Practical Guide to ICP-MS: A Tutorial for Beginners Book

Foreword xvii

Preface xix

Author xxv

Chapter 1 An Overview of ICP Mass Spectrometry 1

Principles of Operation 1

Chapter 2 Principles of Ion Formation 7

Ion Formation 7

Natural Isotopes 8

Chapter 3 Sample Introduction 13

Aerosol Generation 13

Droplet Selection 15

Nebulizers 16

Concentric Design 16

Cross-Flow Design 18

Microflow Design 18

Spray Chambers 20

Double-Pass Spray Chamber 20

Cyclonic Spray Chamber 21

References 22

Chapter 4 Plasma Source 23

The Plasma Torch 24

Formation of an ICP Discharge 26

The Function of the RF Generator 26

Ionization of the Sample 28

References 29

Chapter 5 Interface Region 31

Capacitive Coupling 32

Ion Kinetic Energy 34

Benefits of a Well-Designed Interface 36

References 37

Chapter 6 Ion-Focusing System 39

Role of the Ion Optics 39

Dynamics of Ion Flow 41

Commercial Ion Optic Designs 43

References 46

Chapter 7 Mass Analyzers: Quadrupole Technology 47

Quadrupole Mass Filter Technology 47

Basic Principles of Operation 48

Quadrupole Performance Criteria 49

Resolution 50

Abundance Sensitivity 52

Benefit of Good Abundance Sensitivity 53

References 54

Chapter 8 Mass Analyzers: Double-Focusing Magnetic Sector Technology 57

Magnetic Sector Mass Spectroscopy: A Historical Perspective 57

Use of Magnetic Sector Technology for ICP-MS 58

Principles of Operation of Magnetic Sector Systems 59

Resolving Power 60

Other Benefits of Magnetic Sector Instruments 63

References 63

Chapter 9 Mass Analyzers: Time-of-Flight Technology 65

Basic Principles of TOF Technology 65

Commercial Designs 66

Differences Between Orthogonal and On-Axis TOF 68

Benefits of TOFTechnology for ICP-MS 70

Rapid Transient Peak Analysis 70

Improved Precision 70

Rapid Data Acquisition 71

References 72

Chapter 10 Mass Analyzers: Collision/Reaction Cell and Interface Technology 73

Basic Principles of Collision/Reaction Cells 74

Different Collision/Reaction Cell Approaches 75

Collisional Mechanisms Using Nonreactive Gases and Kinetic Energy Discrimination 76

Reaction Mechanisms with Highly Reactive Gases and Discrimination by Selective Bandpass Mass Filtering 80

The Collision/Reaction Interface 84

Using Reaction Mechanisms in a Collision Cell 85

Detection Limit Comparison 89

Summary 89

References 91

Chapter 11 Ion Detectors 93

Channel Electron Multiplier 93

Faraday Cup 94

Discrete Dynode Electron Multiplier 95

Extending the Dynamic Range 96

Filtering the Ion Beam 96

Using Two Detectors 96

Using Two Scans with One Detector 96

Using One Scan with One Detector 97

Extending the Dynamic Range Using Pulse-Only Mode 98

References 100

Chapter 12 Peak Measurement Protocol 101

Measurement Variables 101

Measurement Protocol 102

Optimization of Measurement Protocol 106

Multielement Data Quality Objectives 107

References 113

Chapter 13 Methods of Quantitation 115

Quantitative Analysis 115

External Standardization 116

Standard Additions 117

Addition Calibration 118

Semiquantitative Analysis 118

Isotope Dilution 120

Isotope Ratios 123

Internal Standardization 123

References 124

Chapter 14 Review of Interferences 125

Spectral Interferences 125

Oxides, Hydroxides, Hydrides, and Doubly Charged Species 127

Isobaric Interferences 128

Ways to Compensate for Spectral Interferences 128

Mathematical Correction Equations 128

Cool/Cold Plasma Technology 130

Collision/Reaction Cells 131

High-Resolution Mass Analyzers 132

Matrix Interferences 132

Compensation Using Internal Standardization 133

Space-Charge-Induced Matrix Interferences 134

References 135

Chapter 15 Contamination Issues Associated with Sample Preparation 137

Collecting the Sample 137

Preparing the Sample 138

Grinding the Sample 138

Sample Dissolution Methods 139

Choice of Reagents and Standards 141

Vessels, Containers, and Sample Preparation Equipment 142

The Environment 145

The Analyst 146

Instrument and Methodology 147

References 149

Chapter 16 Routine Maintenance 151

Sample Introduction System 152

Peristaltic Pump Tubing 152

Nebulizers 152

Spray Chamber 154

Plasma Torch 155

Interface Region 156

Ion Optics 157

Roughing Pumps 158

Air Filters 159

Other Components to Be Periodically Checked 159

The Detector 159

Turbomolecular Pumps 160

Mass Analyzer 160

Chapter 17 Alternative Sample Introduction Techniques 163

Laser Ablation 164

Commercial Systems for ICP-MS 165

Excimer Lasers 165

Benefits of Laser Ablation for ICP-MS 166

Optimum Laser Design Based on Application Requirements 167

Flow Injection Analysis 171

Electrothermal Vaporization 174

Chilled Spray Chambers and Desolvation Devices 178

Water-Cooled and Peltier-Cooled Spray Chambers 178

Ultrasonic Nebulizers 179

Specialized Microflow Nebulizers with Desolvation Techniques 181

Direct Injection Nebulizers 183

Rapid Sampling Procedures 184

References 185

Chapter 18 Coupling ICP-MS with Chromatographic Techniques for Trace Element Speciation Studies 187

HPLC Coupled with ICP-MS 190

Chromatographic Separation Requirements 191

Ion Exchange Chromatography (IEC) 191

Reversed-Phase Ion Pair Chromatography (RP-IPC) 192

Column Material 193

Isocratic or Gradient Elution 193

Sample Introduction Requirements 195

Optimization of ICP-MS Parameters 196

Compatibility with Organic Solvents 197

Collision/Reaction Cell or Interface Capability 197

Optimization of Peak Measurement Protocol 199

Full Software Control and Integration 200

Summary 201

References 202

Chapter 19 ICP-MS Applications 203

Environmental 204

Biomedical 208

Sample Preparation 209

Interference Corrections 210

Calibration 210

Stability 211

Geochemical 211

Determination of Rare Earth Elements 212

Analysis of Digested Rock Samples Using Flow Injection 214

Geochemical Prospecting 215

Isotope Ratio Studies 216

Laser Ablation 218

Semiconductor 219

Nuclear 224

Applications Related to the Production of Nuclear Materials 226

Applications in the Characterization of High-Level Nuclear Waste 227

Applications Involving the Monitoring of the Nuclear Industry's Impact on the Environment 227

Applications Involving Human Health Studies 228

Other Applications 229

Metallurgical Applications 229

Petrochemical and Organic-Based Samples 231

Food and Agriculture 234

Summary 236

References 236

Chapter 20 Comparing ICP-MS with Other Atomic Spectroscopic Techniques 241

Flame Atomic Absorption 242

Electrothermal Atomization 243

Radial-View ICP Optical Emission 243

Axial-View ICP Optical Emission 243

Inductively Coupled Plasma Mass Spectrometry 243

Define the Objective 244

Establish Performance Criteria 244

Define the Application Task 244

Application 244

Installation 245

User 245

Financial 245

Comparison of Techniques 245

Detection Limits 245

Analytical Working Range 246

Sample Throughput 249

Interferences 251

Usability 252

Cost of Ownership 252

Cost per Sample 257

Conclusion 259

References 259

Chapter 21 How to Select an ICP Mass Spectrometer: Some Important Analytical Considerations 261

Evaluation Objectives 261

Analytical Performance 262

Detection Capability 263

Precision 267

Isotope Ratio Precision 269

Accuracy 271

Dynamic Range 272

Interference Reduction 274

Reduction of Matrix-Induced Interferences 281

Sample Throughput 284

Transient Signal Capability 285

Usability Aspects 286

Ease of Use 286

Routine Maintenance 287

Compatibility with Alternative Sampling Accessories 288

Installation of Instrument 288

Technical Support 289

Training 289

Reliability Issues 289

Service Support 290

Financial Considerations 291

The Evaluation Process: A Summary 292

References 293

Chapter 22 Glossary of ICP-MS Terms 295

Chapter 23 Useful Contact Information 333

Index 341