ICP-MS的结构、原理与应用培训（PerkinElmer公司）.pdf

PerkinElmerPerkinElmer公司北京办事处公司北京办事处公司北京办事处公司北京办事处姚继军姚继军姚继军姚继军ICPICP-MSMS的结构、原理与应用培训的结构、原理与应用培训的结构、原理与应用培训的结构、原理与应用培训1、ICP-MS有什么用？有什么用？定性、半定量和定量分析定性、半定量和定量分析ICP-MS在稀土分析中的应用在稀土分析中的应用ICP-MS在稀土分析中的应用在稀土分析中的应用ICP-MS在稀土分析中的应用在稀土分析中的应用ICP-MS在稀土分析中的应用在稀土分析中的应用典型的典型的CDC样品样品綠色產品標記綠色產品標記.台灣 綠色標記台灣 綠色標記Green Mark 德國 藍天使德國 藍天使Blue Angel 加拿大 環保選擇加拿大 環保選擇Environmental Choice 日本 環保標記日本 環保標記Environment Label北歐理事會 白天鵝北歐理事會 白天鵝Nordic Swan 新加坡 綠色標記新加坡 綠色標記Green Label 紐西蘭 環保選擇紐西蘭 環保選擇Environment Choice 歐洲聯盟 環保標記歐洲聯盟 環保標記Environment Label 环保行业的典型控制值环保行业的典型控制值GermanyUSAJapanGermanyUSAJapanElementmg/Lmg/Lmg/LElementmg/Lmg/Lmg/LAg0.010.100.10 Mo 0.07Al0.200.20 Na 150As0.010.01 Ni 0.050.01B1.001.00 P 5.00Ba1.002.00 Pb 0.040.05Be0.004 Pt Ca Sb 0.010.0060.002Cd0.010.0050.01 Se 0.010.050.01Co Si Cr0.050.100.05 Sn Cu3.001.001.00 Sr Fe0.200.300.30 Tl 0.002Hg0.0010.002 V K12.0 Zn 5.005.001.00Li U 0.030.002Mg50.0Mn0.050.050.05Collecting water samplesEPA Sampling TeamICP-MS(Perkins Elmer Elan 6100)同位素比值分析同位素比值分析Pb isotopesPb 1mg/L(ppb)107107Ag/Ag/109109AgAg的同位素比值精密度小于的同位素比值精密度小于的同位素比值精密度小于的同位素比值精密度小于0.08%0.08%Re/OsRe/Os的比值的比值的比值的比值元素形态分析元素形态分析元素形态分析元素形态分析As SpeciationlSeparation of As(III),As(V),MMAs,and DMAs?MMAs=Monomethylarsonic acid?DMAs=Dimethylarsinic acid-Alkaline separation?200mmol/L NaOH/DI water+3%methanol-AS-16 column(Dionex)with gradient elution01000020000300004000050000600000200400600800Time(seconds)Intensity(cps)AsBAs(V)As(III)MMAsDMAsDegradation Products01000200030004000500060007000800090001000002468101214161820Time(min)Intensity(cps)As(V)MMAs(V)RoxAsAs(III)?4-hydroxyphenylarsonic acid3-amino-4-hydroxyphenylarsonic acidGC-ICP-MSLA-ICP-MS微区分析2、ICP-MS为什么能有这些功能？为什么能有这些功能？ICP-MS DefinitionlAn analytical technique to determine Elementsusing Mass Spectrometry from Ions generated by an Inductively Coupled PlasmalMass spectroscopySeparation(by Mass/Charge)and measurementof the mass of individual atoms making up a given materialeg.Na at mass 23 from Mg at mass 24;charge is 1 in argon plasma.ICP-OES GC-MSICP-MSICP-MSFirst developed and introduced in early eighties(1983,SCIEX)ICP.SampleInterfaceMass spectrometerDetectorThe Purpose of the PlasmaDesolvation:Drying DropletsVaporization:Particles to gasExcitation:EmissionAtomization:DissociationIonization:Electron Losse-+n nGround State ElectronGround State Electronn nQuantized Quantized OrbitalsOrbitals-Bohr Model of Hydrogenn nQuantum of energy is addedQuantum of energy is addedn nEnergy SourceEnergy SourceY YHeatHeatY YEnergetic electrons and ionsEnergetic electrons and ionsY YLightLight+Excitationn nElectron returns to lower energy levelElectron returns to lower energy leveln nLight is emitted at a specific wavelengthLight is emitted at a specific wavelengthLight+Decay and EmissionExcitationEmissionEnergyIon Excited StateIon Ground Stateabcda,b excitationc ionizationd ion excitationefghe ion emissionf,g,h atom emissionExcited States 4321Energy Level Diagramn nMany transitions are possibleMany transitions are possiblen nEmitted light depends on energy difference Emitted light depends on energy difference of two statesof two statesDecay with Emission of Light+ExcitedStatesE=h=hc/h=Plancks constant,=frequency,c=velocity of light,=wavelengthOrigins of Atomic SpectraPrinciple of Atomic SpectroscopyHHeLiMEnergyEmission(e)Absorption(a)IonizationAbsorption(a)Emission(e)Ground stateExcitation levelIonizationV:Ionizsation potentialEn,Em:Excitation potential E=En-Em=h EnEmVBeICP-MS双电荷离子干扰双电荷离子干扰0102030405060708090020406080100Atomic numberIonisation efficiency(%)LiBeBCBaMgAlSiPSClKCaScVTiCrMnZnGaGeCuFeNiCoAsSeBrRbSrYZrNbMoTcRuRhPdAgCdInSnSbTeIXeCsNaLanthanoidesHfTaWReOsIrPtAuHgTl PbBiPoRnRaAcNFKrHeONeArElectron temperature:6,680KElectron density:1.4714x 10 cm-1Ar等离子体中元素的离子化效率等离子体中元素的离子化效率ICPICP-MSMS接口接口接口接口大孔径的接口是现代研究用大孔径的接口是现代研究用ICP-MS的标志的标志离子聚焦过程离子聚焦过程-离子穿过锥孔进入离子透镜快速拆卸接口锥，业界最大接口锥孔径（1.1mm、0.9mm)离子穿过锥孔进入离子透镜快速拆卸接口锥，业界最大接口锥孔径（1.1mm、0.9mm)ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆ICP-MS四极杆四极杆脉冲方式鉴别r计数低浓度高浓度ELAN-具有SimulScan的双阶倍增检测器ELAN-具有SimulScan的双阶倍增检测器gate模拟/脉冲系数模拟方式A/V 转换 同时自动获得模拟同时自动获得模拟同时自动获得模拟同时自动获得模拟和脉冲信号和脉冲信号和脉冲信号和脉冲信号 事先不需要知道分事先不需要知道分事先不需要知道分事先不需要知道分析物含量水平析物含量水平析物含量水平析物含量水平 使线性动态范围扩使线性动态范围扩使线性动态范围扩使线性动态范围扩展到展到展到展到9 9 9 9个数量级个数量级个数量级个数量级3、ICP-MS技术是如何发展起来的？技术是如何发展起来的？PerkinElmer PerkinElmer SciexSciexICPICP-MSMS的先行者和创新者的先行者和创新者的先行者和创新者的先行者和创新者1983 ELAN 250世界第一台商用世界第一台商用 ICP-MS1987 ELAN 500第二代第二代 ICP-MS1990 ELAN 5000 第三代第三代ICP-MS，第一个采用分子涡轮泵；环境分析里程碑式的进展，第一个采用分子涡轮泵；环境分析里程碑式的进展1994 ELAN 6000第四代第四代ICP-MS,采用扩展线性范围的检测器，应用于更多的日常分析采用扩展线性范围的检测器，应用于更多的日常分析1999 ELAN 6100第五代第五代ICP-MS,为各种不同的应用领域确立了行业标准为各种不同的应用领域确立了行业标准ELAN 6100 DRC 第一代第一代采用动态反应池技术的采用动态反应池技术的ICP-MS（Dynamic Reaction Cell，DRC）2001 ELAN DRCPlus第二代第二代DRC,采用了轴向场技术采用了轴向场技术（Axial Field Technology，AFT）2002 ELAN 9000第六代第六代 ICP-MSELAN DRC II 第三代第三代 DRCELAN DRC-e 第三代第三代DRCICP-AESMass SprctrometryQ-ICP-MS第1代ICP-MSHR-ICP-MS第2代ICP-MSMC-HR-ICP-MS第3代ICP-MS1970s1980s1990s2000s1960sRCQ-ICP-MSDOSDOS/WINDOWSWINDOWSTOF-ICP-MS等离子体质谱分析技术发展历史等离子体质谱分析技术发展历史DRC-ICP-MS第4代ICP-MSICP-MS测定研究对象变化1970s1980s1990s2000s1960s无机微量元素含量同位素信息同位素比值精密测定元素形态地质冶金半导体环境核材料生命科学等离子体质谱分析的研究热点等离子体质谱分析的研究热点技术方法角度技术方法角度1）基体干扰消除方法研究）基体干扰消除方法研究2）质谱干扰校正技术研究）质谱干扰校正技术研究3）多接收高分辨）多接收高分辨ICP-MS的研究发展的研究发展4）特种进样技术的研究）特种进样技术的研究5）分离技术与）分离技术与ICP-MS检测技术联用检测技术联用研究对象角度研究对象角度5）化学计量学研究）化学计量学研究1）环境毒物）环境毒物2）生物组织）生物组织3）有机材料）有机材料4）微量样品超痕量元素）微量样品超痕量元素为适应对象而研究为适应技术方法而研究电感耦合等离子体质谱仪（ICP-MS）的发展MC-ICP-MSTOF-ICP-MSQ-ICP-MS四极杆四极杆+通道式检测器（通道式检测器（1983）电磁双聚焦）电磁双聚焦+多个多个Faraday杯或者杯或者Daly检测器电磁双聚焦检测器电磁双聚焦+Faraday杯或者杯或者Daly检测器飞行时间检测器飞行时间+ETP检测器检测器SF-ICP-MSCCT-ICP-MSDRC-ICP-MSORS-ICP-MS碰撞池碰撞池+ETP检测器碰撞反应池检测器碰撞反应池+ETP检测器动态反应池检测器动态反应池+ETP检测器检测器PerkinElmer-世界第一的品牌世界第一的品牌Perkin Elmer原子吸收光谱仪原子吸收光谱仪-AAS领航者领航者l1961 世界第一台商品双光束原子吸收光谱仪l1970 世界第一台商品石墨炉原子吸收光谱仪l1988 商品流动注射原子光谱联用仪l1990 横向加热、纵向塞曼效应背景校正的石墨炉原子吸收光谱仪l1994 单道同时多元素分析石墨炉原子吸收光谱仪PerkinElmer-世界第一的品牌世界第一的品牌ELAN Product HistorylELAN 250-1983-First commercially available ICP-MS-Cryogenic pumping system-On-board computer-Manual operationlELAN 500-1987-Improved sensitivity-Improved resolution-new quadrupole and power supply-OmniRange extended dynamic range-Corrosion resistant sample introduction systemPlasmaLok专利接口设计专利接口设计R FR FR F等离子体势能等离子体势能RF H.V.?To Ground?To Ground?RF H.V.RF H.V.?To Ground?RF coil turns0 1.5 30 1.5 3RF coil turnsPlasma potentialPlasma potentialAverage plasma potentialAverage plasma potentialConventional SystemPlasmaLok System0 v0 v+-最适于分析复杂样品的进样系统最适于分析复杂样品的进样系统 标准配置Ryton scott 雾室和十字交叉雾化器-内置三通道蠕动泵，具备Tubing Saver 功能ELAN Product HistorylELAN 5000-1990Improved reliability and ease of use-First turbo pumped ICP-MS-Free running ICP RF generator-New quadrupole and power supply-Improved interface-Windowing,mouse controlled PC software-TotalQuant spectral interpretation and semiquantitative analysis package-On-board continuous system diagnosticsELAN Product HistorySmallest footprint in the industryFirst simultaneous automatic extended dynamic range detection systemImproved ion optical train with improved performanceFaster,more powerful quadrupole systemAdvanced automation and productivitylElan 6000-1994&Elan 6100/DRC-1999易 于 更 换 耐 用 的 离 子 锥易 于 更 换 耐 用 的 离 子 锥专利的专利的AutoLens技术，真正实现免拆洗的强大保证技术，真正实现免拆洗的强大保证偏转 挡板偏转 挡板 偏转偏转Voltage is fixed and frequency changes with mass scanNeutral species from plasmaDRC cell(U+V cos wt)150 vShadow stopAutoLensM+Grounded differential aperture no voltage no driftNon-Extraction SystemELANBackground ions from the interfaceSampling coneSkimmer conePlasmaIons from the sample+3 to 8 V-15 15 V V+Extraction Lens SystemExtraction lens-100v to 4000vIons from the samplePlasmaSampling coneSkimmer coneBackground ions from the interface+Cone MaintenanceGeneral Cleaning ProcedurelRemove cones and O-ringsCheck condition of O-ringslWipe off surface of cones with a Kimwipe or(cotton swab)moistened with 2%HNO3to remove surface depositslPlace cones upside down in a container(shipping container works well)lConfirm nothing is touching tip of coneNote:Failure to clean the cones in anUpside down orientation may causeirreparable damage to the cone.Skimmer ConeWater BathBeakerDetergent Solution自动优化透镜偏压自动优化透镜偏压0.20.40.60.811.213579Lens Voltage(V)Li Co Y In Pb UNormalized SignalMassResponse(normalized to In)61009000Mg 3xELAN 9000 改进低质量元素的灵敏度ELAN 9000 改进低质量元素的灵敏度Sensitivity Improvement With AutoLensELAN系列系列装机量世界第一的装机量世界第一的ICP-MSELAN 9000ELAN 9000-完美的真空系统完美的真空系统l特点-两个集中控制的分子涡轮泵!两个集中控制的分子涡轮泵!?双入口结构双入口结构?空气冷却!空气冷却!?离子透镜和四极杆室分开离子透镜和四极杆室分开l优点-抽真空时间:抽真空时间:?5-10 分钟5-10 分钟-可加装耐腐蚀吹扫装置可加装耐腐蚀吹扫装置-保养离子透镜时不需要打开四极杆盖板保养离子透镜时不需要打开四极杆盖板-维护保养更加方便维护保养更加方便?8 分钟真空室可恢复到常压状态8 分钟真空室可恢复到常压状态两个集中控制的分子涡轮真空泵独立盖板ICP-MS分析中的干扰分析中的干扰红色斜体表示具有较高的离子能，无法在冷等离子体中分析红色斜体表示具有较高的离子能，无法在冷等离子体中分析。棕色阴影的元素具有较高的氧化物结合能，无法在冷等离子体中分析。棕色阴影的元素具有较高的氧化物结合能，无法在冷等离子体中分析。棕色阴影的元素具有较高的氧化物结合能，无法在冷等离子体中分析。棕色阴影的元素具有较高的氧化物结合能，无法在冷等离子体中分析。绿色带下划线的干扰物无法在冷等离子体中除去绿色带下划线的干扰物无法在冷等离子体中除去AnalytemassH2OClSPCNaMgCaKAlCNAs75ArClCa40Ar Co59CaOCr52ArCClOHSOHArCCu63,65PO2 ArNaArMgFe54,56,58ArO,ArNCaOGa69,71ClO2Ge72,74ArSK39ArHClH2MgCCMn55ArOH,ArNKONi58,60CaOSe76,77,78,80ArArArCl46,47,48,49,50O3SO,SNPO,POH51ClOSOHZn64,66,68S2,SO2PO2HArMgCaOTiTiV VChloride Interference on Arsenic:ELAN 6100 and DRC01020304050600200040006000800010000Intensity at m/z 75(cps)Chloride Concentration(mg/L)ELAN 6100ELAN DRCArCl+Signal vs.Chloride ConcentrationCalcium Interference on Arsenic:ELAN 6100 and DRC02004006008001000120014000100200300400500600Calcium Concentration(mg/L)Intensity at m/z 75(cps)ELAN 6100ELAN DRCCaCl+Signal vs.Calcium ConcentrationDetection LimitsInstrumentAsPbCdHgELAN 61000.0720.0200.1500.230ELAN DRC0.0410.0150.0510.068Whole Blood and Urine Detection Limits are the sameUnits=g/LDetermined as 3*SD of 10 separate matrix blanksWithin Run Stability:BioRadUrineAnalysis Time:1 hr.15 min.0204060801001201401601802000510152025ASPBCDHGSample NumberConcentration(g/L)CV1.8%1.8%3.6%2.8%01000200030004000500060007000707580859095Conversion of As+to AsO+Sample:1 ppb As in 1%HNOSample:1 ppb As in 1%HNO3 3As+(std mode)AsO+(DRC mode)O2=0.45 mL/minAs+converted to AsO+Problematic OxideslMoO and ZrO interfere with Cd and Pd isotopeslHfO interferes with most abundant isotopes of PtlTaO interferes with monoisotopic AulZrO and NbO interfere with AglWO interferes with HgCe/CeO scans,Ce+O2 CeO+(No CeO2+observed)10ppb Ce,red-standard mode,blue-0.25mL/min O2Ce+CeO+-with a low flow of O2all the Ce is converted to the oxide238U,UO and UO2 scans,U+O2 UO2+10ppb U,red-standard mode,blue-0.25mL/min O2U+UO+UO2+-all the Uranium is converted to the dioxidePb/PbOH scans,Pb+H2O PbOH+H 10ppb Pb,red-standard mode,blue-0.25mL/min O2Pb+PbOH+-Pb is not oxidized!10ppb Cd+Zr+Mo with Cell Gas 2.25mL/min O2Isotopic fingerprint is based on IUPAC ratiosThe ELAN 6100/6100 DRC plusAward Winning DRCSchematic Diagram of ELAN DRCDetectorShadowStopTurbomolecularpumpsRoughing pumpsAr gas inMain Q-poleDC+AC(U+Vcos t)DRCDC+AC(U+Vcos t)E-LensPre-filterAC only(Vcos t)Gas inletVent valveAxial FieldAxial FieldGradient DCGradient DCScan Line of QScan Line of Q-polepoleMain Q-pole scan lineAC(V)DC(（U)9Be59Co115In238U238U stable regiona=m 2r24 e Uq=m 2r22 e Vpre-filter and collision cell scan lineQQ-pole Scan Line(2)pole Scan Line(2)a9Be59Co115In238UDRC scan linea=m 2r24 e Uq=m 2r22 e VLowHighHighLowMain Q-pole scan lineFrequency()ICP-MS with a Dynamic Reaction CellConesLensMass Analyzer QuadDetectorReaction Cell QuadDRC与与CCT、ORS的区别的区别动态反应池（DRC）技术四极杆设定质量范围准确控制和消除干扰离子通过反向电场来排斥能量较低的干扰离子通过碰撞使分析物离子和干扰离子的能量分开碰撞池（CCT，六极杆）碰撞反应池（ORS，八极杆）DRC与与CCT、ORS的区别的区别lPerkinElmer的设计DRC-ICP-MS?ICP+四极杆+四极杆热电的设计CCT-ICP-MS?ICP+六极杆+四极杆l安捷伦的设计ORS-ICP-MS?ICP+八极杆+四极杆DRC与与CCT、ORS的区别的区别l为什么没有公司设计ICP+六极杆+六极杆ICP+八极杆+八极杆?答案：只有四极杆可以将不同的离子分离开来，六极杆和八极杆本身无法分离不同的离子，所有的离子都可以通过六极杆和八极杆。Stable Diagram of HexapoleMass Filter(at 0.1r0)Stable Diagram of OctopoleMass Filter(at 0.1r0)Hagg and Szabo,IJMSIP(1986),73,277What happens in the Cell?MMH+MO+MN+MC+MOH+MNH+CH+CnHm+CN+Ions coming from plasma generate by-product ions by chain reaction.The ion kinetic energy of by-product ions are relatively lower.H+O+N+C+Ion Energy+1 v-5 v0 vM+M+M+M+M+M+-5 v+1 vM+M+M+M+M+M+M+M+M+M+Ion energy=kinetic+potentialmv2=3eV12Kinetic energy=Kinetic PotentialKinetic PotentialM+M+M+M+M+M+M+M+M+M+M+M+Kinetic Energy DiscriminationPlasma potentialIon lens potentialCell potentialQ-pole potential0 v+-7 eV-1 V+1 V-20 VEffect of Kinetic Energy DiscriminationN.Yamada et al.presented at 2002 Winter Plasma Conference4、ICP-MS和其它仪器相比有哪些优缺点？和其它仪器相比有哪些优缺点？Flammable gasInflammablegasDetectorSlitSlitGrating driven by motorHollow CathodelampSampleFlamePrinciple of Flame Atomic Absorption(FAAS)Advantages of FAAS-not expensiveDisadvantages of FAAS-poor sensitivity-not multi-element-narrow dynamic rangeGraphite TubeAr gasDetectorSlitGrating driven by motorHollow cathode lampAtomizationSlitAtomizationCleaningTemperature program02040608010005001,0001,5002,0002,500Time(second)Temperature(C)Principle of Graphite Furnace Atomic Absorption Spectrometer Graphite TubeCooling water inWater outWater jacketphotonwindowAdvantages of GFAAS-reasonable initial cost.-quite high sensitivity.Disadvantages of GFAAS-slow measurement-interference-narrow dynamic range-some impossible elementsPrinciple of Inductively Coupled Plasma Optical Emission Spectrometry(ICP-OES)Polychrometer system(Multi-channel type)Fixed gratingArplasmaSlitDetectorExit slitMonochrometersystem(Sequential type)SlitDetectorSlitGrating driven by motorEchelle type(Axial view)SlitEchelleInterfaceCCDSample aerosolSample aerosolPhotocurrent(Amperes)-9 10-8 10-7 10-6 10-5 10Wavelength(nm)190270310330230250290210350Pb 100mg/L123456789121110Features of ICP-OESAdvantages of ICP-OES-very fast measurement.-multi-element.-very good stability.-many choice of emission lines.Disadvantages of ICP-OES-sensitivity varies amongelements.-continuous background.-some spectralinterferenceIsotope and IsobarFeAtomic number=26Atomic weight =55.845 gIsotopes Abundance(%)ProtonsNeutrons Electrons54Fe 5.84526282656Fe91.75426302657Fe2.11926312658Fe0.282263226NiAtomic number =28Atomic weight =58.6934 g58Ni68.076928302860Ni26.223128322861Ni1.139928332862Ni3.634528342864Ni0.9256283628AtomHe Atomic number =2Atomic weight =4.002602 g +-+-NucleusProtonElectronNeutronElectron cloud+ProtonNeutron+-Proton1,840 electrons 原子光谱检出限原子光谱检出限1001010.10.010.001火焰原子吸收电感耦合等离子体发射火焰原子吸收电感耦合等离子体发射-径向电感耦合等离子体发射径向电感耦合等离子体发射-轴向氢化物发生原子吸收石墨炉原子吸收电感耦合等离子体质谱检出限范围 轴向氢化物发生原子吸收石墨炉原子吸收电感耦合等离子体质谱检出限范围 g/l7-AS115、ICP-MS如何使用？如何使用？Daily OptimizationX-Y AdjustmentNebulizer GasFlow OptimizationCeO/CeOptimizationLens(AutoLens)OptimizationCheck InstrumentPerformanceELAN Background LevelsPurpose:A scan of the mass range provides information on the following:lPurity of deionized waterlPurity of argonlBackground ion intensitieslContamination in sample introduction systemlContamination on conesComplete OptimizationStartTuning Mass CalibrationResolutionX-Y AdjustmentNebulizer GasFlow OptimizationLens Voltage OptimizationCheck Instrument PerformancePulse Stage Detector OptimizationAnalog Stage DetectorOptimizati