Model P-5000 ICP-MS 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。 Hitachi Ltd. Instruments

Line Up for Elemental Analysis Single Element Multi Element Analysis Analysis Sensitivity P-5000 Z-5010 series ICP-MS ppt ppb ppm Atomic Absorption Furnace&Flame Atomic Absorption Furnace Plasma/MS　 (ICP/MS ､MIP/MS) Ion trap type ICP-MS Atomic Absorption Flame ICP/AES P-6000 0.01 0.1 1 10 100 MIP-MS 日立製作所の微量元素測定の原子吸光光度計、ＩＣＰ発光分析装置、 プラズマ質量分析装置の製品シリーズを示します。 通常ppmレベルの定量にはフレーム原子吸光光度計、およびその迅速化測定の為にＩＣＰ発光分析装置が使用されています。 ppbレベルの濃度試料にはグラファイト炉原子吸光光度計、またその迅速分析のためにpptレベルの感度を持つプラズマ質量分析装置 (ＩＣＰ／ＭＳ)が使用されています。 Through-put (Elements/min) P-4010 ICP-AES Hi-Power MIP-MS

Inductively Coupled Plasma Mass Spectrometry ICP-MS 电感耦合等离子体质谱仪 Inductively Coupled Plasma Mass Spectrometry

等离子体-离子源 质谱 -按原子(分子)质量顺序排列 的图谱 质谱仪- 质量分析仪, 对带电粒子起作用, M/e与离子强度 其他联用技术 　GC-MS HPLC-MS

特点: 无机质谱 分析速度快 线性范围宽 可多元素测定 80多种元素 检出限低 　PPT

Characteristics P-5000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 filtered noise field (FNF) 3. Ion concentration through trapping (a detection limit is ppt level for most elements) ＩＣＰ／ＭＳはInductively Coupled Plasma / Mass Spectrometer （ＩＣＰ質量分析装置）の略で、Ｌｉ～Ｕまでの地球上にあるほとんどの 元素を測定濃度域ｐｐｍ～ｐｐｔで高感度に分析できます。 測定原理は、溶液試料をネブライザーで細かな霧状としてプラズマの中に 導入することで試料中の元素をイオン化させ、イオン化された元素を 質量の違いで分別し、イオンの量により元素の含有量を求めるます。 通常、分析の濃度単位は、ppm、ppb、ppt、ppqで表現されます。 1ppm(parts per million) ＝1×10 －6ｇ/ml＝１ug/ml 1ppb(parts per billion) ＝1×10 －9ｇ/ml＝１ng/ml 1ppt(parts per trillion) ＝1×10－12ｇ/ml＝１pg/ml 1ppq(parts per quadrilion)＝1×10－15ｇ/ml＝１fg/ml

要点: 1. ICP和三维四极离子阱的结合是目前为止最佳的ICP-MS 原因: MS2解决了分子离子的干扰 FNF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

Introduction P-5000 ICP-MS is the first ion trap type ICP-MS in the world. It offers : 1. Low Background signal 2. High sensitivity 3. Wide dynamic range 4. Easy operation ＩＣＰ／ＭＳはInductively Coupled Plasma / Mass Spectrometer （ＩＣＰ質量分析装置）の略で、Ｌｉ～Ｕまでの地球上にあるほとんどの 元素を測定濃度域ｐｐｍ～ｐｐｔで高感度に分析できます。 測定原理は、溶液試料をネブライザーで細かな霧状としてプラズマの中に 導入することで試料中の元素をイオン化させ、イオン化された元素を 質量の違いで分別し、イオンの量により元素の含有量を求めるます。 通常、分析の濃度単位は、ppm、ppb、ppt、ppqで表現されます。 1ppm(parts per million) ＝1×10 －6ｇ/ml＝１ug/ml 1ppb(parts per billion) ＝1×10 －9ｇ/ml＝１ng/ml 1ppt(parts per trillion) ＝1×10－12ｇ/ml＝１pg/ml 1ppq(parts per quadrilion)＝1×10－15ｇ/ml＝１fg/ml

Structure of P-5000 ICP-MS Ion trap Ion guide Detector Skimmer cone Torch Chamber Nebulizer Sampling cone Turbo molecular pumps Rotary pumps Peristaltic pump

Comparison of ion trap and conventional QMS What is Ion trap? Comparison of ion trap and conventional QMS Ion trap : trapping type # Tandem mass spectrometry # Relatively compact instrument QMS: transmitting type # High transmission efficiency in the selected ion monitoring (SIM) mode

提示: 离子阱全能 与ICP结合最佳 四极杆适合选择离子检测 与GC,LC配合更好

What is Ion trap? Ion trap basic action Multi function analysis Ion detection Ions trapping Time (Entrance gate) (Exit gate) open close close close close open Ions Detector Entrance gate Exit gate

Main Features of P-5000 ICP-MS 1. 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 2. Hi-sensitivity and wide dynamic range By changing the ion trapping time , it is possible to change the ion sensitivity. 阱的时间 3. Easy measurement Simultaneous analysis, qualitative, quantitative analysis. 4. Ar-ICP ion source RF : 27 MHz, Maximum Power : 1.4 kW

Main problem of conventional ICP-QMS Main Features of P-5000 ICP-MS Main problem of conventional ICP-QMS It is impossible to distinguish the ions with the same m/z. Measurement ion Molecular ion + Se Se + ArAr + ArAr Impossible to distinguish Same m/z

Main Features of P-5000 ICP-MS In the P-5000 system, next 2 stage 1. Natural decluster 自然去簇 2. Collision-induced dissociation (CID)碰撞诱导分裂 　is used to eliminate the interference from molecular ions. :Measurement Ion :Moleculars :after dissociation

Elimination method for the molecular ions. Main Features of P-5000 ICP-MS Elimination method for the molecular ions. Ion tap Cool plasma + QMS Reaction cell + QMS Ar-molecular ions Sensitivity of other ions Elimination Metal-oxide ions Possible Impossible Good bad Reaction gas He - NH3, H2

Main Features of P-5000 ICP-MS Different of background spectrum ICP-QMS P-5000 Ion trap ICP-MS

Main Features of P-5000 ICP-MS Wide dynamic range 10000 1000 100 10 1　 By changing the ion trapping time , possible to change the ion sensitivity. Intensity 1　　 10　　 100 1000 10000 msec Ion trapping time

Calibration Curve 1.000 50 100 Concentration(ppt) 208 Pb 400 500 600 50 100 Concentration(ppt) 208 Pb 400 500 600 700 Intensity

Analysis of tap water 11B 27Al 52Cr 55Mn 56Fe 60Ni 63Cu 66Zn 75As 15000 11B R2= 1.000 35000 27Al R2= 1.000 50000 52Cr R2= 1.000 0 50 100 Conc.(ug/L) 0 50 100 Conc.(ug/L) 0 25 50 Conc.(ug/L) 70000 55Mn R2= 1.000 70000 56Fe R2= 1.000 30000 60Ni R2= 1.000 4000 2000 0 25 50 Conc.(ug/L) 0 150 300 Conc.(ug/L) 0 5 10 Conc.(ug/L) 80000 63Cu R2= 1.000 60000 66Zn R2= 1.000 60000 75As R2= 0.998 　上図に上水測定に用いた検量線を示します。 各元素について、ブランク・基準値の1/10濃度・基準値濃度の３点(ただし、B，Al，Cu，Znは、0，10，100ug/L)で検量線を作成しました。 各元素の検量線は、良好な直線関係が得られています。 ・ 0 50 100 Conc.(ug/L) 0 50 100 Conc.(ug/L) 0 5 10 Conc.(ug/L)

Analysis of tap water 80Se 98Mo 112Cd 238U 121Sb 208Pb 60000 80Se R2= 0.998 40000 98Mo R2= 1.000 25000 112Cd R2= 1.000 0 40 80 Conc.(ug/L) 0 5 10 Conc.(ug/L) 0 5 10 Conc.(ug/L) 60000 50000 238U R2= 0.999 121Sb R2= 0.999 50000 208Pb R2= 1.000 　上図に上水測定に用いた検量線を示します。 各元素について、ブランク・基準値の1/10濃度・基準値濃度の３点(ただし、B，Al，Cu，Znは、0，10，100ug/L)で検量線を作成しました。 各元素の検量線は、良好な直線関係が得られています。 0 1.0 2.0 Conc.(ug/L) 0 25 50 Conc.(ug/L) 5000 0 1.0 2.0 Conc.(ug/L)

Background Spectrum ---- Efficiency of ion trap ICP-MS (1) --- Pure water Background equivalent concentration of ArO is 5 ppb ( Fe ). 2% HNO3 2% HCl

Analysis of Fe at m/z = 56 Calibration curve of 56Fe ---- Efficiency of ion trap ICP-MS (2) --- 6000 Calibration curve of 56Fe 56Fe Intensity Calibration curve of µg/L range can be obtained for Fe at m/z = 56 under the hot plasma condition. 3000 5 10 Fe conc.(µg/L) Quantity of Fe in Nist 1643d 56Fe (Nist 1643d) Measurement for Fe in the standard sample of river water (NIST SRM1643d) Intensity element Fe measured 88.2 certified 87.3-95.1 R 2 =0.999 20 40 60 80 100 (µg/L) Fe conc.(µg/L)

Analysis of As Quantity of As in Nist 1643d ---- Efficiency of ion trap ICP-MS (3) --- Quantity of As in Nist 1643d 75As(10ug/L)＋0.3%NaCl Measurement for As in the standard sample of river water (NIST SRM1643d) 75As (Nist 1643d) Intensity Intensity 2 R =0.999 10 20 30 40 50 60 70 80 90 100 As conc.(ug/L) 0.3%NaCl element Fe measured 56.5 certified 55.29-56.75 75 m/z (µg/L) Mass Spectrum of As

Analysis of Se at m/z = 80 Calibration curve of 80Se ---- Efficiency of ion trap ICP-MS (4) --- 180000 80 Se 160000 Calibration curve of 80Se 140000 Intensity 120000 100000 Calibration curve of ng/L range can be obtained for Se at m/z = 80 under the hot plasma condition. 80000 60000 40000 R 2 =0.999 20000 200 400 600 800 1000 80Se Conc.(ng/L) Quantity of Se in Nist 1643d 80Se (Nist 1643d) Intensity Measurement for Se in the standard sample of river water (NIST SRM1643d) element Fe measured 11.6 certified 11.26-11.60 R 2 =0.999 10 20 30 40 50 (µg/L) 80Se Conc.(µg/L)

Measurement of 80Se (ng/L) by using CID ---- Efficiency of ion trap ICP-MS (5) --- CID off CID on 50000 5000 80 Se 40000 80 Se 4000 30000 Count(arb. unit) 3000 Count(arb. unit) Highly background　 20000 2000 10000 Eliminate 1000 R 2 =0.998 20 40 60 80 100 20 40 60 80 100 Concentration(ng/l) Concentration(ng/l)

Measurement of 56Fe in Ca by using CID ---- Efficiency of ion trap ICP-MS (6) --- # Interference of metal-oxide ion (eg. CaO＋) can be decreased. # 56Fe can be measured including the high matrix of Ca. CID off 30 ppm Ca CID on 30 ppm Ca 　　+ 1 ppb Fe Intensity (arb. unit) Decreasing by CID Cool plasma or collision cell can not decrease the interference of CaO CID on 30ppm Ca 55.5 56.0 56.5 m/z 1

Simultaneous Measurement for the Sample with Variety Concentration ---- Efficiency of ion trap ICP-MS (7) --- The sample including the elements with over mg/L concentration and under µg/L concentration can be measured simultaneously by changing the ion trapping time. 10000 23 Na 12000 238 U Intensity Intensity r 2 =0.9993 2 r =0.9993 20 40 60 80 100 0.0 0.5 1.0 1.5 2.0 Conc. (mg/L) Conc. (µg/L) Calibration curve of mg/L range of U Calibration curve of µg/L range of U

Specifications ICP ion source Radio frequency : 27.12 MHz Power : 0.7-1.4 kW Fully computer controlled solid state RF generator Stage : X-Y-Z automatic adjustable Sample introduction Torch :Fassel Type Chamber :Scott Type (Option:cooled) Nebulizer :Concentric nebulizer Peristaltic pump Vacuum System 3 stage vacuum Interface vacuum : Rotary pump Ion lens chamber : Turbo pump Analyzer chamber : Turbo pump Analyzer Ion trap type : Compact type MS-MS function : tandem mass spectrometry (MS2)

Specifications Ion detection Electron multiplier Mass range 5 - 300 amu Detection limit : ppt level for most elements Linear dynamic range : 8 orders Size and weight Height : 810 mm Width : 1180 mm Depth : 710 mm Weight : 300 kg

几种附件: 自动进样器 超声波雾化器 氢化物发生器 氢氟酸进样系统

应用(I) *生物和医学 金属蛋白络合物 人血清中的难溶元素 血浆中的Mo 植物中的Pt 尿样中的无机Se和有机Se

应用(II) *环境与食品 气溶胶 大气中的微粒物质 海水中的微量金属 极地冰雪中的铁 环境荷尔蒙 Pb Cd Hg 酒中生物配合物中的Pb

应用(III) *地质 钢铁 稀土材料 贵金属 高纯物质分析 陶瓷 长石 锆石 矿石中的液体包容物 同位素比

销售目标: * 科研 主要市场 环境! * 检测 贵金属 地矿 稀土材料 经典市场!

说法:强调 MS 部分 1.ICP与离子阱是最好的联用方式,离子阱MS2 和储存离子提高灵敏度 5.液相色谱附件 6.体积小巧