreview.Keywords:gaschromatography(GC);pesticideresidue;matrix-inducedresponseenhance-ment;solutions　　2090,,,。Erney[1]。(、、)[2,3]。,,,,。,,,,,。,,　1,:。,,,,,。　　Erney,,[1,4]。Erney。,,。“”,。,,,。,。,,,;,。,。,,,,,。　　,[1,4,5]。(EPA)(FDA),[6,7]。,,,,[8],。　　,,。,,。,,,、,,,。。1　　　,。:、α-、、、、、、、、、p,p-、、、、、、、、、、、、、、、、、、、、、、、、、、。()(),(-P=O)、、、、、(-O-CO-NH-)(-NH-CO-NH-)。-P=S-P=O,。,,。:[9],[10-12],[13],、[14,15],[2,16],[17],[18,19],[20],[21],[22]。2　2.1　　　,。;,。,,,。,,·99·26。,,。,,。,,,,。,,,。,,,。　　,、、,-()[3,10,11,19]、[10,23,24]、[13,14,20,25],[2,6,26-30]。,(),,[7]。Lentza-Rizos[16],Jestoi[22]。,,。,,,。,,。,,。　　,Erney,、(1)。　　,。(4mg/mL)(2mg/mL),(1)。,,。2、()[25]。,1　＊Table1　Effectofmatrixtypeandinjectiontemperatureonmatrix-inducedresponseenhancementforsomeorganophosphoruspesticidesusingon-columninjection＊Temp./℃MatrixAcephateOmethoateDimethoateChlorpyrifos170milk1.671.791.321.33butterfat1.501.181.141.15210milk1.611.791.461.33butterfat1.421.521.311.03230milk1.591.581.241.23butterfat1.281.301.100.94＊Thedataaretheratioofmatrixstandardtomatrix-freestandard.2　、Table2　Effectofconcentrationontherecoveriesofpesti-cidesfromtomatoes,peppersandcucumbersContents/(mg/kg)PesticideMatrixRecoveries/%matrix-freematrix-matched0.02chlorothaloniltomatoes253120(LOQ)()peppers15480cucumbers10580captantomatoes245210()peppers257120cucumbers18470procymidonetomatoes196102()peppers16096cucumbers212120iprodionetomatoes17690()peppers22790cucumbers15795primicarbtomatoes11485()peppers11780cucumbers87870.21-2chlorothaloniltomatoes230115()peppers8886cucumbers9995captantomatoes146106()peppers10490cucumbers15082procymidonetomatoes15090()peppers10570cucumbers13595iprodionetomatoes185105()peppers15089cucumbers124109primicarbtomatoes106100()peppers118102cucumbers9393·100·　1,:。,。3[26]。(GCB),,(Amino)(PSA),C18(SAX),。3　＊Table3　Matrix-inducedresponseenhancementforapplesaftercleanupbysolid-phaseextractiontechniques＊PesticideGCB,AminoGCB,SAXGCB,SAX,PSAGCB,PSAPSAGCBNoneOmethoate()1.201.231.081.161.151.411.45Malaoxon()1.051.111.001.031.051.261.32Phosmet()1.201.080.921.101.111.201.29Acephate()1.121.171.041.081.051.251.22Malathion()0.991.000.990.991.001.041.06Terbufos()0.991.011.051.020.991.000.99　GCB:graphitizedcarbonblack;SAX:stronganionexchange;Amino:aminopropylsiloxane-bondedsilicagel;PSA:primarysec-ondaryamine;None:nosolid-phaseextractionclean-up.＊Thedataaretheratioofmatrixstandardtomatrix-freestandard.　　,,,,,。,。HillReynolds[31],、、()。Martinez[32],,。,。,[6,33],FDA()、()()[6]。,[34]。2.2　　　[4,35-38]。、,,,,。,,;,;,,。2090,,,。,,,,5μL,[21,35,39-43]。　　(PTV),“”,[35]。:,;,。,PTV,PTV,。,PTV,,,。,PTV。　　。,。,,,。,,·101·26;,,。　　,:(DSI)[44,45]“”(DMI)[46,47]。DSI,,,。,,,。DMIDSI,DMI,DSI。。DSI,DMI。,DMIDSI,(),。,DSIDMI。2.3　　　,,[48-50]。,,,,[50]。,,,。1[5]。,,。,,。:Y,YXSC(),(1)XMC()。XMC=A+B×XSC(1)A(aSC-aMC)/bMC,BbSC/bMC,ab。1　(MC)(SC)Fig.1　Calibrationcurvesforomethoateinacetonitrile(SC)andmatrix-matchedmilkextract(MC)　　。　　,,,[51]。:,,,,。,,。,,,。,,,,。　　,[24],。,,。,,,,。,,。·102·　1,:2.4　　　[9,29,47,52-55]。,。ErneyPoole[52],Lehotay[29,47,53,54],。,。,,。,,。Lehotay,,。()、[53,54]。,Lehotay,,。,3--1,2-,γ-,,。,25μL(40mg/mL3--1,2-,4mg/mLγ-,-(7∶3))1.0mL,[47]。2。、、[9,29][55]。,:　　1);　　2)(),;　　3),;　　4)。2　(a)(b)(100ng/mL)Fig.2　Comparisonofresponseenhancementfor100ng/mLofpesticidesinamixedfruitacetoni-trileextract(a)withoutand(b)withaddi-tionofanalyteprotectants(3-ethoxy-1,2-propanediol,gulonolactoneandsorbitolat10,1and1mg/mL,respectively)inthesample　　,,。3　　　,。、,、。,,。　　,,2090,,,[56]。,,[57],·103·26。,,。:[1]　ErneyDR,GillespieAM,GilvydisDM,etal.JChroma-togr,1993,638:57[2]　GillespieAM,DalySL,GilvydisDM,etal.JAOACIn