同位素稀释气相色谱_质谱法测定土壤_底泥中23种有机氯农药

20105Vo.l28No.5May2010ChineseJournalofChromatography476~482特别策划DOI:10.3724/SP.J.1123.2010.00476*:,.Te:l(010)84665737,Emai:[e-mail].:(863)(No.2009AA061603).:20100114/23房丽萍,封跃鹏,刘海萍,吴忠祥*(,100029):(IDGCMS))/23250mL(1!1)24h,,DB5,13C,23,50~1600g/L,60%~110%,15%~18%;020~103g/kg,,/:;;;:O658:A:10008713(2010)05047607Determinationoforganochlorinepesticideresiduesinsoil/sedimentusingisotopedilutiongaschromatographymassspectrometryFANGLiping,FENGYuepeng,LIUHaiping,WUZhongxiang*(InstituteforEnvironmentalReferenceMaterialsofMinistryofEnvironmentalProtection,Beijing100029,China)Abstract:Amethodwasdevelopedforthedeterminationoforganochlorinepesticide(OCP)residuesinsoil/sedimentusinghighresolutiongaschromatographycoupledwithlowresolutionmassspectrometry.TheanalyticalproceduresconsistedofSoxhletextraction,sulfurremovalwithcopperpowder,cleanupwithgelpermeationchromatography(GPC)andaflorisilcolumnofsolidphaseextraction(SPE).TheanalyteswereseparatedonanHP5MScapillarycolumn,detectedinselectedionmonitoring(SIM)modeandquantifiedusinginternalstandardcalibrationcurvesofisotopedilutiontechnique.ThelinearcorrelationsofcalibrationstandardsolutionsweregoodforalltheOCPs.Therecoveriesandrelativestandarddeviationsoflabeledcompoundsolutionsrangedfrom60%to110%andfrom15%to18%,respectively.Thelimitsofdetectionrangedfrom020to103g/kgwereestablishedforthe23OCPs.Themethodshowedsatisfactorycleanupeffectandprecisionquantification.Itissuitableforthedeterminationandconfirmationofpesticidesincomplexmatricessuchassoi,lsediment.Keywords:isotopedilutiongaschromatographymassspectrometry(IDGCMS);organochlorinepesticides(OCPs);soi;lsediment(organochlorinepesticides,OCPs)∀#12(persistentorganicpollutants,POPs),,,[1],,,[2-6]5,:/23∀#9,(DDTs)POPs20041111∀#,[7],,,,,9,8,(hexachlorobenzene)(aldrin)(dieldrin)(endrin)4,4∃(4,4∃DDT)4,4∃(4,4∃DDE)4,4∃(4,4∃DDD)2,4∃(2,4∃DDT)2,4∃(2,4∃DDE)2,4∃(2,4∃DDD)(transchlordane)(cischlordane)(transnonachlor)(cisnonachlor)(oxychlordane)(heptachlor)(transheptachlorepoxide)(cisheptachlorepoxide)(mirex)(BHC)(BHC)!(!BHC)∀(∀BHC)23,(USE)[4,7,8](SE)[3,9](ASE)[10-16](GPC)[2,15-20](SPE)[3,15,16,20,21](GCECD)(GCMS)[22,23]GCECD,,GCMS(),(ID),,GCMS,,,(SIM),/,11.1(Agilent7890A5975C,Agilent),Agilent7693;DB5MS(30m%025mm%025m);(NEVAP,OrganomationAssociates);(Heidolph);(Supelco);(HX1050,);(QL901,)(J.T.Baker);(AlfaAesar,AJohnsonMattayCompany);(LCFlorisi,l12mL,2g,Supelco);(200,);(BioBeadsSX3Beads,200~400,BioRadLaboratories);(),660&6h13COCPs(ES5349L)(1000g/L)(EC5350L)(1000g/L)(ES539910X05)(2000g/L)CambridgeIsotopeLaboratoriesInc.:13C6(hexachlorobenzene13C6)13C12(aldrin13C12)13C12(dieldrin13C12)13C12(endrin13C12)4,4∃13C12(4,4∃DDT13C12)4,4∃13C12(4,4∃DDE13C12)4,4∃13C12(4,4∃DDD13C12)2,4∃13C12(2,4∃DDT13C12)2,4∃13C12(2,4∃DDE13C12)2,4∃13C12(2,4∃DDD13C12)13C10(transchlordane13C10)13C10(transnonachlor13C10)13C10(cisnonachlor13C10)13C10(oxychlordane13C10)13C10(heptachlor13C10)13C10(cisheptachlorepoxide13C10)13C10(mirex13C10)13C6(BHC13C6)13C6(BHC13C6)!13C6(!BHC13C6)∀13C6(∀BHC13C6):4,4∃13C12(4,4∃DiCB13C12,PCB1513C12)2,3∃,4∃,513C12(2,3∃,4∃,5tetraCB13C12,PCB7013C12)∋477∋28:12550200250400L5,1000g/L50L,05mL,CS1CS2CS3CS4CS520086,()1.21.2.1样品提取5g,50L(50ng)5mL,,30min250mL(1!1)24h1.2.2铜粉去硫,6mol/L,1min,3,3,1min,,1~2min3g,30min,;,1~2mL,1.2.3凝胶渗透色谱净化:30gGPCBioBeadsSX3(200~400),(1!1)200mL,12h,,300mm%25mm200,,500mL(1!1),2~3/s,5cmGPC(1!1)GPC,,100mL50mL(1!1),122GPC,70mL(1!1),50mL(1!1)GPC,,1~2mL,1.2.4弗罗里硅土固相萃取柱净化(2g,12mL),,123,35mL(90!10),1mL,50L;1mL2,,100L,,50L(50ng),,GCMS1.31.3.1气相色谱条件:DB5MS(30m%025mm%025m);:100&2min,20&/min160&,5min,2&/min270&;:225&;,1L;:,(99999%,10mL/min1OCPs1OCPsFig.1TotalioncurrentchromatogramsofOCPscalibrationstandardsolutionPeaks:1.BHC;2.hexachlorobenzene;3.BHC;4.!BHC;5.PCB15;6.∀BHC;7.heptachlor;8.aldrin;9.oxychlordane;10.cisheptachlorepoxide;11.transheptachlorepoxide;12.PCB70;13.transchlordane;14.2,4∃DDE;15.cischlordane;16.transnonachlor;17.dieldrin;18.4,4DDE;19.2,4∃DDD;20.endrin;21.cisnonachlor;22.4,4∃DDD;23.2,4∃DDT;24.4,4∃DDT;25.mirex.1.3.2质谱条件,70eV;:230&;:280&;:14min;SIM123OCPsGCMS∋478∋5,:/23123Table1Retentiontimes,characteristicionsandabundanceratiosof23OCPsGroupOCPTimewindow/minRetentiontime/minCharacteristicion(m/z)Abundanceratio*1BHC15.0-22.515.718181/1831.03BHC13C615.701187/1891.04hexachlorobenzene16.205284/2861.26hexachlorobenzene13C616.185290/2921.28BHC17.480181/1831.03BHC13C617.464187/1891.03!BHC17.885181/1831.02!BHC13C617.869187/1891.04PCB1513C1218.728234/2361.59∀BHC19.577181/1831.02∀BHC13C619.555187/1891.042heptachlor22.5-28.023.047272/2741.24heptachlor13C1023.010277/2791.33aldrin25.674263/2651.50aldrin13C1225.636268/2700.683oxychlordane28.0-30.329.019185/1871.28oxychlordane13C1029.989190/1921.05cisheptachlorepoxide28.931353/3551.26cisheptachlorepoxide13C1028.904363/3651.31transheptachlorepoxide29.292353/3551.22PCB7013C1229.484302/3040.794transchlordane30.3-33.030.895373/3751.04transchlordane13C1030.859383/3851.052,4∃DDE31.603246/2481.542,4∃DDE13C1231.571258/2601.57cischlordane32.167373/3751.04transnonachlor32.595407/4090.89transn