GCMS法测定腌制水产品中3种N亚硝胺含量王秀元

62012-09-0520110243(1986-):.E-mail:[e-mail](1966-).E-mail:[e-mail]:1008－830X(2012)06－0521－06GC-MS3N-1222221.、3160042.316021N-。-GC-MSN-NDMA、N-NDEA、N-NDPA3、、。10～1000ng/mL0.9995RSD5%86%～99%NDPA1ng/mLNDMA、NDEA2ng/mLN-。GC-MSN-TS254ADeterminationofThreeN-nitrosocompoundsinSaltedAquaticProductsbyGC-MSWANGXiu-yuan1,ZHAOHua2,JIANGLing-bo2,etal1.FoodandPharmacy&MedicalSchoolofZhejiangOceanUniversity,Zhoushan3160042.ZhoushaninstituteofCalibrationandtestingforQualitativeTechnicalSupervision,Zhoushan316021,ChinaAbstract:AnanalyticalmethodwasdevelopedforthedeterminationfortheextractionofVolatileN-ni－trosaminescompoundsfromsaltedaquaticproductsusingbygaschromatographywithmassspectrometrydetec－tion(GC-MS).ThoughGC-MStodeterminesixkindsofN-nitrosaminecompoundsincludingN-nitrosodimethy－lamine(NDMA),N-nitrosodiethylamine(NDEA),N-nitroso-di-n-propylamine(NDPA).Ontheseparationanddetectionofimpactconditionswereoptimizedfordifferentextractedmethods,solid-phasecolumn,chromato－graphiccolumn.Resultsshowedthat:Undertheoptimizedexperimentalconditions,themethodhadtheadvan－tagesofsimpleandquickpretreatment,easyoperation,widelinearrange(upto10to1000ng/mL),highlin－earcorrelations(upto0.9995),goodreproducibility,highRSD(lessthan5%),highrecoveryrate(upto86%-99%),highsensntivity,andlowdetectionlimits(NDPA:1ng/mL,NDMA、NDEA:2ng/mL).Keywords:Gaschromatography-massspectrometry;saltedaquaticproducts;N-nitrosamine()JournalofZhejiangOceanUniversity(NaturalScience)316201211Vol．31No．6Nov.,2012()311.2.33N-0.1g0.0001g50mLN-2.0mg/mL。N-10ng/mL、50ng/mL、100ng/mL、200ng/mL、1000ng/mL1.2.11.2.21mL。。[1-3]。N-[4-6]。N-[7]。。、、N-N-[8-10]。N-NDMA、N-NDEA[11-12]GB2762-2005《》NDMA、NDEAND－MA≤4μg/kgNDEA≤7μg/kg[13]“-”N-。11.11.1.1-GC/MSAgilentGC7890A/MS5975CAgilentVISIPRETMDLSERJSE09L31USAKQ5200DE。1.1.2N98.0%CILN-99.9%、N-99.9%SUPELCO。1.21.2.1DB-WAX30m×0.250mm×0.25μm250℃He99.999%3mL/min50℃3min10℃/min110℃15℃/min200℃40℃/min240℃1μL。1.2.2EI70eV1671V230℃150℃240℃SIMm/z40～3504min2。3N-1。13N-Tab.1RetentiontimeandGC/MSacquisitionparametersforthreeN-nitrosaminesN-GC/MS.CAS/min123N-N-N-62-75-955-18-5621-64-79.67110.77512.4054243744244561024370113130.52261.2.420.0g50mL30mLIKA1min30℃30min10min220mL40℃1.0mL。22.1DB-5MS30m×0.250mm×0.25μm、DB-WAX30m×0.250mm×0.25μmN-。N-DB-WAX、、、。DB-WAX。2.2。50℃15℃/min、10℃/min、5℃/min15℃/minN-10℃/min5℃/min10℃/min。110℃N-15℃/min。50℃3min10℃/min110℃15℃/min200℃40℃/min240℃。EI70eVSIM3N-1-1200ng/mL。2.32.3.1N-N-。2.3.25。N-1.2.4。332。2。13N--200ng/mLFig.1TotalioncurrentchromatogramofthreeN-nitrosaminesc:200ng/mL25Tab.2Comparisonofclean-upeffectsoffiveSPEcartridges12345C18CartridgesFlorisil83%82%90%71%91%59%49%62%65%83%75%61%67%68%87%72%64%73%68%87%NDMANDEANDPA：GC-MS3N-523()312NDMAAB9.671minFig.2NDMAchromatogram(A)andmassspectrogram(B)ofMIB(9.671min)2.45N-10ng/mL、50ng/mL、100ng/mL、200ng/mL、1000ng/mL。3YXN-、232～4。33N-、、Tab.3Regressionequationgs,correlationcoefficients,linearrangesandLOQsforthreeN-nitrosaminesN-/ng·mL-1/ng·mL-1NDMANDEANDPAy=93.51x+5.400×102y=59.46x+3.455×102y=35.46x+2.478×1020.99980.99950.999610～100010～100010～10002.02.01.03NDBAAB10.775minFig.3NDBAchromatogram(A)andmassspectrogram(B)ofMIB(10.775min)52464。2.63、、①、②、③1.2N-355。30.9995ND－PA1ng/mLNDMA、NDEA2ng/mLppb。2.5200ng/mL64。4NDPAAB12.405minFig.4NDPAchromatogram(A)andmassspectrogram(B)ofMIB(12.405min)4n=6Tab.4PrecisionandrecoveryforthreeN-nitrosaminesn=6N-/ng·mL-1/ng·mL-1/%RSD/%123456NDMANDEANDPA28.0428.9131.65202.34201.69215.78215.32216.56217.28211.26209.87215.30224.65221.49223.99218.63216.59220.77227.68217.35227.2687.15～99.8286.39～96.2991.82～97.814.893.822.5653N-Tab.5DeterminationresultsofthreeN-nitrosaminesinrealsamplesN-N-/ng·mL-1①②③NDMANDEANDPA35.2333.1925.6231.6932.72N.D28.0428.9131.65N.D.：GC-MS3N-525()315Fig.5SIMchromatogramofsaltedsnail3-3N-。、、N-NDMA、N-NDEA、N-NDPA3DB-WAX30m×0.250mm×0.25μm。86%～99%10～1000ng/mLNDPA1ng/mLNDMA、NDEA2ng/mLppbN-。[1]HONIKELK.Theuseandcontrolofnitrateandnitritefortheprocessingofmeatproducts[J].MeatScience,2007,78:68-76.[2].[J].,2002(4):74-75.[3].[M].:,1988:128-172.[4]YURCHENKOS,MOLDERU.TheoccurrenceofvolatileN-nitrosaminesinEstonianmeatproducts[J].FoodChemistry,2007,100:1713-1721.[5],,,.N-[J].,2006,35(4):21-23.[6].、[J].:,2004,22(2):87-89.[7].[M].:,2003:248-259.[8],,.N-[J].,2005(12):8-14.[9],,,.N-[J].,2008(4):49-53.[10],,,.N-[J].,2009(4):360-363.[11],,.N-[J].,2008,29(7):484.[12].GB/T5009.26-2003N-[S].:,2004.[13],.GB2762-2005[S].:,2006.526