PRACTICAL GUIDE TO ICP-MS A Tutorial for Beginners
（SECOND EDITION）
Contents
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
Microf ow 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
Benef ts 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
Benef t 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 Benef ts 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
Benef ts of TOF Technology 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
Benef ts 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 Microf ow 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
Def ne the Objective ...................................................................................244
Establish Performance Criteria ...................................................................244
Def ne 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
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