环境中痕量铜、钴、镍的检测新方法研究

南华大学硕士学位论文环境中痕量铜、钴、镍的检测新方法研究姓名：杨静申请学位级别：硕士专业：卫生毒理学指导教师：廖力夫20070501II1.0.18mol/L(Cu2+)0.01~0.50µg/mL(∆A)A=1.1053ρ(µg/mL)+0.133(r=0.9993)6.43ng/mL1.1~3.2%98.3~102.0%2.Co2+1-(2-)-2-TANSDBSpH8.0BRCo2+342nmCo2+Co2+7.5~600ng/mLγ0.99902.25ng/mLB1297.8~105.4%3.NiII1-2--2-PANPANSDBS∆INiIINiII545nm∆IRLS=4502.9ρ(µg/mL)+271.82III15.2~500ng/mLγ0.99754.57ng/mLNiII50ng/mL200ng/mL400ng/mL113.5%3.0%1.7%4.MLRK-TritonX-100——CoNiPANK-Matlab7.0——MLRCoNi99.6%93.2%K-CoNi105.0%95.5%CoNi100.5%97.8%MLRK-PCRCoNi12.2%4.0%2.6%3.7%1.2%2.1%IVDeterminationofTraceCopper(II),Cobalt(II)andNickel(II)inEnvironmentAbstract1.In0.18mol/LH2SO4medium,tracecoppercansignificantlycatalyzethereactionofammoniummolybdatewithiso-propylalcoholtoproducemolybdenumbluebytheirradiationofhigh-pressmercurylamp.Basedonthis,anovelmethodforthedeterminationoftracecopperwithphotochemicalcatalyticspectrophotometryhasbeendeveloped.Inthismethod,∆AislineartotheconcentrationofCu2+intherangeof0.01~0.50µg/mLwiththecorrelationcoefficientof0.9993,thelinearequationisA=1.1053ρ(µg/mL)+0.133andthedetectionlimitis6.43ng/mL.Themethodhasbeenusedtodeterminetracecopperinriverwaterwiththerecoveryof98.3~102.0%andtherelativestandarddeviationof1.1~3.2%.2.TheresonancescatteringspectraofCobaltwith1-(2-thiazolylazo)-2-naphathol(TAN)andsodiumdodecylbenzenesulfonate(SDBS)havebeenstudied.TheRRSofthesystemisgreatlyenhancedwiththeincreasingofCobaltinpH8.0BRbuffersolution,themaxmiumscatteringwavelengthislocatedat342nm,theenhancedintensityofRRSisproportionaltotheconcentrationofCobalt.Thus,amethodofRRSforthedeterminationofCobaltisestablished.Thelinearrangeis7.5~600ng/mLwithacorrelationcoefficientof0.9990.Thedetectionlimitis2.25ng/mL.ThismethodhasbeenappliedtothedeterminationofCobaltinhumanhair,teasandvitamin12withtherecoveryof97.8~105.4%.3.Aresonancelightscattering(RLS)enhancementmethodisdevelopedforthedeterminationofnickel.TheproposedmethodisbasedontheenhancedeffectontheresonancelightscatteringofPANaftertheformationofNi-PANcomplexinthepresenceofSDBSwhichactedassensitizerinthealkalinemedium.ThemaximumVRLSwavelengthislocatedat545nm.Underoptimalconditions,∆IisproportionaltotheconcentrationofNi2+intherangeof15.2~500ng/mL,thelinearregressequationis∆IRLS=4502.9ρ(µg/mL)+271.82(γ0.9975),thedetectionlimitis4.57ng/mL,therelativestandarddeviationis3.5%,3.0%and1.7%fortheNi2+concentrationof50ng/mL,200ng/mLand400ng/mL,respectively.4.Theapplicationofmultivariatelinearityregress(MLR),K-matrixmethodandprincipalcomponentregressionmethod(PCR)forthesimultaneousdeterminationofcobaltandnickelinmixturesystembyspectrophotometrycoupledwithcloudpointextraction(CPE)hasbeenstudied.ThemethodisbasedoncloudpointphenomenonofnonionicsurfactantTritonX-100.Theformationoftwodistinctphases——asurfactant-richphaseandanaqueousphaseoccurs,whenthetemperatureofthesystemreachsthecloudpointofTritonX-100.Theion-associatedcomplexofCo-PANandNi-PANareextractedintothesurfactant-richphase.ThemaineffectsofinfluencingonCPEarestudieddetailedly.TheoverlappedspectraareresolvedbymultivariatecalibrationsuchasMLR,K-matrixandPCR.ThedataaredealtwithMatlab7.0programwrittenbyourselves.Thus,anewmethodforthesimultaneousdeterminationofcobaltandnickel——multivariatecalibrationspectrophotometrycoupledwithcloudpointextractionisdeveloped.Therecoveriesandtherelativestandarddeviationsare99.6%and93.2%,12.2%and4.0%forcobaltandnickelintheMLRmethod,105.0%and95.5%,2.6%and3.7%intheK-matrixmethod,100.5%and97.8%,1.2%and2.1%intheprincipalcomponentregressionmethod.Postgraduate:JingYang(HygienicToxicology)Directedby:Prof.LifuLiaoKeywords:copper,Cobalt,Nickel,photochemicalcatalyticspectrophotometry,resonancelightscatteringmethod,cloudpointextraction,multivariatecalibration11[1][2][1][3][4][5][6-10][11-12][13~15]2[15]II6.43ng/mL-2[16]B12[17][18][19]1-2--2-PAN2-[(5--2-)--5-5-Br-PADAP1-(2-)-2-TAN2-2--5-TAMBII[20~21]3240.72nm-0.07µg/mL1%[22]-96.0~104%0.28~1.61%[23]-0.03µg/L0.03ng/g[24]Co2+-5-Br-PADAP0.15mol/LNaOH-0.90V5.0×10-9mol/L[25]-0.25V-0.25~1.15V20µA60sNi2+Co2+-0.94V-1.00VNi2+Co2+ICP-MS[25]ResonanceRayleighScatteringRRS-PastermackRRS[26~28][29][30][31][32]Co2+1-(2-)-2-TANpH8.0BRSDBS342nmCo2+4γ0.99902.25ng/mLB1297.8~105.4%3[1]VIII123PANpH8.0Tris-HClSDBS44.15MultipleLinearRegressionMLRK-PrincipalComponentRegressionPCRArtificialNeuralNetworkANN[33~34][35~36][37][38][39]CrIIICrVICrIIICrVI[40~41]1234.26(cloudpointCP)5%—[42~44][45][46][47]K-241[68][69][70][71]Ni2+PANpH8.0Tris-HClSDBS22.1F-4500UVVis8500/pHS-3C()1mg/mL1.0000g500mL1+115mL1LPAN2×10-4mol/LSDBS0.025%m/vTris-HClpH8.02.210mLNi2+pH8.0Tris-HCl0.6mLPAN1.2mLSDBS0.5mL50oC30minλem=λex545nmIRRSI05.0nm3253.13-1RRS3-1PANSDBS250~650nmRRS12SDBSNi2+IRRS3SDBSIRRS4~7SDBSNi-PAN545612nmRRS545nm612nmRRS544nm605nm545612nm3-1Fig.3-1RRSspectraofthesystem1.Tris-HCl+SDBS2.Tris-HCl+PAN3.Ni+Tris-HCl+PAN4~7.Ni+Tris-HCl+PAN+SDBS.CNi(µg/mL):3.0.2;4.0.05;5.0.1;6.0.2;7.0.3;PAN:2.4×10-5mol/L;SDBS:0.00125%;Tris-HCl:0.6mL,pH=8.03-23-2PAN470nmNiNi2+PAN544605nmNi2+NiPANPAN3-13-2263-2Fig.3-2AbsorptionspectraofthesystemPAN:2.4×10-5mol/L;SDBS:0.00125%;Tris-HCl:0