Microprobe techniques in the earth sciences

418 Pages·1995·47.096 MB·English

by  P J Potts, Mineralogical Society (Great Britain)

Microprobe Techniques in the Earth Sciences
Mineralogical Society Series
Series editor
Dr A.P. Jones
The aim of the series is to provide up-to-date reviews through the selected
but specialized contributions of leading experts. A particularly attractive
feature of the series is the tutorial element, making it suitable for third year
undergraduates and researchers of all levels not solely within the Earth
Sciences. Each volume is purpose-designed, highly illustrated and serves as
an excellent reference tool.
TITLES AVAILABLE
1 Deformation Processes in Minerals, Ceramics and Rocks
Edited by D.J. Barber and P.G. Meredith
2 High-temperature Metamorphism and Crustal Anatexis
Edited by J.R. Ashworth and M. Brown
3 The Stability of Minerals
Edited by Geoffrey D. Price and Nancy L. Ross
4 Geochemistry of Clay-Pore Fluid Interactions
Edited by D.A.C. Manning, P.L. Hall and C.R. Hughes
5 Mineral Surfaces
Edited by D.J. Vaughan and R.A.D. Pattrick
6 Microprobe Techniques in the Earth Sciences
Edited by Philip J. Potts, John F.W. Bowles, Stephen J.B. Reed
and Mark R. Cave
Microprobe Techniques
in the Earth Sciences
Edited by Philip J. Potts
Department of Earth Sciences, The Open University, Milton Keynes MK7
6AA, UK
John F.W. Bowles
Mineral Science Ltd, Chesham HP5 2PZ, UK
Stephen J.B. Reed
Department of Earth Sciences, University of Cambridge CB2 3EQ, UK
and
Mark R. Cave
Analytical Geochemistry Group, British Geological Survey, Keyworth,
Nottingham NG12 5GG, UK
Published in association with
The Mineralogical Society of Great Britain and Ireland
CHAPMAN &. HALL
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First edition 1995
© 1995 The Mineralogical Society
Typeset in 10/12 Times by Best-set Typesetter Ltd .. Hong Kong
ISBN 0 -112 55100 -I
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Contents
Colour plates appear between pages 20 and 21; other plates appear
between pages 68 and 69, and 292 and 293.
List of contributors IX
Preface Xl
1 Microanalysis from 1950 to the 1990s 1
James V.P. Long
1.1 Introduction 1
1.2 Microscope methods with image-plane selection 1
1.3 Microprobe methods 3
1.4 The possibilities: primary and secondary beams 3
1.5 Some history 5
1.6 Quantitative analysis 11
1.7 Precision, accuracy and resolution 14
1.8 Other techniques using electrons and/or X-rays 25
1.9 Selected-area mass spectrometry with direct excitation 33
1.10 Selected-area mass spectrometry with indirect excitation 39
1.11 Laser heating 39
1.12 Detection of molecular species 41
1.13 Which technique? Analytical strategy and tactics 42
References 46
2 Electron microprobe microanalysis 49
Stephen J.B. Reed
2.1 Introduction 49
2.2 X-ray spectroscopy 52
2.3 Wavelength-dispersive spectrometers 57
2.4 Energy-dispersive spectrometers 60
2.5 The electron column 65
2.6 Scanning and mapping 70
2.7 Qualitative analysis 73
2.8 Quantitative analysis - experimental 75
2.9 Quantitative analysis - data reduction 81
References 87
Further reading 88
CONTENTS
3 Analytical electron microscopy 91
Pamela E. Champness
3.1 Introduction 91
3.2 The X-ray analysis of thin specimens 96
3.3 Electron energy-loss spectroscopy 124
3.4 EDS versus EELS 135
3.5 Future directions of AEM instrumentation 135
Acknowledgements 136
References 136
4 The nuclear microprobe - PIXE, PIGE, RBS, NRA and 141
ERDA
Donald G. Fraser
4.1 Introduction 141
4.2 The proton microprobe 142
4.3 The PIXE technique 144
4.4 Geological applications of PIXE 151
4.5 Nuclear reaction analysis (NRA) and PIGE 156
4.6 Rutherford backscattering (RBS) 157
4.7 Elastic recoil detection analysis (ERDA) 159
4.8 Conclusions 159
Acknowledgements 160
References 160
5 Synchrotron X-ray microanalysis 163
Joseph V. Smith and Mark L. Rivers
5.1 Introduction 163
5.2 Synchrotron storage rings 173
5.3 Beamline and experimental stations 186
5.4 Specimen preparation 201
5.5 Analysis 204
5.6 Illustrative applications and future advances 213
Acknowledgements 221
Invitation 222
Appendix SA Notation and abbreviations 222
References 223
Further reading 227
6 Ion microprobe analysis in geology 235
Richard W. Hinton
6.1 Introduction 235
6.2 Instrumentation 235
6.3 Secondary ion production 246
6.4 Analytical procedures 255
vi
CONTENTS
6.5 Applications: elemental analysis 262
6.6 Applications: isotopic analysis 273
6.7 Future developments 281
Acknowledgements 282
References 282
7 Mineral microanalysis by laserprobe inductively coupled
plasma mass spectrometry 291
William T. Perkins and Nicholas J.G. Pearce
7.1 Introduction 291
7.2 Inductively coupled plasma mass spectrometry 291
7.3 Laser ablation and ICP-MS 300
7.4 Analytical rationale 302
7.5 History of laser ablation analysis 303
7.6 Bulk sampling with LA-ICP-MS: an alternative to solution
preparation 304
7.7 Analytical methodology 304
7.8 Detection limits 313
7.9 Applications 316
7.10 Future trends 321
7.11 Conclusions 323
References 323
8 Ar-Ar dating by laser microprobe 327
Simon P. Kelley
8. J Introduction 327
8.2 The ·j()Ar-3~Ar dating technique 329
8.3 Estimation of errors 334
8.4 Instrumentation 336
8.5 Methodology 347
8.6 Applications of the laser microprobe technique 349
References 356
9 Stable isotope ratio measurement using a laser microprobe 359
Ian P. Wright
9.1 Introduction 359
9.2 Stable isotope geochemistry 360
9.3 Conventional preparation of gases for stable isotope studies 361
9.4 Stable isotope ratio mass spectrometry 362
9.5 Historical development of the laser microprobe 364
9.6 Application of the laser microprobe to stable isotope studies 365
9.7 Instrumentation 367
9.8 Carbon and oxygen isotopic analyses of carbonates 369
9.9 Sulphur isotopic measurements of sulphides 373
vii
CONTENTS
9.10 Oxygen isotopic analyses of silicates and oxides 375
9.11 Nitrogen isotope analyses 380
9.12 Conclusions 382
Acknowledgements 383
References 383
10 Micro-Raman spectroscopy in the Earth Sciences 387
Stephen Roberts and Ian Beattie
10.1 Introduction 387
10.2 Principles 387
10.3 Instrumentation 392
lOA Sample handling and routine operation 394
10.5 Advantages and disadvantages of the Raman technique 394
10.6 Some applications of micro-Raman spectroscopy in the Earth
Sciences 395
10.7 Other applications of micro-Raman spectroscopy in the Earth
Sciences 405
10.8 Other Raman techniques and closing remarks 406
Acknowledgements 406
References 406
Index 409
Vlll
Contributors
Ian Beattie Department of Geology, University of
Southampton, Highfield, Southampton S09 5NH.
UK.
Pamela E. Department of Geology. University of Manchester.
Champness Oxford Road, Manchester M13 9PL, UK.
Donald G. Fraser Department of Earth Sciences. University of
Oxford. Parks Road, Oxford OXl 3PR, UK.
Richard W. Hinton Department of Geology and Geophysics. Uni
versity of Edinburgh, West Mains Road, Edinburgh
EH9 3JW, UK.
Simon P. Kelley Department of Earth Sciences, The Open Uni
versity, Walton Hall, Milton Keynes MK7 6AA.
UK.
James V.P. Long Department of Earth Sciences. Bullard Labora
tories, University of Cambridge. Madingley Rise.
Madingley Road, Cambridge CB3 OEZ, UK.
Nicholas G.B. Pearce Institute of Earth Studies, University of
Wales - Aberystwyth, Aberystwyth SY23 3DB. UK.
William T. Perkins Institute of Earth Studies. University of Wales -
Aberystwyth, Aberystwyth, SY23 3DB, UK.
Stephen J.B. Reed Department of Earth Sciences. University of
Cambridge. Downing Street. Cambridge CB2 3EQ.
UK.
Mark L. Rivers Department of Geophysical Sciences and Center
for Advanced Radiation Studies, University of
Chicago, 5734 South Ellis Avenue. Chicago IL
60637, USA
Stephen Roberts Department of Geology, University of Sou
thampton, Highfield, Southampton S09 5NH, UK.
Joseph V. Smith Department of Geophysical Sciences and Center
for Advanced Radiation Studies, University of
Chicago, 5734 South Ellis Avenue, Chicago IL
60637, USA.
IX
LIST OF CONTRIBUTORS
Ian P. Wright Planetary Sciences Unit, Department of Earth
Sciences, The Open University, Walton Hall,
Milton Keynes MK7 6AA, UK.
x