1、Hitachi Ltd.Instruments此文本为一会议报告，不属仪器分析课程要求的内容。有兴趣的同学可以看一看。ICP/AESAtomic Absorption FurnacePlasma/MS (ICP/MS MIP/MS)ppt ppb ppmThrough-put(Elements/min)0.01 0.1 1 10 100 Single Element Multi Element Analysis AnalysisAtomic Absorption FlameP-5000P-4010Z-5010 seriesP-6000Atomic Absorption Furnace&Flam
2、eICP-AESICP-MSMIP-MSSensitivityIon trap type ICP-MSHi-Power MIP-MSICP-MS电感耦合等离子体质谱仪Inductively Coupled Plasma Mass Spectrometry等离子体等离子体-离子源离子源质谱质谱-按原子按原子(分子分子)质量顺序排列质量顺序排列 的图谱的图谱质谱仪质谱仪-质量分析仪质量分析仪,对带电粒子对带电粒子起作用起作用,M/e,M/e与离子强度与离子强度其他联用技术其他联用技术 GC-MS HPLC-MSGC-MS HPLC-MS特点特点:无机质谱无机质谱 分析速度快分析速度快 线性范围宽线
3、性范围宽 可多元素测定可多元素测定 80 80多种元素多种元素 检出限低检出限低 PPTPPTCharacteristics P-5000的优势的优势Combination of an inductively coupled plasma ion source and an ion trap for elemental analysis.1.Reduction of matrix ions derived from argon by using tandem mass spectrometry(MS2)2.Space charge effects suppressed by using fil
4、tered noise field(FNF)3.Ion concentration through trapping(a detection limit is ppt level for most elements)要点要点:1.ICP1.ICP和三维四极离子阱的结合是目前为止和三维四极离子阱的结合是目前为止最佳的最佳的ICP-MSICP-MS 原因原因:MS2:MS2解决了分子离子的干扰解决了分子离子的干扰 FNF FNF解决了空间电荷效应抑制问题解决了空间电荷效应抑制问题 离子阱的储存离子功能提高灵明度离子阱的储存离子功能提高灵明度IntroductionP-5000 ICP-MS is
5、the first ion trap type ICP-MS in the world.It offers:1.Low Background signal2.High sensitivity 3.Wide dynamic range4.Easy operation Structure of P-5000 ICP-MSDetectorIon trapIon guideSampling coneSkimmer coneTorchChamberNebulizerRotary pumpsTurbo molecular pumpsPeristaltic pumpComparison of ion tra
6、p and conventional QMS#Tandem mass spectrometry#Relatively compact instrument#High transmission efficiency in the selected ion monitoring(SIM)modeQMS:transmitting typeIon trap:trapping type提示提示:离子阱全能离子阱全能 与与ICPICP结合最佳结合最佳 四极杆适合选择离子检测四极杆适合选择离子检测 与与GC,LCGC,LC配合更好配合更好Ion trap basic action(Entrance gate
7、)(Exit gate)IonsDetectorIons trapping Ion detectionTimeMulti functionanalysisopenclosecloseclosecloseopenEntrance gateExit gate1.Low background signal In a P-5000 system,collision-induced dissociation is used to eliminate the interference from molecular ions.碰撞诱导分裂碰撞诱导分裂2.Hi-sensitivity and wide dyn
8、amic rangeBy changing the ion trapping time,it is possible to change the ion sensitivity.阱的时间阱的时间3.Easy measurement Simultaneous analysis,qualitative,quantitative analysis.4.Ar-ICP ion source RF:27 MHz,Maximum Power:1.4 kWMain problem of conventional ICP-QMSMolecular ionIt is impossible to distingui
9、sh the ions with the same m/z.Measurement ionSame m/zSeSe+ArArArAr+SeSe+ArArArAr+Impossible to distinguish:Measurement Ion :Moleculars:after dissociationIn the P-5000 system,next 2 stage1.Natural decluster 自然去簇自然去簇2.Collision-induced dissociation(CID)碰撞诱导分裂碰撞诱导分裂is used to eliminate the interference
10、 from molecular ions.Elimination method for the molecular ions.Ion tap Cool plasma+QMS Reaction cell+QMSAr-molecular ionsSensitivity of other ionsEliminationMetal-oxide ionsPossible Possible PossiblePossible Impossible ImpossibleGoodbadbadReaction gasHe-NH3,H2Different of background spectrumICP-QMSP
11、-5000Ion trap ICP-MSBy changing the ion trapping time,possible to change the ion sensitivity.IntensityIon trapping time1 10 100 1000 1000010000 1000 100 10 1msecWide dynamic rangeCalibration Curve1.000 050100Concentration(ppt)208 Pb400500600700Intensity 11BR2=1.00027AlR2=1.00055MnR2=1.00056FeR2=1.00
12、063CuR2=1.00066ZnR2=1.000 15000 0 50 100 Conc.(ug/L)350000 50 100 Conc.(ug/L)070000 0 0 25 50 Conc.(ug/L)70000 4000 0 150 300 Conc.(ug/L)080000 0 50 100 Conc.(ug/L)060000 0 50 100 Conc.(ug/L)052CrR2=1.00060NiR2=1.00075AsR2=0.9980 25 50 Conc.(ug/L)30000 2000 0 5 10 Conc.(ug/L)0 60000 0 5 10 Conc.(ug/
13、L)50000 0Analysis of tap water80SeR2=0.99898MoR2=1.000112CdR2=1.000121SbR2=0.999208PbR2=1.000238UR2=0.9990 5 10 Conc.(ug/L)40000 0 0 40 80 Conc.(ug/L)250000 5 10 Conc.(ug/L)0 0 1.0 2.0 Conc.(ug/L)600005000 50000 0 25 50 Conc.(ug/L)50000 0 0 1.0 2.0 Conc.(ug/L)600000 0Analysis of tap waterBackground
14、Spectrum-Efficiency of ion trap ICP-MS(1)-Pure water 2%HNO3 2%HClBackground equivalent concentration of ArO is 5 ppb(Fe).Analysis of Fe at m/z=56-Efficiency of ion trap ICP-MS(2)-Calibration curve of 56FeCalibration curve of g/L range can be obtained for Fe at m/z=56 under the hot plasma condition.I
15、ntensityFe conc.(g/L)020406080100R2=0.999IntensityFe conc.(g/L)0300060000510Measurement for Fe in the standard sample of river water(NIST SRM1643d)measured 88.2elementFeQuantity of Fe in Nist 1643d56Fe56Fe(Nist 1643d)(g/L)certified87.3-95.1Measurement for As in the standard sample of river water(NIS
16、T SRM1643d)measured 56.5elementFe(g/L)certified55.29-56.75 750.3%NaCl75As(10ug/L)0.3%NaCl Intensitym/zMass Spectrum of AsAnalysis of As-Efficiency of ion trap ICP-MS(3)-Quantity of As in Nist 1643dR2=0.999Intensity010 20 30 40 50 60 70 80 90 100As conc.(ug/L)75As(Nist 1643d)0200400600800100002000040
17、000600008000010000012000014000016000018000080Se01020304050R2=0.99980Se Conc.(g/L)IntensityIntensity80Se Conc.(ng/L)R2=0.999Analysis of Se at m/z=80-Efficiency of ion trap ICP-MS(4)-Calibration curve of ng/L range can be obtained for Se at m/z=80 under the hot plasma condition.Measurement for Se in t
18、he standard sample of river water(NIST SRM1643d)measured 11.6elementFeQuantity of Se in Nist 1643d(g/L)certified11.26-11.60Calibration curve of 80Se80Se(Nist 1643d)Measurement of 80Se(ng/L)by using CID-Efficiency of ion trap ICP-MS(5)-02040608010001000020000300004000050000Highly background Concentra
19、tion(ng/l)Count(arb.unit)020406080100010002000300040005000 Count(arb.unit)R2=0.998Concentration(ng/l)CID offCID onEliminate80Se80Se#Interference of metal-oxide ion(eg.CaO)can be decreased.#56Fe can be measured including the high matrix of Ca.CID on30 ppm Ca+1 ppb Fe CID on30ppm Ca CID off30 ppm Ca m
20、/z55.556.056.50Decreasing by CIDCool plasma or collision cell can not decrease the interference of CaOMeasurement of 56Fe in Ca by using CID-Efficiency of ion trap ICP-MS(6)-Intensity(arb.unit)Simultaneous Measurement for the Sample with Variety Concentration-Efficiency of ion trap ICP-MS(7)-The sam
21、ple including the elements with over mg/L concentration and under g/L concentration can be measured simultaneously by changing the ion trapping time.02040608010001000023Na r2=0.9993IntensityConc.(mg/L)0.00.51.01.52.0012000238U2r=0.9993IntensityConc.(g/L)Calibration curve of g/L range of UCalibration
22、 curve of mg/L range of USpecificationsICP ion sourceRadio frequency:27.12 MHzPower:0.7-1.4 kWFully computer controlled solid state RF generatorStage:X-Y-Z automatic adjustableSample introductionTorch:Fassel TypeChamber:Scott Type(Option:cooled)Nebulizer:Concentric nebulizerPeristaltic pumpVacuum Sy
23、stem3 stage vacuumInterface vacuum:Rotary pumpIon lens chamber:Turbo pumpAnalyzer chamber:Turbo pumpAnalyzerIon trap type:Compact typeMS-MS function:tandem mass spectrometry(MS2)SpecificationsIon detectionElectron multiplierMass range5-300 amuDetection limit:ppt level for most elementsLinear dynamic
24、 range:8 orders Size and weight Height:810 mmWidth:1180 mmDepth:710 mmWeight:300 kg 几种附件几种附件:自动进样器自动进样器 超声波雾化器超声波雾化器 氢化物发生器氢化物发生器 氢氟酸进样系统氢氟酸进样系统应用应用(I)I)*生物和医学生物和医学 金属蛋白络合物金属蛋白络合物 人血清中的难溶元素人血清中的难溶元素 血浆中的血浆中的MoMo 植物中的植物中的PtPt 尿样中的无机尿样中的无机SeSe和有机和有机SeSe应用应用(II)II)*环境与食品环境与食品 气溶胶气溶胶 大气中的微粒物质大气中的微粒物质 海水
25、中的微量金属海水中的微量金属 极地冰雪中的铁极地冰雪中的铁 环境荷尔蒙环境荷尔蒙 Pb Cd Pb Cd HgHg 酒中生物配合物中的酒中生物配合物中的PbPb 应用应用(III)III)*地质地质 钢铁钢铁 稀土材料稀土材料 贵金属贵金属 高纯物质分析高纯物质分析 陶瓷陶瓷 长石长石 锆石锆石 矿石中的液体包容物矿石中的液体包容物 同位素比同位素比销售目标销售目标:*科研科研 主要市场主要市场 环境环境!*检测检测 贵金属贵金属 地矿地矿 稀土材料稀土材料 经典市场经典市场!说法说法:强调强调 MS MS 部分部分1.ICP1.ICP与离子阱是最好的联用方式与离子阱是最好的联用方式,离子阱离子阱MSMS2 2 和储存离子提高灵敏度和储存离子提高灵敏度2.2.分子离子干扰处理的很好分子离子干扰处理的很好,空间电荷效应空间电荷效应抑制得到解决抑制得到解决,这是其他常规这是其他常规ICP-MSICP-MS做不到做不到3.3.碰撞诱导分裂碰撞诱导分裂-独特独特!MSMS2 2的功能的功能4.4.目前只有日立有目前只有日立有ICPICP与离子阱联用仪器与离子阱联用仪器5.5.液相色谱附件液相色谱附件6.6.体积小巧体积小巧
