Isotopic Analysis: Fundamentals and Applications

542 Pages·2012·6.32 MB·English

by  Frank Vanhaecke, Patrick Degryse

ffirs 30March2012;18:4:26
Isotopic Analysis
Editedby
FrankVanhaeckeand
PatrickDegryse
ffirs 30March2012;18:4:26
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ffirs 30March2012;18:4:26
Edited by Frank Vanhaecke and Patrick Degryse
Isotopic Analysis
Fundamentals and Applications Using ICP-MS
WILEY-VCH Verlag GmbH & Co. KGaA
ffirs 30March2012;18:4:26
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|
V
Contents
Preface XV
List of Contributors XIX
1 The Isotopic Composition of the Elements 1
FrankVanhaeckeandKurtKyser
1.1 AtomicStructure 1
1.2 Isotopes 2
1.3 RelationBetweenAtomicStructureandNaturalAbundanceof
ElementsandIsotopes 3
1.4 NaturalIsotopicCompositionoftheElements 5
1.4.1 ElementswithRadiogenicNuclides 7
1.4.1.1 RadioactiveDecay 7
1.4.1.2 ElementswithRadiogenicNuclides 9
1.4.2 EffectsCaused byNowExtinctRadionuclides 13
1.4.3 Mass-DependentIsotopeFractionation 13
1.4.3.1 IsotopeFractionationinPhysical Processes 15
1.4.3.2 IsotopeFractionationinChemical Reactions 16
1.4.4 Mass-IndependentIsotopeFractionation 20
1.4.5 InteractionofCosmicRayswithTerrestrialMatter 23
1.4.6 Human-Made Variations 24
References 26
2 Single-Collector Inductively Coupled Plasma
Mass Spectrometry 31
FrankVanhaecke
2.1 MassSpectrometry 31
2.2 TheInductivelyCoupledPlasmaIonSource 32
2.3 BasicOperatingPrinciplesofMassSpectrometers 34
2.3.1 MassSpectrometerCharacteristics 34
2.3.1.1 MassResolution 34
IsotopicAnalysis:FundamentalsandApplicationsUsingICP-MS,
FirstEdition.EditedbyFrankVanhaeckeandPatrickDegryse.
r2012WILEY-VCHVerlagGmbH&Co.KGaA,Weinheim.
Published2012byWILEY-VCHVerlagGmbH&Co.KGaA
ftoc 2April2012;14:18:37
VI| Contents
2.3.1.2 AbundanceSensitivity 35
2.3.1.3 MassSpectralRange 36
2.3.1.4 ScanningSpeed 36
2.3.2 QuadrupoleFilter 36
2.3.3 Double-Focusing SectorFieldMassSpectrometer 38
2.3.4 Time-of-Flight Analyzer 43
2.3.5 ComparisonofCharacteristics 45
2.4 Quadrupole-BasedICP-MS 45
2.5 SampleIntroductionStrategiesinICP-MS 47
2.6 SpectralInterferences 50
2.6.1 CoolPlasmaConditions 51
2.6.2 MultipoleCollision/Reaction Cell 52
2.6.2.1 OvercomingSpectralInterference viaChemicalResolution 53
2.6.2.2 OvercomingSpectralInterference viaCollisionalDeceleration
andKineticEnergyDiscrimination 55
2.6.3 HighMassResolutionwithSectorFieldICP-MS 55
2.7 MeasuringIsotopeRatioswithSingle-CollectorICP-MS 56
2.7.1 IsotopeRatioPrecision 57
2.7.1.1 PoissonCountingStatistics 57
2.7.1.2 IsotopeRatioPrecisionwithSingle-CollectorICP-MS 58
2.7.2 DetectorIssues 62
2.7.2.1 ElectronMultiplierOperatingPrinciples 62
2.7.2.2 DetectorDeadTime 62
2.7.3 InstrumentalMassDiscrimination 66
References 68
3 Multi-Collector Inductively Coupled Plasma
Mass Spectrometry 77
MichaelWieser,JohannesSchwieters,and CharlesDouthitt
3.1 Introduction 77
3.2 EarlyMulti-CollectorMassSpectrometers 78
3.3 VariableMulti-Collector MassSpectrometers 79
3.4 MassResolutionandResolvingPower 81
3.5 Three-IsotopePlotsforMeasurementValidation 84
3.6 DetectorTechnologiesforMulti-Collection 87
3.7 Conclusion 90
References 91
4 Advances in Laser Ablation–Multi-Collector Inductively
Coupled Plasma Mass Spectrometry 93
TakafumiHirata
4.1 PrecisionofIsotopeRatioMeasurements 93
4.2 StableSignalIntensity Profiles:WhySoImportant? 94
4.3 SignalSmoothingDevice 99
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Contents |VII
4.4 MultipleIonCounting 101
4.5 IsotopeFractionationDuringLaserAblationand
Ionization 102
4.6 StandardizationoftheIsotopeRatioData 107
Acknowledgments 108
References 108
5 Correction of Instrumental Mass Discrimination for Isotope
Ratio Determination with Multi-Collector Inductively
Coupled Plasma Mass Spectrometry 113
JurisMeija,LuYang,Zolta´nMester,andRalphE.Sturgeon
5.1 HistoricalIntroduction 113
5.2 MassBias inMC-ICP-MS 114
5.3 SystematicsofMassBiasCorrectionModels 115
5.3.1 ExternalGravimetricCalibration 116
5.3.2 InternalDouble-SpikeCalibration 117
5.3.3 InternalCalibration(Inter-Element) 117
5.3.4 ExternalBracketingCalibration(Inter-Element) 117
5.4 LogicofConventionalCorrectionModels 118
5.5 PitfallswithSomeCorrectionModels 119
5.5.1 LinearLaw 119
5.5.2 ExponentialVersusthePowerLaw 120
5.6 IntegrityoftheCorrectionModels 120
5.6.1 Russell’sLaw 120
5.6.2 DiscriminationExponent 121
5.6.3 DiscriminationFunction 122
5.6.4 Second-OrderTerms 124
5.7 TheRegressionModel 124
5.8 CalibrationwithDoubleSpikes 126
5.8.1 CaveatoftheModelChoice 129
5.9 CalibrationwithInternalCorrection 130
5.9.1 Intra-ElementalCorrection 130
5.9.2 Inter-ElementalCorrection 130
5.10 UncertaintyEvaluation 131
5.10.1 UncertaintyModeling andtheDoubleSpikes 132
5.11 Conclusion 133
References 134
6 Reference Materials in Isotopic Analysis 139
JochenVoglandWolfgangPritzkow
6.1 Introduction 139
6.2 Terminology 140
6.3 DeterminationofIsotopeAmountRatios 145
6.4 IsotopicReferenceMaterials 149
ftoc 2April2012;14:18:38
VIII| Contents
6.4.1 General 149
6.4.2 HistoricalDevelopment 149
6.4.3 RequirementsforIsotopicReferenceMaterials 151
6.5 PresentStatus,RelatedProblems,andSolutions 153
6.5.1 PresentStatus 153
6.5.2 RelatedProblems 154
6.5.3 Solution 156
6.6 ConclusionandOutlook 157
References 158
7 Quality Control in Isotope Ratio Applications 165
ThomasMeisel
7.1 Introduction 165
7.2 TerminologyandDefinitions 168
7.3 MeasurementUncertainty 174
7.3.1 InfluenceQuantities 177
7.3.1.1 Sampling 177
7.3.1.2 SamplePreparation 177
7.3.1.3 IsotopeAmountRatioDetermination 177
7.3.1.4 DataPresentationwithIsotopeNotation 179
7.3.2 ExampleofUncertaintyBudgetEstimationWhen
UsingIsotopeDilution 180
7.3.3 AlternativeApproach 181
7.3.4 HowtoEstablishMetrologicalTraceability 181
7.3.5 MethodValidation 182
7.3.5.1 LimitsofDetection,ofDetermination,andofQuantitation 182
7.3.5.2 Inter-LaboratoryStudies 184
7.4 Conclusion 185
References 185
8 Determination of Trace Elements and Elemental Species
Using Isotope Dilution Inductively Coupled Plasma Mass
Spectrometry 189
KlausG.Heumann
8.1 Introduction 189
8.2 Fundamentals 190
8.2.1 PrinciplesofIsotopeDilutionMassSpectrometry 190
8.2.2 ElementsAccessible toICP-IDMSAnalysis 194
8.2.3 SelectionofSpikeIsotopeandOptimizationofItsAmount 195
8.2.4 UncertaintyBudget andLimitofDetection 199
8.3 SelectedExamplesofTraceElementDeterminationvia
ICP-IDMS 200
8.3.1 TrendsinICP-IDMSTraceAnalysis 200
ftoc 2April2012;14:18:38
Contents |IX
8.3.2 DirectDeterminationofTraceElementsinSolidSamples
viaLaserAblationandElectrothermalVaporizationICP-IDMS 201
8.3.3 RepresentativeExamples ofTraceElementDetermination
viaICP-IDMS 203
8.3.3.1 DeterminationofTraceAmountsofSiliconinBiological
Samples 203
8.3.3.2 TraceElementAnalysisofFossilFuels 205
8.3.3.3 TraceElementAnalysisviaOn-Line PhotochemicalVapor
Generation 207
8.3.3.4 DeterminationofTraceAmountsofPlatinum
GroupElements 208
8.3.3.5 DeterminationofUltra-TraceAmountsofTransuranium
Elements 211
8.3.4 ICP-IDMSinElementalSpeciation 212
8.3.4.1 PrinciplesofICP-IDMSinElementalSpeciation 212
8.3.4.2 Species-SpecificICP-IDMS 214
8.3.4.3 Species-UnspecificICP-IDMS 221
References 230
9 Geochronological Dating 235
MarlinaA. Elburg
9.1 Geochronology:Principles 235
9.1.1 SinglePhaseandIsochronDating 235
9.1.2 ClosureTemperature 237
9.2 Practicalities 240
9.2.1 IsobaricOverlap 240
9.2.2 ICP-MSversusTIMS forGeochronology 241
9.3 VariousIsotopicSystems 242
9.3.1 U/Th-Pb 242
9.3.1.1 LA–ICP-MSU–PbDatingofZircon 244
9.3.1.2 LaserAblationU/Th-PbDatingofOtherPhases 254
9.3.1.3 SolutionPb–PbDating 257
9.3.2 Lu–HfSystem 257
9.3.2.1 Lu–HfIsochronswithGarnet 258
9.3.2.2 Lu–HfonPhosphates 259
9.3.2.3 ZirconHfIsotopicModelAges 259
9.3.3 Re(-Pt)–OsSystem 261
9.3.3.1 Re–OsMolybdeniteDating 262
9.3.3.2 Re–OsDatingofBlackShales 262
9.3.3.3 Pt-Re–OsonMantlePeridotites 263
9.4 SystemsforWhichICP-MSAnalysisBringsFewer
Advantages 265
Acknowledgments 266
References 266
ftoc 2April2012;14:18:38