Table Of ContentPractical Inductively Coupled
Plasma Spectrometry
Practical Inductively Coupled
Plasma Spectrometry
Second Edition
John R. Dean
Northumbria University
Newcastle‐upon‐Tyne
United Kingdom
This edition first published 2019
© 2019 John Wiley & Sons Ltd
Edition History
Practical Inductively Coupled Plasma Spectrometry, First Edition, Wiley 2005.
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Library of Congress Cataloging‐in‐Publication Data applied for
ISBN: 9781119478683
Cover Design: Wiley
Cover Image: Courtesy of John R Dean
Set in 10/12pt WarnockPro by SPi Global, Chennai, India
Printed in the UK by Bell & Bain Ltd, Glasgow
10 9 8 7 6 5 4 3 2 1
This book is dedicated to my wife, Lynne and our two now grown‐up children,
Sam and Naomi, and our newest family member, Harris, the border terrier.
Each of you is pursuing your own goals and ambitions.
vii
Contents
About the Author xiii
Preface xv
Acknowledgements xix
Acronyms, Abbreviations and Symbols xxiii
1 The Analytical Approach 1
1.1 Introduction 1
1.2 Essentials of Practical Work 2
1.3 Health and Safety 3
1.4 SI Units and Their Use 4
1.5 Significant Figures 11
1.6 Calibration and Quantitative Analysis 12
1.7 Making Notes of Practical Work and Observations 13
1.8 Data Analysis 14
1.9 Data Treatment 17
1.10 Data Quality 18
1.11 Data Interpretation and Context 21
1.12 Analytical Terms and Their Definitions 21
1.13 Summary 26
2 Sampling and Storage 27
2.1 Introduction 27
2.2 Sampling Soil 28
2.3 Sampling Water 31
2.4 Sampling Air 32
2.5 Sample Storage 34
2.6 Sample Preservation 36
2.7 Summary 37
3 Sample Preparation 39
3.1 Introduction 39
3.2 Aqueous Samples 40
3.2.1 Liquid–Liquid Extraction 40
viii Contents
3.2.1.1 Procedure for APDC Extraction in to MIBK 42
3.2.2 Ion Exchange 42
3.2.2.1 Procedure for Batch Ion Exchange Extraction 43
3.3 Solid Samples 43
3.3.1 Decomposition Techniques 45
3.3.1.1 Procedure for Acid Digestion A 46
3.3.1.2 Procedure for Acid Digestion B 46
3.3.1.3 Procedure for Microwave Acid Digestion 49
3.3.2 Alternate Decomposition Techniques 49
3.3.2.1 Procedure for Dry Ashing 49
3.3.2.2 Procedure for Fusion 50
3.4 Extraction Procedures 51
3.4.1 Procedure for Extractable Mercury from Soil and Sediment 52
3.4.2 Procedure for Speciation of Extractable Mercury from Soil
and Sediment 52
3.4.3 Procedure for Arsenic Species Extraction 52
3.4.4 Single Extraction Methods 57
3.4.4.1 Procedure for EDTA Extraction 57
3.4.4.2 Procedure for AA Extraction 58
3.4.4.3 Procedure for Diethylenetriaminepentaacetic Acid (DTPA)
Extraction 58
3.4.4.4 Procedure for Calcium Chloride (CaCl ) Extraction 58
2
3.4.4.5 Procedure for Ammonium Nitrate (NH NO ) Extraction 59
4 3
3.4.4.6 Procedure for Sodium Nitrate (NaNO ) Extraction 60
3
3.4.5 Sequential Extraction 60
3.4.5.1 Procedure for Stage 1 Extraction 62
3.4.5.2 Procedure for Stage 2 Extraction 62
3.4.5.3 Procedure for Stage 3 Extraction 63
3.4.6 CISED 63
3.4.6.1 Procedure for CISED 64
3.4.7 In Vitro Gastrointestinal Extraction Method 65
3.4.7.1 Procedure for Gastric Extraction 66
3.4.7.2 Procedure for Gastric + Intestinal Extraction 67
3.4.8 In Vitro Simulated Epithelium Lung Fluid Method 67
3.4.8.1 Procedure for Inhalation Bioaccessibility Extraction 69
3.5 Summary 69
Reference 69
3.A Extraction Reagents for Single Extraction Methods 70
3.A.1 Preparation of EDTA, 50 mM 70
3.A.2 Preparation of AA, 0.43 M 70
3.A.3 Preparation of Diethylenetriaminepentaacetic Acid (DTPA),
5 mM 70
3.A.4 Preparation of Ammonium Nitrate (NH NO ), 1 M 70
4 3
Contents ix
3.A.5 Preparation of Calcium Chloride (CaCl ), 0.01 M 70
2
3.A.6 Preparation of Sodium Nitrate (NaNO ), 0.1 M 71
3
3.B Extraction Reagents for the Sequential Extraction Method 71
3.B.1 Preparation of Solution A (Acetic Acid, 0.11 M) 71
3.B.2 Preparation of Solution B (Hydroxylamine Hydrochloride or
Hydroxyammonium Chloride, 0.5 M) 71
3.B.3 Preparation of Solution C (Hydrogen Peroxide [300 mg g−1],
8.8 M) 71
3.B.4 Preparation of Solution D (Ammonium Acetate, 1 M) 71
3.C Extraction Reagents for the Unified Bioaccessibility Method 72
3.C.1 Preparation of Simulated Saliva Fluid 72
3.C.2 Preparation of Simulated Gastric Fluid 72
3.C.3 Preparation of Simulated Duodenal Fluid 72
3.C.4 Preparation of Simulated Bile Fluid 73
3.D Extraction Reagents for the In Vitro SELF 73
3.D.1 Preparation of SELF 73
4 Sample Introduction 75
4.1 Introduction 75
4.2 Nebulizers 76
4.3 Spray Chambers and Desolvation Systems 79
4.4 Discrete Sample Introduction 83
4.5 Continuous Sample Introduction 87
4.6 Hydride and Cold‐Vapour Generation Techniques 91
4.7 Summary 93
References 93
5 The Inductively Coupled Plasma 95
5.1 Introduction 95
5.2 Radiofrequency Generators 96
5.3 Inductively Coupled Plasma Formation and Operation 96
5.4 Processes Within the ICP 106
5.5 Signal Processing and Instrument Control 106
5.6 Summary 107
References 108
6 Inductively Coupled Plasma–Atomic Emission Spectrometry 109
6.1 Introduction 110
6.2 Fundamentals of Spectroscopy 110
6.2.1 Origins of Atomic Spectra 111
6.2.2 Spectral Line Intensity 113
6.2.3 Spectral Line Broadening 114
6.3 Plasma Spectroscopy 116
x Contents
6.4 Spectrometers 118
6.4.1 Sequential Spectrometer 122
6.4.2 Simultaneous Spectrometers 122
6.5 Detectors 125
6.5.1 Photomultiplier Tube 127
6.5.2 Charge‐Transfer Devices 128
6.6 Interferences 130
6.7 Summary 131
References 132
7 Inductively Coupled Plasma–Mass Spectrometry 133
7.1 Introduction 133
7.2 Fundamentals of Mass Spectrometry 134
7.2.1 Some Terminology 134
7.3 Inorganic Mass Spectrometry 135
7.3.1 The Ion Source: ICP 137
7.3.2 The Interface 138
7.4 Mass Spectrometers 139
7.4.1 Quadrupole Mass Spectrometer 140
7.4.2 High‐Resolution Mass Spectrometers 142
7.4.3 Ion‐Trap Mass Spectrometer 150
7.4.4 Time‐of‐Flight Mass Spectrometer 152
7.5 Detectors 153
7.6 Interferences 156
7.6.1 Isobaric Interferences 156
7.6.2 Molecular Interferences 158
7.6.3 Remedies for Molecular Interferences 161
7.6.3.1 Charge Transfer 161
7.6.3.2 Proton Transfer 162
7.6.3.3 Hydrogen‐Atom Transfer 162
7.6.3.4 Atom Transfer 162
7.6.3.5 Adduct Formation 162
7.6.4 Non‐Spectral Interferences: Matrix‐Induced 164
7.7 Isotope Dilution Analysis 165
7.8 Summary 176
References 176
8 Inductively Coupled Plasma: Current and Future Developments 177
8.1 Introduction 177
8.2 Comparison of ICP–AES and ICP–MS 177
8.3 Applications 182
8.4 Current and Future Developments 183
8.4.1 In General, for the ICP 184
Contents xi
8.4.2 For ICP–MS 185
8.4.3 For ICP–AES 189
8.5 Useful Resources 191
References 198
Further Reading 198
9 Inductively Coupled Plasma: Troubleshooting and Maintenance 201
9.1 Introduction 201
9.2 Diagnostic Issues 201
9.3 Tips to Reduce… 202
9.3.1 Potential Autosampler Issues 202
9.3.2 Contamination 202
9.4 Tips to Improve… 203
9.4.1 Sample Preparation 203
9.5 How To … 203
9.5.1 Unblock a Blocked Pneumatic Concentric Nebulizer 203
9.5.2 Clean the Spray Chamber 203
9.5.3 Clean the Plasma Torch 204
9.6 What to do About… 204
9.6.1 Plasma Ignition Problems 204
9.7 Shut Down Procedure (At the End of the Day) 204
9.8 Regular Maintenance Schedule 205
The Periodic Table 207
SI Units and Physical Constants 209
Index 213
xiii
About the Author
John R. Dean DSc, PhD, DIC, MSc, BSc, FRSC,
CChem, CSci, PFHEA
Since 2004, John R. Dean has been Professor of
Analytical and Environmental Sciences at
Northumbria University where he is also currently
Head of Subject in Analytical Sciences, which cov-
ers all Chemistry and Forensic Science Programmes.
His research is both diverse and informed, covering
such topics as the development of novel methods
to investigate the influence and risk of metals and
persistent organic compounds in environmental
and biological matrices, to development of new chromatographic methods for
environmental and biological samples using gas chromatography and ion
mobility spectrometry and development of novel approaches for pathogenic
bacterial detection/identification. Much of the work is directly supported by
industry and other external sponsors.
He has published extensively (over 200 papers, book chapters and books) in
analytical and environmental science. He has also supervised over 30 PhD
students.
John remains an active member of the Royal Society of Chemistry (RSC) and
serves on several of its committee’s including Analytical Division Council,
Committee for Accreditation and Validation of Chemistry Degrees, Research
Mobility Grant committee and is the International Coordinator for the Schools’
Analyst Competition.
After a first degree in Chemistry at the University of Manchester Institute of
Science and Technology (UMIST), this was followed by an MSc in Analytical
Chemistry and Instrumentation at Loughborough University of Technology,
and finally a PhD and DIC in Physical Chemistry at the Imperial College of
Science and Technology (University of London). He then spent two years as a
postdoctoral research fellow at the Government Food Laboratory in Norwich.
