Stable Isotope Geochemistry

219 Pages·1980·4.609 MB·English

by  Professor Dr. Jochen Hoefs (auth.)

Minerals and Rocks 9
Editor in Chief
P. J. Wyllie, Chicago, IL
Editors
A. El Goresy, Heidelberg
W von Engelhardt, Tiibingen · T. Hahn, Aachen
Jochen Hoefs
Stable Isotope
Geochemistry
Second, Completely Revised and Updated Edition
With 52 Figures
Springer-Verlag
Berlin Heidelberg GmbH 1980
Professor Dr. JocHEN HoEFS
Geochemisches Institut der Universitiit
GoldschmidtstraBe 1, 3400 Gottingen, FRG
Volumes 1 to 9 in this series appeared under the title
Minerals, Rocks and Inorganic Materials
ISBN 978-3-662-02292-4 ISBN 978-3-662-02290-0 (eBook)
DOl 10.1007/978-3-662-02290-0
Library of Congress Cataloging in Publication Data. Hoefs, Jochen. Stable
isotope geochemistry. (Minerals and rocks; v. 9). Bibliography: p. Includes Index.
l. Geochemistry. 2. Isotope geology. I. Title. II. Series. QE515.H54 1980
551.9 80-11439
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©by Springer-Verlag Berlin Heidelberg 1973 and 1980.
Originally published by Springer-Verlag Berlin Heidelberg New York in 1980
Softcover reprint of the hardcover 2nd edition 1980
The use of registered names, trademarks, etc. in this publication does not imply,
even in the absence of a specific statement, that such names are exempt from the
relevant protective laws and regulations and therefore free for general use.
2132/3130-543210
Preface to the Second Edition
Since the first edition of this book appeared in 1973
knowledge in the field of isotope geochemistry has
grown so fast that it appeared necessary to revise it ac
cordingly. Although the main subdivisions have re
mained the same, the book has been totally revised and
rewritten. Some reviewers of the first edition have crit
icized the subdivisions and proposed a more appropriate
subdivision of the book along the line of different
chemical elements. Since this book is mainly written
for earth scientists and not for chemists, I believe the
present subdivision to be more appropriate. I am fully
aware that any subdivision is problematical and debat
able (nature is indivisible), however, for practical pur
poses, geochemists have, for a long time, tried to sub
divide the earth into certain "spheres". This book fol
lows the classical scheme of subdivision with all its dis
advantages, because I have no better one.
I am especially grateful to my colleagues who, during
the various stages of the preparation of the manuscripts
have read and criticized parts or whole drafts of the
manuscript. I owe my deepest thanks to the following
persons (in alphabetical order): W. Deuser (Woods
Hole, Mass.), R. Harmon (East Kilbride, Scotland),
T. Hoering (Washington, D.C.), H. Hubberten (Karls
ruhe, Germany), Y. Kolodny (Jerusalem), J. O'Neil
(Menlo Park, Calif.), B. Robinson (Wellington, N .Z.),
W. Sackett (College Station, Texas), H. Sakai (Misasa,
Japan), M. Schoen (Hannover, Germany), E. Usdowski
(Gottingen, Germany).
However, I take, of course, full responsibility for
any shortcomings.
Gottingen, January 1980 JOCHEN HOEFS
Preface to the First Edition
Over 10 years have passed since Rankama's second
book, Progress in Isotope Geology, surveyed the liter
ature on isotope abundance determinations. In the
meantime the number of measurements and publica
tions has increased enormously. Therefore, it seems
necessary to summarize the knowledge in this field in
the light of more recent developments.
The title of this book was chosen because the whole
field of radioactive isotope geochemistry has been de
liberately omitted.
The book is divided into three parts. Section A
gives the theory of isotope effects and the technical
background, both aspects being discussed rather brief
ly. The author regrets some shortcomings in the intro
ductory section, especially in the theoretical treatment
of isotope fractionation, but he has been trained main
ly in earth sciences rather than in physical chemistry.
Section B gives a summary of the fractionation
mechanisms affecting the most important elements -
hydrogen, carbon, oxygen, and sulfur. Further, it sur
veys some other elements that have not yet been as
thoroughly investigated.
Section C surveys the most important results from a
geological stand-point. In some cases the opinions of
different authors on the same subject are summarized
without comment, because the field of stable isotope
geology is growing so rapidly that a final answer can
not be given at the moment.
It is obvious that in writing this book, which is of
the survey type, the author could not rely only on his
own experiments and experience. He has therefore
been careful to conserve as much of their original flavor
as possible and to quote his sources.
VIII Preface to the First Edition
The author believes that he has included the most
significant recent contributions to the literature on
stable isotopes. It was not, however, his intention to
offer a compendium of all published work in this field,
nor to write something like a handbook of stable iso
tope geochemistry.
This book is not so much for the specialist active in
the field, but more for students interested in investigat
ing it. The author's hope is that this book may also
have some impact on those earth scientists who are not
intensively engaged in this subject. He has tried to de
monstrate the broad possibilities of stable isotope de
terminations in solving problems in geochemistry and
cosmochemistry.
This book would not have been written without the
encouragement of Prof. Dr. C .W. Correns. Dr. Nielsen
introduced me into the basic principles of mass spectro
metry and isotope geochemistry. His advice and con
structive criticism is gratefully acknowledged. Valuable
discussions with Professor K.H. Wedepohl have support
ed the progress of the manuscript. Drs. H.P. Schwarcz,
S.M.F. Sheppard, W. Stahl, and D.H. Welte have kindly
reviewed an early draft of the manuscript. Special
thanks go to Dr. P.G. Coomer, who has improved the
English considerably.
Gottingen, April 1973 JOCHEN HOEFS
Contents
Chapter 1 Theoretical and Experimental
Principles . . . . . . . . . . . . . . . . . . . . . . 1
1.1 General Characteristics of Isotopes ...... . 1
1.2 Isotope Effects ..................... . 1
1.3 Isotope Fractionation Processes ........ . 6
1.3.1 Isotope Exchange ................... . 6
1.3.2 Kinetic Effects ..................... . 12
1.3 .3 Diffusion .......................... . 13
1.3.4 Variation of Isotopic Composition with
Chemical Composition and Crystal
Structure .......................... . 14
1.4 Basic Principles of Mass Spectrometry .... . 15
1.5 Standards ......................... . 18
1.6 General Remarks on Sample Handling 19
1.7 Some General Trends in Stable Isotope
Geochemistry ...................... . 20
Chapter 2 Isotopic Properties of Selected
Elements . . . . . . . . . . . . . . . . . . . . . . . 23
2.1 Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.1.1 Preparation Techniques and Mass Spectro-
metric Measurement . . . . . . . . . . . . . . . . . . 24
2.1.2 Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.3 Fractionation Mechanisms. . . . . . . . . . . . . . 25
2.2 Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.1 Preparation Techniques........ . . . . . . . . 27
2.2.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2.3 Fractionation Mechanisms. . . . . . . . . . . . . . 28
2.2.4 Interactions Between the Carbonate-Carbon
Reservoir and Organic Carbon Reservoir . . . 3 2
X Contents
2.3 Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.1 Preparation Techniques............ . . . . 32
2.3.2 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.3.3 Fractionation Mechanisms..... . . . . . . . . . 35
2.3 .4 Mineral-Water Interaction . . . . . . . . . . . . . . 41
2.4 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.4.1 Standard . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.4.2 Preparation Techniques. . . . . . . . . . . . . . . . 44
2.4.3 Fractionation Mechanisms. . . . . . . . . . . . . . 45
2.4.4 Experimental Determination of Sulfide
Systems ........................... . 50
2.5 Selenium .......................... . 51
2.6 Nitrogen .......................... . 52
2.7 Silicon ............................ . 54
2.8 Boron ............................ . 55
2.9 Alkaline and Alkaline Earth Metals ....... . 56
2.9.1 Lithium ........................... . 56
2.9.2 Potassium ......................... . 57
2.9.3 Magnesium ........................ . 57
2.9.4 Calcium ........................... . 58
Chapter 3 Variations of Stable Isotope Ratios in
Nature......................... 60
3.1 Extraterrestrial Materials. . . . . . . . . . . . . . . 60
3.1.1 Meteorites. . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.1.2 Tektites....... . . . . . . . . . . . . . . . . . . . . . 66
3.1.3 The Moon. . . . . . . . . . . . . . . . . . . . . . . . . . 66
3.1.4 Mars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.1.5 Other Galactic Systems. . . . . . . . . . . . . . . . 69
3.2 Igneous Rocks................. . . . . . . 69
3.2.1 180/160 Ratios of Various Igneous Rock
Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
3.2.2 D/H Ratios in Igneous Rocks . . . . . . . . . . . 79
3.2.3 Carbon Isotopic Composition... . . . . . . . . 79
3 .2 .4 Sulfur Isotopic Composition . . . . . . . . . . . . 81
3.2.5 Nitrogen Isotopic Composition... . . . . . . . 82
3.3 Volcanic Gases and Hot Springs . . . . . . . . . 82
3.3 .1 Hot Springs . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.3.2 Volcanic Gases . . . . . . . . . . . . . . . . . . . . . . 85
Contents XI
3 .3 .3 Fluid Inclusions in Minerals and Rocks . . . . 88
3 .4 Ore Deposits . . . . . . . . . . . . . . . . . . . . . . . . 89
3.4 .1 Origin of Ore Fluids . . . . . . . . . . . . . . . . . . 90
3 .4 .2 Sulfur Isotope Composition of Hydrothermal
Ore Deposits . . . . . . . . . . . . . . . . . . . . . . . . 92
3.4.3 Hydrothermal Carbonates.............. 97
3.4.4 Hydrothermal Sulfates . . . . . . . . . . . . . . . . 99
3 .4 .5 Biogenic Sulfides. . . . . . . . . . . . . . . . . . . . . 10 0
3.4.6 6 34 S Variation in Metamorphosed Deposits 100
3.4.7 Wall Rock Alteration .................. 101
3.5 Hydrosphere . . . . . . . . . . . . . . . . . . . . . . . . 10 2
3.5 .1 Meteoric Waters - Rain, Snow, Ice . . . . . . . 10 3
3.5 .2 Groundwater. . . . . . . . . . . . . . . . . . . . . . . . 10 8
3.5.3 Ocean Water ........................ 109
3.5.4 Pore Water .......................... 113
3.5.5 Formation Waters and Oil Field Brines .... 114
3.5.6 Water in Hydrated Salt Minerals ......... 115
3 .5. 7 The Isotopic Composition of Dissolved
Compounds in Natural Water . . . . . . . . . . . 115
3.6 Atmosphere. . . . . . . . . . . . . . . . . . . . . . . . . 120
3.6.1 Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
3.6 .2 Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
3.6 .3 Carbon Dioxide. . . . . . . . . . . . . . . . . . . . . . 122
3.6.4 Hydrogen .......................... 124
3.6 .5 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
3.7 Biosphere . . . . . . . . . . . . . . . . . . . . . . . . . . 126
3.7.1 Carbon ............................ 127
3.7.2 Hydrogen .......................... 138
3.7.3 Oxygen ............................ 139
3.7 .4 Sulfur ............................. 140
3.7.5 Nitrogen ........................... 141
3.8 Sedimentary Rocks ................... 142
3.8.1 Clay Minerals ........................ 143
3 .8 .2 Cherts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.8 .3 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . 14 7
3.8.4 Phosphates ......................... 154
3.8 .5 Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 5
3.8 .6 Sedimentary Sulfides. . . . . . . . . . . . . . . . . . 15 5
3.8.7 Native Sulfur Deposits ................. 157
3.9 Metamorphic Rocks . . . . . . . . . . . . . . . . . . 157