Jochen Hoefs Stable Isotope Geochemistry

Transcription

1 Jochen Hoefs Stable Isotope Geochemistry

2 Springer-Verlag Berlin Heidelberg GmbH

3 Jochen Hoefs Stable Isotope Geochemistry 4th, Completely Revised, Updated, and Enlarged Edition With 73 Figures and 22 Tables Springer

4 Professor Dr. Jochen Hoefs Institute of Geochemistry University of Gottingen GoldschmidtstraBe 1 D Gottingen Germany Library of Congress Cataloging-in-Publication Data Hoefs, Jochen. Stable isotope geochemistry/jochen Hoefs. - 4th. completely rev., updated, and en!. ed. p. cm. Includes bibliographical references and index. ISBN ISBN (ebook) DOI / Geochemistry. 2. Isotope geology. I. Title. QE515.H dc This work is subject to copyright. All rights are reserved, whether the whole or part of material is concerned, specifically the rights of translation, 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 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 regulations and therefor free for general use SPIN / Printed on acid-free paper

5 Preface Stable isotope geochemistry has become an essential part of geochemistry and has contributed significantly to the solution of a wide variety of geological problems, which span the whole field of earth sciences, from paleoclimatology to cosmochemistry, from oceanography to mantle geochemistry, to list only a few. In some fields such as ore deposit studies, stable 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 I have again tried to give a well-balanced discussion of the whole field, although I do not claim that every aspect has been considered and that no omission can be found. The book is not written primarily for the specialist in the field of stable isotope geochemistry, but more for the non-specialist and graduate student, who needs practical knowledge of how to interpret stable isotope ratios. My colleagues Tony Fallick, Russ Harmon, and Antonio Longinelli have reviewed an early draft of the manuscript, which is gratefully acknowledged. Special thanks go to Russ Harmon, who has considerably improved the clarity of style and presentation. I take full responsibility, however, for any shortcomings that remain. Gottingen, April 1996 Jochen Hoefs

6 Table of Contents Chapter! Theoretical and Experimental Principles General Characteristics of Isotopes... Isotope Effects Isotope Fractionation Processes Isotope Exchange Fractionation Factor (ex) The Delta Value (6) Evaporation-Condensation Processes Kinetic Effects Diffusion... Other Factors Influencing Isotopic Fractionations Chemical Composition... Crystal Structure... Non-Mass-Dependent Isotope Effects... Isotope Geothermometers... Theoretical Calculations... Experimental Calibrations... Basic Principles of Mass Spectrometry... Standards General Remarks on Sample Handling New Microanalytical Techniques Laser Microprobe Gas Chromatography Combined with Gas Mass Spectrometry Secondary Ion Mass Spectrometry Chapter 2 Isotope Fractionation Mechanisms of Selected Elements 2.1 Hydrogen Preparation Techniques and Mass Spectrometric Measurements... 29

7 Standards Fractionation Mechanisms Equilibrium Exchange Reactions Kinetic Isotope Effects Other Fractionation Effects Lithium Boron Carbon Preparation Techniques Standards Fractionation Mechanisms Inorganic Carbon System Carbon Isotope Fractionations During Photosynthesis Interactions Between the Carbonate-Carbon Reservoir and Organic Carbon Reservoir Nitrogen... Oxygen... Preparation Techniques... Standards... Fractionation Mechanisms... Fluid-Rock Interactions Silicon Sulfur Preparation Techniques Fractionation Mechanisms Bacterial Reduction of Sulfate Thermochemical Reduction of Sulfate Isotope Exchange Reactions Chlorine Chapter 3 Variations of Stable Isotope Ratios in Nature Extraterrestrial Materials... Meteorites... Hydrogen... Carbon Nitrogen Sulfur The Moon and the Neighboring Planets Mars and Venus The Moon Mars Venus

8 3.1.3 Comets Interplanetary Dust Particles Isotopic Composition of the Upper Mantle Oxygen Hydrogen Carbon Sulfur Nitrogen Magmatic Rocks Fractional Crystallization Differences Between Volcanic and Plutonic Rocks 80 Low-Temperature Alteration Processes Assimilation of Crustal Rocks Basaltic Rocks from Different Tectonic Settings. 81 Ocean Water/Basaltic Crust Interactions Granitic Rocks Volatiles in Magmatic Systems Glasses Hydrogen Carbon Nitrogen Sulfur Volcanic Gases and Hot Springs Water Carbon Sulfur Isotope Thermometers in Geothermal Systems.. 89 Ore Deposits and Hydrothermal Systems Origin of Ore Fluids Seawater Meteoric Waters Juvenile Water Magmatic Water Metamorphic Water Formation Waters Wall-Rock Alteration Fossil Hydrothermal Systems Hydrothermal Carbonates Sulfur Isotope Composition of Ore Deposits Importance of Changing f0 2 and ph Reservoir Effect Recent Sulfide Deposits at Mid-Ocean Ridges Magmatic Ore Deposits Magmatic Hydrothermal Deposits Base and Precious Metal Vein Deposits Volcanic-Associated Massive Sulfide Deposits

9 Shale/Carbonate-Hosted Massive Sulfide Deposits 102 Mississippi Valley Type Deposits Biogenic Deposits Metamorphosed Deposits Hydrosphere Meteoric Water csd-cs 1B O Relationship Ancient Meteoric Waters Ice Cores Groundwater Isotope Fractionations During Evaporation Ocean Water Pore Waters Formation Water Water in Hydrated Salt Minerals Isotopic Composition of the Ocean During Geological History Oxygen Carbon Sulfur Isotopic Composition of Dissolved and Particulate Compounds in Ocean and Fresh Waters Carbon Species in Water Bicarbonate in Ocean Water Particulate Organic Matter Carbon Isotope Composition of Pore Waters Carbon in Fresh Waters Nitrogen Oxygen Sulfate '" Atmosphere Nitrogen Oxygen Ozone Carbon Dioxide Carbon Oxygen Long-Term Variations in the CO 2 Concentration 130 Methane Hydrogen Sulfur Biosphere Living Organic Matter Bulk Carbon Chemical Components of Plant Material

10 Isotope Fractionations of Other Elements During Photosynthesis Hydrogen Oxygen Nitrogen Sulfur ).10.3 Stable Isotopes as Indicators of Diet and Metabolism Recent Organic Matter Fossil Organic Matter in Sediments Oil Coal Natural Gas Biogenic Gas Thermogenic Gas Abiogenic Methane ).12 4 Sedimentary Rocks Clay Minerals Clastic Sedimentary Rocks Biogenic Silica and Cherts Marine Carbonates Oxygen Carbon Diagenesis of Limestones Meteoric Pathway Burial Pathway Dolomites Freshwater Carbonates Phosphates Iron Oxides Sedimentary Sulfur Metamorphic Rocks Regional Metamorphism Lower Crustal Rocks Contact Metamorphism Thermometry References Subject Index