ICP Mass Spectrometry Handbook 英文版.pdf

P1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38Inductively Coupled Plasma MassSpectrometry HandbookiInductively Coupled Plasma Mass Spectrometry Handbook Edited by Simon M.Nelms 2005 Blackwell Publishing Ltd.ISBN:978-1-405-10916-1P1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38Inductively Coupled Plasma MassSpectrometry HandbookEdited byDr Simon M.NelmsThermo Electron,Ion Path,Road Three,Winsford,Cheshire,CW7 3BXiiiP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38C?2005 by Blackwell Publishing LtdEditorial offices:Blackwell Publishing Ltd,9600 Garsington Road,Oxford OX4 2DQ,UKTel:[phone]Blackwell Publishing Asia Pty Ltd,550 Swanston Street,Carlton,Victoria 3053,AustraliaTel:[phone]ISBN10:1-4051-0916-5ISBN-13:978-1-4051-0916-5Published in the USA and Canada(only)byCRC Press LLC,2000 Corporate Blvd.,N.W.,BocaRaton,FL 33431,USAOrders from the USA and Canada(only)toCRC Press LLCUSA and Canada only:ISBN10:0-8493-2381-9The right of the Author to be identified as the Authorof this Work has been asserted in accordance with theCopyright,Designs and Patents Act 1988.All rights reserved.No part of this publication may bereproduced,stored in a retrieval system,ortransmitted,in any form or by any means,electronic,mechanical,photocopying,recording or otherwise,except as permitted by the UK Copyright,Designs andPatents Act 1988,without the prior permission of thepublisher.This book contains information obtained fromauthentic and highly regarded sources.Reprintedmaterial is quoted with permission,and sources areindicated.Reasonable efforts have been made topublish reliable data and information,but the authorand the publisher cannot assume responsibility for thevalidity of all materials or for the consequences oftheir use.Trademark notice:Product or corporate names maybe trademarks or registered trademarks,and are usedonly for identification and explanation,without intentto infringe.First published 2005Library of Congress Cataloging-in-Publication Data:A catalog record for this title is available from theLibrary of CongressBritish Library Cataloguing-in-Publication Data:A catalogue record for this title is available from theBritish LibrarySet in 9.5/12pt Times and Optimaby Techbooks,IndiaPrinted and bound in Indiaby Gopsons Paper Ltd,NoidaThe publishers policy is to use permanent paper frommills that operate a sustainable forestry policy,andwhich has been manufactured from pulp processedusing acid-free and elementary chlorine-free practices.Furthermore,the publisher ensures that the text paperand cover board used have met acceptableenvironmental accreditation standards.For further information on Blackwell Publishing,visitour web site:ivP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38To all the many authors of this book,for their hard work and dedication in preparing themanuscripts and to my wife,Liz,whose encouragement and support throughout the productionof this text proved so valuable to me.vP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38ContentsForwardixPrefacexiContributors Listxiii1Plasma Generation,Ion Sampling and Focusing11.1Plasma generation11.2Sampling interface design and function101.3Ion extraction and focusing152Mass Spectrometers262.1Quadrupole mass spectrometers262.2Magnetic sector field instruments412.2.1Single collector instruments412.2.2Multi-collector devices542.3ICP-time-of-flight mass spectrometry692.4Ion trap mass spectrometry843Ion Detection1173.1Introduction1173.2Electron multipliers1173.3Pulse-counting detectors1273.4Analog detectors1333.5Extended dynamic range detectors1353.6Time-of-flight detectors1403.7Analog multiplier signal processing1413.8Data handling1434Calibration Strategies and Quality Assurance1474.1Terminology1474.2Practical considerations1504.3Spectral interference correction1534.4Semi-quantitative calibration1564.5External calibration1574.6Standard addition1594.7Internal standardisation1604.8Calibration with certified reference materials161viiP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38viiiContents4.9Isotope ratio measurements1614.10Isotope dilution mass spectrometry1694.11Measurement uncertainty1744.12Quality assurance1755Liquid Sample Introduction and Electrothermal Vaporisationfor ICP-MS:Fundamentals and Applications1825.1Nebulisers,spray chambers and desolvation systems overview1825.2Flow Injection sample introduction for ICP-MS1955.3Electrothermal vaporisation as a means of sample introduction in ICP-MS2156Laser Ablation ICP-MS2286.1Introduction2286.2Lasers2286.3Laser ablation sample cells2366.4Quantification procedures for laser ablation ICP-MS2416.5Applications2477Trace Metal Speciation with ICP-MS Detection2597.1Introduction2597.2Sampling and storage for speciation analysis2617.3Speciation with CE-ICP-MS2667.4Speciation with HPLC-ICP-MS2767.5GC-ICP-MS2867.6Speciation using ICP-MS with reaction/collision cell technology3067.7Speciation using high resolution and MC-ICP-MS3108Collision and Reaction Cells3368.1Fundamentals3368.2.Implementation and applications3529ICP-MS Applications3859.1Clinical applications of ICP-MS3859.2Emerging bioanalysis applications for ICP-MS3979.3Environmental analysis4109.4Geological analysis4329.5Measurement of enviromental and biological radionuclides4519.6Semiconductor applications462Index481P1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38ForewordInductively coupled plasma mass spectrometry(ICP-MS)had a humble beginning in the mid-1970s.Loops of twisted wire were important structural components,at least in the instrumentbuilt in Ames,and a barricade of human bodies between the ICP and the recording electronicswas found to be an effective way to shield RF noise.For humanitarian reasons,the latter methodwas used only when necessary to produce data to show at a conference,usually the day beforedeparture!The thrill of generating such last-minute results remains in ICP-MS research to thisday.From these dubious origins,ICP-MS has become a highly developed analytical technique forelemental and isotopic analysis.Over 4000 such instruments have been produced,and they arewidely used in many important scientific applications.For example,the laptop computer usedto write this Foreword would not have anything like its present performance without ICP-MSto determine trace metal impurities in the purity of the reagents and chips used.The successof ICP-MS in this application also illustrates the value of plain old good luck in science.Fourelements for which performance is improved greatly by use of the cool ICP are Na,K,Ca andFe.By great good fortune,these just happen to be key impurity elements in semiconductorproduction!Itisthiswidespreadapplicationbase,theenablingofnewtypesofmultielementmeasurementsat concentration levels previously inaccessible,that represents the scientific value of ICP-MS.Indeed,the detection limits are now restricted more by the cleanliness of the blank than by thesensitivity of the ICP-MS instrument,at least for most samples and elements.ICP-MS has improved substantially since the earlier Handbook by Jarvis,Gray and Houk,published in 1991;the use of low-flow nebulizers,magnetic sectors and collision cells was justbeginning back then.Some instruments now fit onto a benchtop;most have something like theNike Swoosh emblazoned somewhere on the cover.Decorations aside,the present book pro-vides detailed descriptions of current instrumentation and capabilities,analytical considerationslike interferences,and key applications of ICP-MS.The information herein is very valuableto scientists using ICP-MS,as well as those seeking further improvements in performance.The method is not quite plug-and-play,and background knowledge of the instrumentation,itsstrengths and limitations is important in the production of valid results.This book fills that need,and I congratulate the editor and the authors for this very valuable contribution.R.S.HoukProfessor of ChemistryAmes Laboratory U.S.Department of EnergyIowa State UniversityAmes,Iowa 50011 USAixP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38PrefaceInductively coupled plasma mass spectrometry(ICP-MS)is arguably the most versatile traceelemental analysis technique available today.Depending on the individual instrument configu-ration,sample types ranging from sea waters and rock digests to ultra-pure semiconductor gradechemicals can be routinely analysed,for almost all the elements in the Periodic Table,fromlow pg/mL(in most cases)to high g/mL concentration levels.It is this versatility that has ledto the rapid acceptance and subsequent growth of the technique.Since the launch of the firstcommercial quadrupole ICP-MS instruments in 1983,the technology has evolved from large,floor-standing,manually operated systems,with limited functionality and relatively poor detec-tionlimitcapabilities,tocompact,sensitiveandhighlyautomatedroutineanalyticalinstruments.From the outset,it was observed that although ICP-MS spectra were much less complex thanICP optical emission spectra,interferences were nonetheless present and as ICP-MS has grown,considerableattentionhasbeenfocusedonachievingwhollyinterference-freeanalysis.Thefirststep towards achieving this objective was the development of high resolution ICP-MS in the late1980s,whereby analytes could be resolved from interferences using a magnetic field,by virtueof the mass differences between analyte/interference pairs.This technology,although effectivein resolving a wide range of polyatomic interferences,lacks the power to resolve isobaric in-terferences(i.e.overlap between isotopes of the same nominal mass,such as87Rb and87Sr).More recently,the advent of collision/reaction cell technology has revolutionised quadrupoleICP-MS.Born out of existing technology for triple quadrupole organic mass spectrometers,col-lision/reactioncellshavetakeninterferencereductionadramaticstepforward.Throughcollisionand reaction with appropriate gases in a cell preceding the analyser quadrupole,interferencessuch as40Ar2+can be almost completely eliminated whilst leaving analyte ions(80Se in thiscase)relatively unaffected.As with high resolution ICP-MS,collision/reaction cells cannot pro-vide a complete solution to isobaric interference,although through the use of carefully selectedreaction conditions,some isobaric interferences can be shifted to higher masses as molecularspecies(for example separating Rb and Sr using CH3F as the reaction gas to selectively formSrF).Collision/reaction cell technology makes up a large part of current research into ICP-MSand this is reflected in the substantial section devoted to the subject in this book.The aim of truly interference-free analysis may ultimately be realised by the future develop-ment of Fourier transform ion cyclotron resonance(FT-ICR)ICP-MS.This technique,althoughin its infancy(and currently prohibitively expensive),has demonstrated a resolution capabilityof 88000 and is theoretically capable of resolution in excess of 1106,rendering it the onlycurrently available technique that has the potential to directly resolve isobaric interferences.Theprinciples and applications of this exciting technology are discussed in the second chapter ofthis book.xiP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38xiiPrefaceExtensive advances and improvements have been made in the area of sample introduction forICP-MS and this subject forms a large part of this text.The currently available liquid and solidsampling systems,from nebulisers and spray chambers to electrothermal vaporisation and laserablation,are described and discussed in detail herein.In addition to the advances in ICP-MS instrument and sample introduction accessories designthat have occurred,applications of the technique,particularly in the field of speciation analysis,have also evolved considerably during this time.Speciation analysis(the science of measuringelemental species)has grown significantly in importance and application in recent years,as aresult of the realisation that the bioavailability and corresponding nutritional or toxic propertiesof an element depend on the chemical form in which it is present.In practice,species separationis performed using chromatographic techniques such as CE,HPLC or GC,prior to on-linedetection using a variety of detectors.The popularity of ICP-MS as a detector for speciationstudies at the trace levels encountered in real-world samples can be attributed to the relativeease with which it can be coupled to chromatography equipment and its ability to handle lowconcentration,transient signals.The present state-of-the-art and future potential of speciationanalysis with ICP-MS detection is described in Chapter 7 of this book.This book aims to provide a background to this exciting technology,with chapters devotedto plasma generation,ion sampling and focusing,mass analysis,ion detection and sample in-troduction.Calibration and quantitative analysis methodologies are also reviewed together withsubstantial discussion on quality assurance and result validation.Finally,this book also aims toupdate the reader with recent developments in the main application areas.P1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38Contributors ListAndrew FisherSchool of Earth,Ocean and Environmental Sciences,Plymouth University,Drake Circus,Plymouth,Devon,PL4 8AA,United KingdomAlison HollidayLCABIE CNRS UMR 5034,Helioparc,2,Avenue duPresident Angot,64053 Pau,Cedex 9,FranceBill SpenceThermo Electron,Ion Path,Road Three,Winsford,Cheshire,CW7 3BX,United KingdomCarla VogtInstitute of Inorganic Chemistry,Department ofAnalytical Chemistry,University of Hannover,Callinstrasse 9,D-30167 Hannover,GermanyChristopher LatkoczyGloriasteig 5,8044 Zurich,SwitzerlandDiethard K.BohmeDepartment of Chemistry,York University,4700 KeeleStreet,Toronto,Ontario,M3J 1P3,CanadaDavid WrayEarth and Environmental Sciences Department,University of Greenwich at Medway,Pembroke,Central Avenue,Chatham Maritime,Kent,ME4 4AW,United KingdomDick StresauETP Electron Multipliers,31 Hope Street,P.O.Box143,Ermington,2115 New South Wales,AustraliaDmitry R.BanduraMDS Sciex,71 Four Valley Drive,Concord,Ontario,L4K 4V8,CanadaEva KruppLCABIE CNRS UMR 5034,Helioparc,2,Avenue duPresident Angot,64053 Pau,Cedex 9,FranceFrank VanhaeckeLaboratory of Analytical Chemistry,Gent University,Proeftuinstraat 86,B-9000 Gent,BelgiumFabienne SabyLCABIE CNRS UMR 5034,Helioparc,2,Avenue duPresident Angot,64053 Pau,Cedex 9,FrancexiiiP1:FCG/SPHP2:FCGBY047-NelmsJuly 6,20055:38xivContributors ListGeoff M.NowellDepartment of Earth Sciences,University of Durham,Science Laboratories,Durham,DH1 3LE,UnitedKingdomGregory C.EidenAnalytical Chemistry Group,Pacific NorthwestNational Laboratory,Mail Stop P7-07,Richland,WA99352,USAGunda KllenspergerInstitute of Chemistry,University of AgriculturalSciences(BOKU),Muthgasse 18,A-1190 Vienna,AustriaGregory K.KoyanagiDepartment of Chemistry,York University,4700 KeeleStreet,Toronto,Ontario,M3J 1P3,CanadaHeidi Goenaga-InfanteLaboratory of the Government Chemist(LGC),Specialised Techniques,Queens Road,Teddington,Middlesex,TW11 0LY,United KingdomJos e L.TodoliDepartment of Ana