1 The Isotopic Composition of the Elements 1
Frank Vanhaecke and Kurt Kyser
1.1 Atomic Structure 1
1.2 Isotopes 2
1.3 Relation Between Atomic Structure and Natural Abundance of
Elements and Isotopes 3
1.4 Natural Isotopic Composition of the Elements 5
1.4.1 Elements with Radiogenic Nuclides 7
1.4.1.1 Radioactive Decay 7
1.4.1.2 Elements with Radiogenic Nuclides 9
1.4.2 Effects Caused by Now Extinct Radionuclides 13
1.4.3 Mass-Dependent Isotope Fractionation 13
1.4.3.1 Isotope Fractionation in Physical Processes 15
1.4.3.2 Isotope Fractionation in Chemical Reactions 16
1.4.4 Mass-Independent Isotope Fractionation 20
1.4.5 Interaction of Cosmic Rays with Terrestrial Matter 23
1.4.6 Human-Made Variations 24
References 26
2 Single-Collector Inductively Coupled Plasma
Mass Spectrometry 31
Frank Vanhaecke
2.1 Mass Spectrometry 31
2.2 The Inductively Coupled Plasma Ion Source 32
2.3 Basic Operating Principles of Mass Spectrometers 34
2.3.1 Mass Spectrometer Characteristics 34
2.3.1.1 Mass Resolution 34
2.3.1.2 Abundance Sensitivity 35
2.3.1.3 Mass Spectral Range 36
2.3.1.4 Scanning Speed 36
2.3.2 Quadrupole Filter 36
2.3.3 Double-Focusing Sector Field Mass Spectrometer 38
2.3.4 Time-of-Flight Analyzer 43
2.3.5 Comparison of Characteristics 45
2.4 Quadrupole-Based ICP-MS 45
2.5 Sample Introduction Strategies in ICP-MS 47
2.6 Spectral Interferences 50
2.6.1 Cool Plasma Conditions 51
2.6.2 Multipole Collision/Reaction Cell 52
2.6.2.1 Overcoming Spectral Interference via Chemical Resolution 53
2.6.2.2 Overcoming Spectral Interference via Collisional Deceleration
and Kinetic Energy Discrimination 55
2.6.3 High Mass Resolution with Sector Field ICP-MS 55
2.7 Measuring Isotope Ratios with Single-Collector ICP-MS 56
2.7.1 Isotope Ratio Precision 57
2.7.1.1 Poisson Counting Statistics 57
2.7.1.2 Isotope Ratio Precision with Single-Collector ICP-MS 58
2.7.2 Detector Issues 62
2.7.2.1 Electron Multiplier Operating Principles 62
2.7.2.2 Detector Dead Time 62
2.7.3 Instrumental Mass Discrimination 66
References 68
3 Multi-Collector Inductively Coupled Plasma
Mass Spectrometry 77
Michael Wieser, Johannes Schwieters, and Charles Douthitt
3.1 Introduction 77
3.2 Early Multi-Collector Mass Spectrometers 78
3.3 Variable Multi-Collector Mass Spectrometers 79
3.4 Mass Resolution and Resolving Power 81
3.5 Three-Isotope Plots for Measurement Validation 84
3.6 Detector Technologies for Multi-Collection 87
3.7 Conclusion 90
References 91
4 Advances in Laser Ablation–Multi-Collector Inductively
Coupled Plasma Mass Spectrometry 93
Takafumi Hirata
4.1 Precision of Isotope Ratio Measurements 93
4.2 Stable Signal Intensity Profiles: Why So Important? 94
4.3 Signal Smoothing Device 99
4.4 Multiple Ion Counting 101
4.5 Isotope Fractionation During Laser Ablation and
Ionization 102
4.6 Standardization of the Isotope Ratio Data 107
Acknowledgments 108
References 108
5 Correction of Instrumental Mass Discrimination for Isotope
Ratio Determination with Multi-Collector Inductively
Coupled Plasma Mass Spectrometry 113
Juris Meija, Lu Yang, Zolta′n Mester, and Ralph E. Sturgeon
5.1 Historical Introduction 113
5.2 Mass Bias in MC-ICP-MS 114
5.3 Systematics of Mass Bias Correction Models 115
5.3.1 External Gravimetric Calibration 116
5.3.2 Internal Double-Spike Calibration 117
5.3.3 Internal Calibration (Inter-Element) 117
5.3.4 External Bracketing Calibration (Inter-Element) 117
5.4 Logic of Conventional Correction Models 118
5.5 Pitfalls with Some Correction Models 119
5.5.1 Linear Law 119
5.5.2 Exponential Versus the Power Law 120
5.6 Integrity of the Correction Models 120
5.6.1 Russell’s Law 120
5.6.2 Discrimination Exponent 121
5.6.3 Discrimination Function 122
5.6.4 Second-Order Terms 124
5.7 The Regression Model 124
5.8 Calibration with Double Spikes 126
5.8.1 Caveat of the Model Choice 129
5.9 Calibration with Internal Correction 130
5.9.1 Intra-Elemental Correction 130
5.9.2 Inter-Elemental Correction 130
5.10 Uncertainty Evaluation 131
5.10.1 Uncertainty Modeling and the Double Spikes 132
5.11 Conclusion 133
References 134
6 Reference Materials in Isotopic Analysis 139
Jochen Vogl and Wolfgang Pritzkow
6.1 Introduction 139
6.2 Terminology 140
6.3 Determination of Isotope Amount Ratios 145
6.4 Isotopic Reference Materials 149
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