Stable Isotope Geochemistry

212 Pages·1997·11.844 MB·English

by  Professor Dr. Jochen Hoefs (auth.)

Jochen Hoefs
Stable Isotope Geochemistry
Springer-Verlag Berlin Heidelberg GmbH
Jochen Hoefs
Stable Isotope
Geochemistry
4th, Completely Revised, Updated, and Enlarged Edition
With 73 Figures and 22 Tables
Springer
Professor Dr. Jochen Hoefs
Institute of Geochemistry
University of Gottingen
GoldschmidtstraBe 1
D-37077 Gottingen
Germany
Library of Congress Cataloging-in-Publication Data
Hoefs, Jochen.
Stable isotope geochemistry/Jochen Hoefs. - 4th. completely rev., up
dated, and en!. ed. p. cm. Includes bibliographical references and index.
ISBN 978-3-662-03379-1 ISBN 978-3-662-03377-7 (eBook)
DOI 10.1007/978-3-662-03377-7
1. Geochemistry. 2. Isotope geology. I. Title. QE515.H54 1997
551.9-dc20 96-31362
This work is subject to copyright. All rights are reserved, whether the
whole or part of material is concerned, specifically the rights of translati
on, reprinting, reuse of illustrations, recitation, boardcastin, reproduktion
on microfIlm or in any other way, and storage in data banks. Duplication
of the publication or parts thereof is permitted only under the provisions
of the German Copyright Law of September 9, 1965, in its current version,
and permission for use must always be obtained from Springer-Verlag.
Violations are liable for prosecution unter German Copyright Law.
© Springer-Verlag Berlin Heidelberg 1997, 1987, 1980, 1973
Originally published by Springer-Verlag Berlin Heidelberg New York in 1997.
Softcover reprint of the hardcover 4th edition 1997
The use of general descriptive names, registered names, trademarks, etc. in
this publication dos nor imply, even in the absence of a specific statement,
that such names are exempt from the relevant protective laws and regula
tions and therefor free for general use
SPIN 10510065 32/3135 - 5 43210 - Printed on acid-free paper
Preface
Stable isotope geochemistry has become an essential part of
geochemistry and has contributed significantly to the solu
tion of a wide variety of geological problems, which span the
whole field of earth sciences, from paleoclimatology to cos
mochemistry, from oceanography to mantle geochemistry, to
list only a few. In some fields such as ore deposit studies, sta
ble isotopes have played an integral part for many years; in
others such as environmental studies the application of stable
isotopes is still growing. In recent years new microanalytical
techniques, permitting relatively precise analysis of very
small sample sizes, have opened up exciting research avenues
which will allow the investigation of a new generation of
problems.
These latest developments make a complete revision of the
3rd edition necessary. Although the new edition follows the
subdivision of the earlier ones, it has been totally rewritten on
the basis of the literature which has appeared since 1987. I have
again tried to give a well-balanced discussion of the whole
field, although I do not claim that every aspect has been con
sidered and that no omission can be found. The book is not
written primarily for the specialist in the field of stable iso
tope geochemistry, but more for the non-specialist and grad
uate student, who needs practical knowledge of how to inter
pret stable isotope ratios.
My colleagues Tony Fallick, Russ Harmon, and Antonio Lon
ginelli have reviewed an early draft of the manuscript, which
is gratefully acknowledged. Special thanks go to Russ Har
mon, who has considerably improved the clarity of style and
presentation. I take full responsibility, however, for any short
comings that remain.
Gottingen, April 1996 Jochen Hoefs
Table of Contents
Chapter!
Theoretical and Experimental Principles
1.1 General Characteristics of Isotopes ..................... .
1.2 Isotope Effects ........................................................ . 3
1.3 Isotope Fractionation Processes .......................... . 5
1.3.1 Isotope Exchange ................................................... . 5
1.3·1.1 Fractionation Factor (ex) ....................................... . 7
1.3.1.2 The Delta Value (6) ................................................ . 8
1·3·1·3 Evaporation-Condensation Processes ................. . 9
1.3.2 Kinetic Effects ........................................................ . 10
1.3·3 Diffusion ................................................................. . 11
1.3-4 Other Factors Influencing Isotopic Fractionations 14
1.3·4·1 Chemical Composition ......................................... . 14
1.3.4.2 Crystal Structure ................................................... . 14
1.3·4·3 Non-Mass-Dependent Isotope Effects ................. . 14
1.3·5 Isotope Geothermometers .................................... . 15
1.3·5·1 Theoretical Calculations ....................................... . 16
1.3.5.2 Experimental Calibrations .................................... . 17
1.4 Basic Principles of Mass Spectrometry ............... . 19
1.5 Standards ................................................................ . 22
1.6 General Remarks on Sample Handling ................ 24
1.7 New Microanalytical Techniques.......................... 25
1.7.1 Laser Microprobe ................................................... 25
1.7.2 Gas Chromatography Combined with Gas Mass
Spectrometry .......................................................... 25
1.7.3 Secondary Ion Mass Spectrometry....................... 26
Chapter 2
Isotope Fractionation Mechanisms
of Selected Elements
2.1 Hydrogen................................................................. 28
2.1.1 Preparation Techniques and Mass Spectrometric
Measurements......................................................... 29
2.1.2 Standards................................................................. 29
2.1·3 Fractionation Mechanisms .................................... 30
2·1.3·1 Equilibrium Exchange Reactions.......................... 32
2.1·3·2 Kinetic Isotope Effects ........................................... 33
2·1.3·3 Other Fractionation Effects ................................... 34
2.2 Lithium.................................................................... 34
2·3 Boron....................................................................... 36
2·4 Carbon..................................................................... 38
241 Preparation Techniques ......................................... 39
242 Standards................................................................. 39
2·4·3 Fractionation Mechanisms ............................ ........ 39
2·4·3-1 Inorganic Carbon System ...................................... 40
2-4.3.2 Carbon Isotope Fractionations During
Photosynthesis........................................................ 41
Interactions Between the Carbonate-Carbon
Reservoir and Organic Carbon Reservoir .... ........ 42
2·5 Nitrogen .................................................................. 43
2.6 Oxygen ..................................................................... 47
2.6.1 Preparation Techniques ......................................... 47
2.6.2 Standards................................................................. 49
2.6.3 Fractionation Mechanisms ............ ........................ 49
2.6·4 Fluid-Rock Interactions ........................................ 53
2.7 Silicon ...................................................................... 56
2.8 Sulfur ....................................................................... 57
2.8.1 Preparation Techniques ......................................... 58
2.8.2 Fractionation Mechanisms .................................... 59
2.8.2.1 Bacterial Reduction of Sulfate............................... 59
2.8.2.2 Thermochemical Reduction of Sulfate................. 60
2.8.2.3 Isotope Exchange Reactions .................................. 60
2.9 Chlorine................................................................... 62
Chapter 3
Variations of Stable Isotope Ratios in Nature
3·1 Extraterrestrial Materials .................................... .. 65
3·1.1 Meteorites................................................................ 65
3·1.1.1 Hydrogen................................................................. 67
3·1.1.2 Carbon..................................................................... 68
3.1.1.3 Nitrogen ................................................................ .. 69
3.1.1.4 Sulfur ...................................................................... . 69
3·1.2 The Moon and the Neighboring Planets Mars and
Venus ....................................................................... 70
3.1.2.1 The Moon ................................................................ 70
3.1.2.2 Mars ........................................................................ . 71
3.1.2.3 Venus ...................................................................... . 72
3.1.3 Comets..................................................................... 72
3.1.4 Interplanetary Dust Particles ................................ 72
3·2 Isotopic Composition of the Upper Mantle ......... 73
3.2.1 Oxygen..................................................................... 74
3·2.2 Hydrogen................................................................. 75
3.2.3 Carbon..................................................................... 76
3·2·4 Sulfur ....................................................................... 78
3·2·5 Nitrogen .................................................................. 79
3·3 Magmatic Rocks ..................................................... 79
3.3.1 Fractional Crystallization ...................................... 80
3·3·2 Differences Between Volcanic and Plutonic Rocks 80
3·3-3 Low-Temperature Alteration Processes................ 80
3-3·4 Assimilation of Crustal Rocks............................... 81
3-3·5 Basaltic Rocks from Different Tectonic Settings. 81
3.3.6 Ocean Water/Basaltic Crust Interactions............. 83
3·3-7 Granitic Rocks ........................................................ 84
3·4 Volatiles in Magmatic Systems.............................. 84
3-4-1 Glasses ..................................................................... 85
3-4-1.1 Hydrogen................................................................. 85
3-4-1.2 Carbon..................................................................... 85
3-4-1.3 Nitrogen .................................................................. 86
3-4-1.4 Sulfur ....................................................................... 86
3-4-2 Volcanic Gases and Hot Springs ........................... 87
3-4-2.1 Water........................................................................ 87
3.4.2•2 Carbon..................................................................... 88
3.4.2.3 Sulfur ....................................................................... 89
3-4-3 Isotope Thermometers in Geothermal Systems.. 89
3·5 Ore Deposits and Hydrothermal Systems ............ 90
3·5·1 Origin of Ore Fluids ............................................... 91
3·5·1.1 Seawater................................................................... 92
3.5.1.2 Meteoric Waters ...................................................... 93
3·5·1·3 Juvenile Water ......................................................... 93
3·5·1.4 Magmatic Water...................................................... 93
3·5·1.5 Metamorphic Water ............................................... 94
3·5·1.6 Formation Waters ................................................... 94
3.5.2 Wall-Rock Alteration....................................... ....... 94
3·5·3 Fossil Hydrothermal Systems................................ 95
3·5·4 Hydrothermal Carbonates ..................................... 96
3·5·5 Sulfur Isotope Composition of Ore Deposits ...... 97
3·5·5·1 Importance of Changing f0 and pH ................... 97
2
3.5.5.2 Reservoir Effect ...................................................... 99
3·5·5·3 Recent Sulfide Deposits at Mid-Ocean Ridges..... 100
3·5·5·4 Magmatic Ore Deposits ......................................... 100
3·5·5·5 Magmatic Hydrothermal Deposits ....................... 101
3·5·5·6 Base and Precious Metal Vein Deposits................ 101
3·5·5·7 Volcanic-Associated Massive Sulfide Deposits.... 101
3.5·5·8 Shale/Carbonate-Hosted Massive Sulfide Deposits 102
3·5·5·9 Mississippi Valley Type Deposits .......................... 102
3·5·5·10 Biogenic Deposits ................................................... 103
3.5.5.11 Metamorphosed Deposits ..................................... 103
3·6 Hydrosphere............................................................ 103
3·6.1 Meteoric Water ........................................................ 104
3·6.1.1 cSD-cS1BO Relationship ............................................. 106
3.6.1.2 Ancient Meteoric Waters........................................ 107
3·6.2 Ice Cores .................................................................. 107
3·6·3 Groundwater ........................................................... 109
3.6-4 Isotope Fractionations During Evaporation ........ 110
3.6·5 Ocean Water ............................................................ 111
3·6.6 Pore Waters ............................................................. 113
3·6·7 Formation Water..................................................... 113
3·6.8 Water in Hydrated Salt Minerals........................... 115
3·7 Isotopic Composition of the Ocean During
Geological History.................................................. 116
3.7.1 Oxygen ..................................................................... 117
3.7.2 Carbon ..................................................................... 117
3·7·3 Sulfur ....................................................................... 118
3.8 Isotopic Composition of Dissolved and Particulate
Compounds in Ocean and Fresh Waters .............. 120
3·8.1 Carbon Species in Water ........................................ 120
3·8.1.1 Bicarbonate in Ocean Water .................................. 120
3·8.1.2 Particulate Organic Matter .................................... 121
3·8·1.3 Carbon Isotope Composition of Pore Waters ...... 122
3·8·1.4 Carbon in Fresh Waters.......................................... 123
3·8.2 Nitrogen .................................................................. 123
3·8·3 Oxygen ..................................................................... 124
3·8·4 Sulfate '" ............. ............................. ................ ......... 124
3·9 Atmosphere............................................................. 125
3·9·1 Nitrogen .................................................................. 126
3.9.2 Oxygen ..................................................................... 127
3·9·3 Ozone ....................................................................... 127
3·9·4 Carbon Dioxide ...................................................... 127
3.9-4.1 Carbon ..................................................................... 127
3·9·4·2 Oxygen ..................................................................... 129
3·9·4·3 Long-Term Variations in the CO2 Concentration 130
3·9·5 Methane................................................................... 131
3·9·6 Hydrogen................................................................. 131
3·9·7 Sulfur ....................................................................... 132
3.10 Biosphere................................................................. 133
3.10.1 Living Organic Matter ............................................ 133
3.10.1.1 Bulk Carbon ............................................................ 133
3.10.1.2 Chemical Components of Plant Material............. 135