有机磷农药在蔬菜和土壤中的降解规律研究

成都信息工程学院硕士学位论文有机磷农药在蔬菜和土壤中的降解规律研究姓名：杨怀金申请学位级别：硕士专业：环境科学指导教师：叶芝祥20070510IMAE-GC()IEA()MAE-GC()2.3%4.3%84.0%104.8%1.34d4.91d1.10d0.97d2.01d6.11d5.82d0.19dIIIEA,IIIStudyontheDegradationRegularityofOrganophosphorusPesticideinVegetablesandSoilMajor:EnvironmentalScienceM.S.Candidate:YangHuai-jinSupervisor:Prof.YeZhi-xiangAbstractOrganophosphoruspesticideresiduesincludingdimethoateanddichlorvos,invegetablesamplesandsoilsamples,wereextractedbymicrowaveheatinganddeterminedbythequantificationcarriedonthegaschromatographyusingFPDasdetector.Theretardationkineticmodel,nonlinearkineticmodelandself-adaptivenonlinearkineticmodel,werefirstappliedtodescribethedegradationregularityoforganophosphoruspesticides(dimethoateanddichlorvos)invegetableandsoil,andtheparametersineverymodelswerealsooptimizedbyimmuneevolutionaryalgorithm(IEA).Theobtainedresultsinthepresentworkwereillustratedasfollows:Itwasfoundthattherelativestandarddeviationsonthedeterminedcontentsofdimethoateanddichlorvosinvegetablesamplesandsoilsamples,were2.3~4.3%andtheirrecoverieswere84.0~104.8%,showingthattheextractionbyusingmicrowaveirradiationandthedetectionbyFPDequippedonGCmethodwereabletomeettheanalysisoforganophosphoruspesticideresidues.Theself-adaptivenonlinearkineticsmodelcouldsimulatethedegradationregularityofdimethoateexistedinspinachfromtheplasticshed,andthenonlinearkineticmodelcouldsimulatethosefromthefield.TheretardationkineticmodelIVcouldsimulatethedegradationregularityofbothdichlorvosanddimethoateexistedinspinachfromboththeplasticshedandthefield.Thehalf-lifeofdimethoate,existedinspinachfromtheplasticshedandfromthefield,wascalculatedtobe1.34and4.91days,respectively,andhoweverdichlorvoswere1.10and0.97days,respectively.Thehalf-lifeofdimethoate,exitedinsoilsfromtheplasticshedandthefield,was2.01and6.11days,andhoweverdichlorvosbeing5.82and0.19days,respectively.Thusitcouldbeobservedthatthedegradationrateofdimethoateexistedinspinachfromtheplasticshedwasfasterthanfromthefield.Andatthesametime,thedegradationrateofdichlorvosexistedinspinachfromtheplasticshedwasslowerthanfromthefield.Furthermore,IEAwasprovedtobesimple,convenientandfeasiblefortheoptimizationparametersinthekineticmodelsofthepesticidedegradation.Therefore,itwouldcarveoutanewtheoreticalwayfortheestablishmentofthepesticideresidualmodelandtheresearchofpesticidedegradationinagricultureecologicalenvironment.Keywords:Organophosphoruspesticide;Gaschromatography;Immuneevolutionaryalgrorithm(IEA);KineticModel6364164170%70%32.8%[1][2-3][4-5]WTO70[6][7]2,,,,,,,,,[8]20014,,264[9]GB18406.1-2001[10]1.0mg/kg0.2mg/kgGB18406.1-2001()33.1,,,[11][12]364SFE[13-14]SPE[15-16]LLESPME[17-19]MAEASE3.2,SFE-GC[16]RH-GC[20]SPE-GC[21]GC-MS[22-26]LCMS[27-30][31]LC-MS[32-33]70%GC,,,,GC,,,,,GC,GC,,,,(ECD),(FPD)4,,,,464,,[34-35],pH[36]70%80%[36]57080[37][38][39],[40][41][42]48%[43][44][45][46],,564[47-62][47]Rayleigh[57],[58][59][60]RayleighGM(1,1)[61][62],(pH),,,[63-64],(),(),[65]k,(2/1T)k,,,,[65]664,,,,,S[65],,[65-67],,,VerhulstLogistic,,[65][66][67],,[65-67]Gauss-Newton:[68][69-71]Gauss-Newton(Marquardt)[66,72]764[73];[70]GeneticAlgrorithmGA[74][75-78],[74,79],GA[70,71,73]ImmuneEvolveAlgrorithmIEAGA[80],[81-82]IEAIEAMAE-GC()()864122.12.22.2.1GC-2010FPDDB-1mmmmµ25.025.030××XT-9900P1000W50100%P,(HC-TP11-2,)2.2.240%80%98%Dr100mLg/µmLg/13.0µ±100mLg/µmLg/15.0µ±964100mLg/µmLg/15.0µ±99.5%:AR99.999%99.999%99.999%2.3[83]40%100080%120024500g50g2.4-MAE-GC2.4.1MAE-GC2.4.1.12.4.1.21g(PTFE),15mL,,,,6min2-1,10640.45mµ,10mL5mL2-1kg(%P)(s)115060237012034801802.4.1.3Lµ12.4.2MAE-GC2.4.2.12.4.2.21g(PTFE),15mL,,,,8min2-2,0.45mµ,10mL5mL11642-2kg(%P)(s)1150602260120343470801201802.2.4.2.3Lµ12.52.5.11mLg/µ100mLg/µ1mL100mL1mLg/µ1mLg/µ100mLg/µ1mL100mL1mLg/µ2.5.211.0mg98%10mL5.5mL2mLmg/2mLmg/100mLg/µ2.5.3100mLg/µ1mL100mL1mLg/µ12642.6DB-1mmmmµ25.025.030××100C°0.4min40C°/min220C°5min250C°99min/88.2mL57.1cm/secFPD280C°99.999%min/80mLmin/85mLmin/0.3mL2.72.7.1mlg/25.0µmLg/15.0µ2.7.239C0,[84]2.7.32.7.3.1mLg/5.0µmLg/25.0µLµ12-14.37min5.26min2.7.3.2mLg/10.0µmLg/15.0µLµ12-22.43min4.04min13642-1mLg/5.0µmLg/25.0µ2-2mLg/10.0µmLg/15.0µ14642.7.42.7.4.10.10mLg/µ0.20mLg/µ0.50mLg/µ1.0mLg/µ0.25mLg/µ1LµiAsAiCsC2-30.99760.00.51.01.52.02.53.03.54.04.50.00.51.01.52.02.5Y(Ai/As)X(Ci/Cs)y=-0.1515+0.6592xR=0.99762-32.7.4.20.01mLg/µ0.10mLg/µ0.20mLg/µ0.4mLg/µ0.80mLg/µ1.0mLg/µ0.15mLg/µ1LµiAsAiCsC15642-40.9924012345670.00.51.01.52.0y=-0.04678+0.30005xR=0.9924X(Ci/Cs)Y(Ai/As)2-42.7.52.7.5.1MAE-GCMAE-GCMAE-GC1Lµ2-3103.3%2-3MAE-GCmg/kgmg/kg12.10762.07622.06172.09532.07182.08042.05092.12952.035102.022*=3.3%16642.7.5.2MAE-GCMAE-GCMAE-GC1Lµ2-4103.7%2-4MAE-GCmg/kgmg/kg10.822960.893020.868670.904230.838780.871040.866690.923650.8559100.8640*=3.7%2.7.5.3MAE-GCMAE-GCMAE-GC1Lµ2-5104.3%2-5MAE-GCmg/kgmg/kg11.26861.24521.34171.28931.29581.31441.20591.29951.212101.204*=4.3%17642.7.5.4MAE-GCMAE-GCMAE-GC1Lµ2-6102.3%2-6MAE-GCmg/kgmg/kg10.514260.535720.490770.507430.491080.546740.477490.508650.5271100.5403*=2.3%2.7.62.7.6.1MAE-GCMAE(GC)kgmg/6.0kgmg/9.0kgmg/20.1,kgmg/6.0kgmg/9.0kgmg/20.12-72-7MAE-GC84.0%