Edited by a very well-known and respected scientist in the field, this excellent practical guide is the first to cover the fundamentals and a wide range of applications, as well as showing readers how to efficiently use this increasingly important technique. A must-have guide for newcomers as well as established scientists seeking an overview of ICP-MS.

Frank Vanhaecke (?1966) is Professor in Analytical Chemistry at Ghent University (Belgium), where he leads the 'Atomic & Mass Spectrometry & A&MS' research unit that focuses on the determination, speciation and isotopic analysis of (trace) elements via ICP-mass spectrometry (ICPMS).One of the specific topics studied, is isotope ratio determination using single- and multi-collector ICP-MS in the context of elemental assay via isotope dilution, tracer experiments with stable isotopes and the use of small natural variations in the isotopic composition of metals and metalloids for provenance determination and for obtaining better insight into biological, environmental and geological problems. Frank is (co-)author of some 200 scientific papers in international journals, 15 book chapters and more than 350 conference presentations and is a Fellow of the Royal Society of Chemistry RSC. In 2011, he received a 'European Award for Plasma Spectrochemistry' for his contributions to the field.

Patrick Degryse (?1974) is Professor of Archaeometry at the department of Earth and Environmental Sciences and director of the Centre for Archaeological Sciences at the Katholieke Universiteit Leuven (Belgium). His main research efforts focus on the use of mineral raw materials in ancient ceramic, glass, metal and building stone production, using petrographical, mineralogical and isotope geochemical techniques. He teaches geology, geochemistry, archaeometry and natural sciences in archaeology, and outside the lab is active in several field projects in the eastern Mediterranean. Patrick is author of over 100 scientific papers in international journals, conference proceedings and books and is an A. von Humboldt Fellow and European Research Council Grantee.

Preface XV

List of Contributors XIX

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

6.4.1 General 149

6.4.2 Historical Development 149

6.4.3 Requirements for Isotopic Reference Materials 151

6.5 Present Status, Related Problems, and Solutions 153

6.5.1 Present Status 153

6.5.2 Related Problems 154

6.5.3 Solution 156

6.6 Conclusion and Outlook 157

References 158

7 Quality Control in Isotope Ratio Applications 165
Thomas Meisel

7.1 Introduction 165

7.2 Terminology and Definitions 168

7.3 Measurement Uncertainty 174

7.3.1 Influence Quantities 177

7.3.1.1 Sampling 177

7.3.1.2 Sample Preparation 177

7.3.1.3 Isotope Amount Ratio Determination 177

7.3.1.4 Data Presentation with Isotope Notation 179

7.3.2 Example of Uncertainty Budget Estimation When Using Isotope Dilution 180

7.3.3 Alternative Approach 181

7.3.4 How to Establish Metrological Traceability 181

7.3.5 Method Validation 182

7.3.5.1 Limits of Detection, of Determination, and of Quantitation 182

7.3.5.2 Inter-Laboratory Studies 184

7.4 Conclusion 185

References 185

8 Determination of Trace Elements and Elemental Species Using Isotope Dilution Inductively Coupled Plasma Mass Spectrometry 189
Klaus G. Heumann

8.1 Introduction 189

8.2 Fundamentals 190

8.2.1 Principles of Isotope Dilution Mass Spectrometry 190

8.2.2 Elements Accessible to ICP-IDMS Analysis 194

8.2.3 Selection of Spike Isotope and Optimization of Its Amount 195

8.2.4 Uncertainty Budget and Limit of Detection 199

8.3 Selected Examples of Trace Element Determination via ICP-IDMS 200

8.3.1 Trends in ICP-IDMS Trace Analysis 200

8.3.2 Direct Determination of Trace Elements in Solid Samples via Laser Ablation and Electrothermal Vaporization ICP-IDMS 201

8.3.3 Representative Examples of Trace Element Determination via ICP-IDMS 203

8.3.3.1 Determination of Trace Amounts of Silicon in Biological Samples 203

8.3.3.2 Trace Element Analysis of Fossil Fuels 205

8.3.3.3 Trace Element Analysis via On-Line Photochemical Vapor Generation 207

8.3.3.4 Determination of Trace Amounts of Platinum Group Elements 208

8.3.3.5 Determination of Ultra-Trace Amounts of Transuranium Elements 211

8.3.4 ICP-IDMS in Elemental Speciation 212

8.3.4.1 Principles of ICP-IDMS in Elemental Speciation 212

8.3.4.2 Species-Specific ICP-IDMS 214

8.3.4.3 Species-Unspecific ICP-IDMS 221

References 230

9 Geochronological Dating 235
Marlina A. Elburg

9.1 Geochronology: Principles 235

9.1.1 Single Phase and Isochron Dating 235

9.1.2 Closure Temperature 237

9.2 Practicalities 240

9.2.1 Isobaric Overlap 240

9.2.2 ICP-MS versus TIMS for Geochronology 241

9.3 Various Isotopic Systems 242

9.3.1 U/Th-Pb 242

9.3.1.1 LA–ICP-MS U–Pb Dating of Zircon 244

9.3.1.2 Laser Ablation U/Th-Pb Dating of Other Phases 254

9.3.1.3 Solution Pb–Pb Dating 257

9.3.2 Lu–Hf System 257

9.3.2.1 Lu–Hf Isochrons with Garnet 258

9.3.2.2 Lu–Hf on Phosphates 259

9.3.2.3 Zircon Hf Isotopic Model Ages 259

9.3.3 Re(-Pt)–Os System 261

9.3.3.1 Re–Os Molybdenite Dating 262

9.3.3.2 Re–Os Dating of Black Shales 262

9.3.3.3 Pt-Re–Os on Mantle Peridotites 263

9.4 Systems for Which ICP-MS Analysis Brings Fewer Advantages 265

Acknowledgments 266

References 266

10 Application of Multiple-Collector Inductively Coupled Plasma Mass Spectrometry to Isotopic Analysis in Cosmochemistry 275
Mark Rehka¨mper, Maria Scho¨nba¨chler, and Rasmus Andreasen

10.1 Introduction 275

10.2 Extraterrestrial Samples 276

10.2.1 Introduction 276

10.2.2 Classification of Meteorites 277

10.2.3 Chondritic Meteorites 279

10.2.4 Non-Chondritic Meteorites 281

10.3 Origin of Cosmochemical Isotopic Variations 281

10.3.1 Radiogenic Isotope Variations from the Decay of Long-Lived Radioactive Nuclides 282

10.3.2 Radiogenic Isotope Variations from the Decay of Extinct Radioactive Nuclides 282

10.3.3 Nucleosynthetic Isotope Anomalies 283

10.3.4 Mass-Dependent Isotope Fractionation 284

10.3.5 Cosmogenic Isotope Anomalies 284

10.4 Use of MC-ICP-MS in Cosmochemistry 285

10.4.1 Specific Advantages of MC-ICP-MS 286

10.4.2 Analytical Procedures 287

10.5 Applications of MC-ICP-MS in Cosmochemistry 289

10.5.1 Nucleosynthetic Isotope Anomalies 289

10.5.2 Long-Lived Radioactive Decay Systems 293

10.5.2.1 The 87Rb87Sr Decay System 293

10.5.2.2 The 147Sm143Nd Decay System 293

10.5.2.3 The 176Lu176Hf Decay System 294

10.5.2.4 The U/Th-Pb Decay Systems 295

10.5.3 Extinct Radioactive Decay Systems 297

10.5.4 Stable Isotope Fractionation 300

10.5.5 Cosmogenic Isotope Variations 306

10.6 Conclusion 307

Acknowledgments 308

References 308

11 Establishing the Basis for Using Stable Isotope Ratios of Metals as Paleoredox Proxies 317
Laura E. Wasylenki

11.1 Introduction 317

11.2 Isotope Ratios of Metals as Paleoredox Proxies 319

11.2.1 Molybdenum Isotope Ratios and Global Ocean Paleoredox 320

11.2.2 Cr Isotope Ratios and Paleoredox Conditions of the Atmosphere 329

11.2.3 Uranium Isotope Ratios and Marine Paleoredox 338

11.3 Diagenesis: a Critical Area for Further Work 344

References 346

12 Isotopes as Tracers of Elements Across the Geosphere–Biosphere Interface 351
Kurt Kyser

12.1 Description of the Geosphere–Biosphere Interface 351

12.2 Elements That Typify the Geosphere–Biosphere Interface 354

12.3 Microbes at the Interface 355

12.4 Element Tracing in Environmental Science and Exploration of Metal Deposits 356

12.5 Isotopes as Indicators of Paleoenvironments 360

12.6 Tracing the Geosphere Effect on Vegetation and Animals 360

12.7 Tracing in the Marine Environment 364

12.8 Future Directions 367

References 368

13 Archeometric Applications 373
Patrick Degryse

13.1 Introduction 373

13.2 Current Applications 375

13.2.1 Lead 375

13.2.2 Strontium 377

13.2.2.1 Inorganics: Glass and Iron 377

13.2.2.2 Organics: Skeletal Matter 378

13.2.3 Neodymium 379

13.2.4 Osmium 379

13.3 New Applications 380

13.3.1 Copper 380

13.3.2 Tin 380

13.3.3 Antimony 380

13.3.4 Boron 381

13.4 Conclusion 382

References 382

14 Forensic Applications 391
Mart?´n Resano and Frank Vanhaecke

14.1 Introduction 391

14.1.1 What is Forensics? 391

14.1.2 The Role of ICP-MS in Forensics 391

14.2 Forensic Applications Based on ICP-MS Isotopic Analysis 393

14.2.1 Crime Scene Investigation 393

14.2.2 Nuclear Forensics 396

14.2.3 Food Authentication 399

14.2.4 Monitoring Environmental Pollution 404

14.2.5 Other Applications 408

14.3 Future Outlook 411

Acknowledgments 412

References 412

15 Nuclear Applications 419
Scott C. Szechenyi and Michael E. Ketterer

15.1 Introduction 419

15.2 Rationale 419

15.3 Process Control and Monitoring in the Nuclear Industry 422

15.4 Isotopic Studies of the Distribution of U and Pu in the Environment 424

15.5 Nuclear Forensics 429

15.6 Prospects for Future Developments 431

Acknowledgment 431

References 432

16 The Use of Stable Isotope Techniques for Studying Mineral and Trace Element Metabolism in Humans 435
Thomas Walczyk

16.1 Essential Elements 435

16.2 Stable Isotopic Labels Versus Radiotracers 436

16.3 Quantification of Stable Isotopic Tracers 438

16.4 Isotope Labeling Techniques 442

16.5 Concepts of Using Tracers in Studies of Element Metabolism in Humans 444

16.5.1 Overview 444

16.5.2 Fecal Balance Studies (Single Isotopic Label) 444

16.5.3 Fecal Balance Studies (Double Isotopic Label) 445

16.5.4 Plasma Appearance 446

16.5.5 Urinary Monitoring 447

16.5.6 Compartmental Modeling 447

16.5.7 Tissue Retention 448

16.5.8 Element Turnover Studies 449

16.5.9 Isotope Fractionation Effects 450

16.6 ICP-MS in Stable Isotope-Based Metabolic Studies 451

16.6.1 Measurement Precision 451

16.6.2 Mass Spectrometric Sensitivity 454

16.6.3 Measurement Accuracy and Quality Control 454

16.7 Element-by-Element Review 458

16.7.1 Calcium 458

16.7.2 Iron 462

16.7.3 Zinc 464

16.7.4 Magnesium 469

16.7.5 Selenium 471

16.7.6 Copper 474

16.7.7 Molybdenum 476

Acknowledgments 477

References 478

17 Isotopic Analysis via Multi-Collector Inductively Coupled Plasma Mass Spectrometry in Elemental Speciation 495
Vladimir N. Epov, Sylvain Berail, Christophe Pecheyran, David Amouroux, and Olivier F.X. Donard

17.1 Introduction 495

17.2 Advantage of On-Line versus Off-Line Separation of Elemental Species 497

17.3 Coupling Chromatography with MC-ICP-MS 498

17.3.1 Instrumentation: LC, GC, HPLC, and IC Coupled with MC-ICP-MS 498

17.3.1.1 Liquid Chromatography 500

17.3.1.2 Gas Chromatography 500

17.3.2 Acquisition, Mass Bias Correction, and Data Treatment Strategy 503

17.3.2.1 Signal Acquisition 503

17.3.2.2 Mass Bias Correction 504

17.3.2.3 Data Treatment Strategy 504

17.3.3 Consequences of the Transient Nature of the Signal 507

17.3.3.1 Shape and Width of the Peak 507

17.3.3.2 Drift of the Isotope Ratios During Peak Elution 507

17.4 Environmental and Other Applications 509

17.4.1 Mercury 509

17.4.2 Lead 511

17.4.3 Sulfur 511

17.4.4 Antimony 512

17.4.5 Halogens 512

17.5 Conclusion and Future Trends 513

References 515

Index 519

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