Table Of ContentHandbook of Inductively Coupled Plasma Spectrometry
Handbook of
Inductively Coupled Plasma
Spectrometry
Second Edition
MICHAEL THOMPSON, BSc, PhD, ARCS, CChem., FRSC
Department of Chemistry
Birkbeck College
University of London
J. NICHOLAS WALSH, BSc, PhD
Department of Geology
Royal Holloway and Bedford New College
University of London
with additional invited chapters from
S.J. Walton and G.E.M. Hall
Blackie
Glasgow and London
Published in the USA by
Chapman and Hall
New York
Blackie and Son Ltd
Bishopbriggs, Glasgow G64 2NZ
7 Leicester Place, London WC2H 7BP
Published in the USA by
Chapman and Hall
a division of Routledge, Chapman and Hall, Inc.
29 West 35th Street, New York, NY 10001-2291
© 1989 Blackie & Son Ltd
Softcover reprint of the hardcover 1st edition 1989
First published 1983
Reprinted 1984, 1985, 1986
This edition 1989
All rights reserved.
No part of this publication may be reproduced,
stored in a retrieval system, or transmitted,
in any form or by any means,
electronic, mechanical, recording or otherwise,
without prior permission of the Publishers.
British Library Cataloguing in Publication Data
Thompson, Michael, 1942-
Handbook of inductively coupled plasma
spectrometry. -2nd ed.
I. Chemical analysis. Inductively coupled
plasma emission spectroscopy
I. Title II. Walsh, J. Nicholas (John Nicholas)
543'.0858
ISBN-13: 978-1-4612-8037-8 e-ISBN: 978-1-4613-0697-9
DOl: 10.1007/978-1-4613-0697-9
Library of Congress Cataloging-in-Publication Data
Thompson, Michael, Ph.D.
Handbook of inductively coupled plasma spectrometry.
"A complete revision with additional invited
chapters from S.J. Walton and G.E.M. Hall."
Bibliography: p.
Includes index.
\. Plasma spectroscopy. I. Walsh, J.N. (John
Nicholas) II. Title.
QD96.P62T48 1988 543'.0858 88-20270
Phototypesetting by Thomson Press (India) Limited, New Delhi
Preface
The first edition of our Handbook was written in 1983. In the preface to
the first edition we noted the rapid development of inductively coupled
plasma atomic emission spectrometry and its considerable potential for
elemental analysis. The intervening five years have seen a substantial
growth in ICP applications; much has happened and this is an appropriate
time to present a revised edition.
The basic approach of the book remains the same. This is a handbook,
addressed to the user of the technique who seeks direct, practical advice.
A concise summary of the technique is attempted. Detailed, theoretical
treatment of the background to the method is not covered. We have,
however, thoroughly revised much of the text, and new chapters have
been added. These reflect the changes and progress in recent years. We
are grateful to Mr Stephen Walton, Dr Gwendy Hall and London and
Scandinavian Metallurgical Co. Ltd for their contributions. Chapter 3
(Instrumentation) has been rewritten by Mr Walton, the new Chapter on
ICP-mass spectrometry has been written by Dr Hall, and London and
Scandinavian provided much of the information for the chapter on metals
analysis by ICP-AES. These chapters have been integrated into the book,
and a conscious effort has been made to retain the unity of style within the
book. New material has been added elsewhere in the book, archaeological
materials are considered, pre concentration methods and chemometrics
covered more fully. Other sections of the Handbook have stood the test of
time and remain much as before. The chapter on 'ICP and the future' has
been omitted-the future is with us now.
It is our intention that this Handbook will provide an introduction to
ICP spectrometry for those using the technique in routine analytical
applications. It is designed to present general background information on
ICP-AES analysis for those who need to familiarize themselves with the
reality and the potential of the technique. The book brings together a
systematic collection of information on the background and operation of
the ICP. It also provides detailed methods for those involved in routine
analysis. In our revision of the book we have tried to expand its usefulness
to cover a greater range of areas of application. We hope that it will be
both a laboratory manual and a general reference text.
We should like to acknowledge our considerable debt to all those
friends and colleagues who have contributed to this book, directly or
v
vi PREFACE
indirectly, by way of material assistance, collaboration, technical dis
cussion or simply tolerating us while we were writing. One of us (JNW) is
indebted to the Natural Environment Research Council, the University of
London and Philips for financial support, and to Jan Barker and Alison
Warren for their support and assistance.
Contents
1 Introduction 1
1.1 Preliminary-purpose and scope of book 1
1.1.1 The ICP as a spectroscopic source 1
1.1.2 Applications of the ICP 3
1.1.3 Simplicity of the ICP technique 3
1.1.4 The literature of ICP-AES 4
1.2 Historic development of ICP spectrometry 5
1.3 Background to quantitative ICP analysis 7
1.3.1 Sample introduction (nebulization) 8
1.3.2 Sample excitation system 9
1.3.3 Analysis and quantification of emission spectrum 12
1.4 Range of determinable elements in geological materials 14
2 Analytical characteristics 16
2.1 Introduction 16
2.2 Simultaneous analysis 19
2.2.1 Compromise operating conditions 19
2.3 Sequential analysis ICP system 23
2.4 Detection limits 24
2.5 Calibration range oflCP-AES 25
2.6 Interferences 26
2.6.1 Spectral overlaps 27
2.6.2 Stray light interference 29
2.6.3 Matrix effect 30
2.7 Precision and accuracy 32
2.7.1 Chemometric improvements to data quality 34
2.8 Experimental considerations 37
2.8.1 Solution volumes and sample weights 37
2.8.2 Number of elements determined in liquid samples 38
2.8.3 Number of elements determined in solid samples 39
2.9 The injection of organic liquids into an ICP 40
3 Instrumentation for ICP-AES 43
3.1 Introduction 43
3.2 Spectrometers 45
3.2.1 General requirements 45
3.2.2 Simultaneous spectrometers 47
3.2.3 Sequential spectrometers 55
3.2.4 Combined simultaneous/sequential spectrometers 59
3.3 Plasma torches 59
3.3.1 Nomenclature 59
3.3.2 The Greenfield torch 60
3.3.3 The Fassel torch 60
3.3.4 The Minitorch™ 64
3.3.5 Torch maintenance 65
3.4 Nebulizer systems 66
3.4.1 Introduction 66
3.4.2 Concentric pneumatic nebulizers 66
vii
viii CONTENTS
3.4.3 Cross-flow nebulizers 72
3.4.4 Babington-type nebulizers 74
3.4.5 Frit-type nebulizers 75
3.4.6 Ultrasonic nebulizers 76
3.4.7 Direct nebulization 77
3.4.8 Spray chambers 77
3.5 Radiofrequency generators and source 80
3.6 Electronics, computers and software 81
3.6.1 Software requirements 82
3.6.2 Trends 83
3.7 Fourier transform spectrometers 83
3.8 ICP-atomic fluorescence spectrometry 85
3.9 Direct current plasmas (DCP) 86
3.10 Microwave plasmas (MIP) 88
3.11 Choice of an ICP system 88
3.11.1 ICP-AES in relation to AAS 88
3.11.2 ICP-AES and X-ray fluorescence 89
3.11.3 ICP-AES and DCP emission spectrometry 90
3.11.4 ICP-AES and ICP-mass spectrometry 90
3.11.5 ICP-AES and other excitation methods 9 I
3.11.6 Evaluation of an ICP-AES system 92
4 Silicate rock analysis 93
4.1 Dissolution methods for silicates 93
4.1.1 Introduction 93
4.1.2 Fusion dissolution methods 93
4.1.3 Hydrofluoric acid dissolution methods-open evaporation 95
4.1.4 Hydrofluoric acid dissolution methods-closed digestion 96
4.2 Instrument calibration 99
4.3 Major element determinations 100
4.4 Trace element analysis 105
4.5 Rare earth element determinations 120
4.5.1 Introduction 120
4.5.2 Dissolution procedure 122
4.5.3 REE separation 124
4.5.4 REE spectral lines 125
4.5.5 Evaluation of results 127
5 Multielement applications of ICPS in applied geochemistry 130
5.1 The nature and evolution of applied geochemistry 130
5.1.1 Introduction 130
5.2 General aspects of applied geochemical analysis 131
5.2.1 Analytical requirements in applied geochemistry 131
5.2.2 Analytical quality control procedures 133
5.3 ICP instrumentation in relation to the requirements of applied geochemistry 137
5.3.1 Introduction 137
5.3.2 Translational interference effects 138
5.3.3 Rotational interference effects 14 I
5.3.4 Other instrumental constraints in multielement analysis 145
5.4 Decomposition procedures in applied geochemical analysis 147
5.4.1 Introduction 147
5.4.2 General aspects of large-batch analysis 150
5.4.3 Decomposition with nitric acid and perchloric acid 155
5.4.4 Decomposition with hydrofluoric acid, nitric acid and perchloric acid
(test tube version) 156
CONTENTS ~
6 Gas phase sample injection 161
6.1 The development of gas phase injection methods 161
6.2 Methodology of the hydride injection system 164
6.2.1 Equipment 164
6.2.2 Operating conditions 166
6.2.3 Performance of the hydride generation/ICP system 167
6.2.4 Interference effects and their avoidance 170
6.2.5 Arsenic speciation methods 173
6.3 Applications of the hydride injection system 173
6.3.1 General introduction 173
6.3.2 Traces of arsenic, antimony and bismuth in soils and sediments 174
6.3.3 Traces of arsenic, antimony and bismuth in plant materials 176
6.3.4 Trace concentrations of selenium in soils and sediments 177
6.3.5 The determination of trace concentrations of arsenic, antimony,
bismuth, selenium and tellurium in waters 178
6.3.6 The determination of tin in rock, soils and sediments 180
7 Injection methods for solid samples 183
7.1 Introduction to solid sample injection methods 183
7.2 Sample injection following electrothermal vaporization 184
7.3 Direct sample injection from a graphite rod 187
7.4 Discrete sample injection by means of laser ablation 188
7.4.1 General introduction 188
7.4.2 The Lasertrace system 190
7.4.3 The LMAIO laser-ICP microprobe system 191
7.5 Nebulization of slurries 199
8 Water analysis by ICP-AES 201
8.1 Introduction 20 I
8.2 General aspects of water analysis 203
8.2.1 Sampling 203
8.2.2 Filtration 203
8.2.3 Storage 204
8.2.4 Stabilization 204
8.2.5 Avoidance of contamination 204
8.3 Direct water analysis by ICP-AES 205
8.3.1 Pneumatic nebulizers 205
8.3.2 Alternative nebulizers 207
8.3.3 Gas phase injection 208
8.3.4 Electrothermal vaporization and other discrete methods 208
8.4 Water analysis with preconcentration 209
8.4.1 Evaporation methods 209
8.4.2 Mixed-bed ion exchange method 210
8.4.3 Selective ion exchange methods 210
8.4.4 Solvent extraction methods 210
8.4.5 A chelation-solvent extraction procedure 211
8.4.6 Coprecipitation methods 213
9 The analysis of environmental materials by ICP-AES 215
9.1 Introduction 2 I 5
9.2 Air analysis 216
9.2.1 Volatile contaminants 216
9.2.2 Particle contaminants 217
9.3 Sewage sludge 219
x CONTENTS
9.4 Domestic dust, road dust and industrial dust 220
9.4.1 Domestic dusts 220
9.4.2 Road dusts 220
9.4.3 Industrial dusts 223
9.5 Domestic and industrial refuse 223
9.6 The analysis of animal and plant tissues 224
9.6.1 General introduction 224
9.6.2 Sample decomposition of biological materials 227
9.6.3 Destruction of organic matter in plant and animal tissue with perchloric
acid-nitric acid mixtures 230
10 The analysis of archaeological materials by ICP-AES 232
10.1 Introduction 232
10.2 Archaeological materials 233
10.2.1 Analysis of flints 233
10.2.2 Pottery and clay analysis 235
10.2.3 Analysis of bricks, tiles, glazes, etc. 236
10.2.4 Analysis of metals 236
10.2.5 Analysis of slags and ores 237
11 Inductively coupled plasma mass spectrometry 238
ILl Instrumentation 238
11.2 Optimization 242
11.3 Interferences 243
11.3.1 Spectral interferences 243
11.3.2 Non-spectral interferences 246
11.4 Calibration strategies 247
11.4.1 External 248
11.4.2 Isotope dilution 249
11.4.3 Standard additions 251
1l.5 Applications of ICP-MS with sample introduction by nebulization 251
11.5.1 Elemental analysis of solubilized geological samples 252
11.5.2 Isotope ratio measurements 257
11.5.3 Analysis of waters 260
11.6 Other modes of sample introduction 262
11.6.1 Electrothermal vaporization (ETV) 262
11.6.2 Direct sample insertion device (DSID) 265
11.6.3 Laser ablation of solids 265
11.6.4 Arc nebulization (solid sampling) 267
11.6.5 Slurry nebulization (solid sampling) 267
11.7 Future directions 268
12 Analysis of metals by ICP-AES 270
12.1 Introduction 271
12.1.1 Instrument calibration 272
12.1.2 Internal standards 272
12.1.3 Sample preparation and dissolution 273
12.2 Analysis of iron and steel 274
12.2.1 Spectral lines 274
12.2.2 Sample dissolution 274
12.3 Analysis of other metals 276
12.3.1 Virgin aluminium program 277
12.3.2 Titanium-boron-aluminium program 278
12.3.3 Zirconium-aluminium program 279
12.3.4 Chromium program 280
12.3.5 Chrome carbon program 281
