Stable Isotope Geochemistry (Springer Textbooks in Earth Sciences, Geography and Environment)

528 Pages·2021·7.375 MB·English

by  Jochen Hoefs

Jochen Hoefs
Stable Isotope
Geochemistry
Ninth Edition
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Jochen Hoefs
Stable Isotope
Geochemistry
Ninth Edition
123
JochenHoefs
Abteilung Isotopengeologie,
Geowissenschaftliches Zentrum
UniversitätGöttingen
Göttingen, Germany
ISSN 2510-1307 ISSN 2510-1315 (electronic)
SpringerTextbooks inEarth Sciences, GeographyandEnvironment
ISBN978-3-030-77691-6 ISBN978-3-030-77692-3 (eBook)
https://doi.org/10.1007/978-3-030-77692-3
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Preface
ThenineeditionsofStableIsotopeGeochemistryhaveappearedoveratimespanof
nearly50years.Thefirstedition(1973)appearedasaslimbookof135pages.Due
totherapiddevelopmentofthefield,extendededitionsbecamenecessaryfromtime
to time. The first 4 editions centered on the classical light elements, so-called
CHONS. From the 5th edition 2004—with the introduction of the
Multicollector-ICP-Mass Spectrometry—the book had to be enlarged, because
many more elements—47 elements in the 9th edition—can be measured with the
necessary high precision. The increase of the number of elements, together with
advances in the calculation of equilibrium isotope fractionation using ab initio
methods, has led to an unbelievable rise of publications, making again a rewriting
with substantial major revisions and extensions necessary. To follow the recom-
mendationsoftheInternationalUnionofPureandAppliedChemistry(IUPAC),the
term dD has been replaced by d2H in the new edition.
The general structure of the book has been kept. Chapter 1 gives a general
introduction to the theoretical and experimental principles.
Chapter 2 is divided in two parts: Part I discusses the “traditional” elements
hydrogen, carbon, oxygen, nitrogen, and sulfur measured by gas-source
mass-spectrometry. Part II presents the “non-traditional isotopes”, measured pre-
dominantly by multi-collector inductively coupled mass-spectrometry. At places
elements with close geochemical relationships are discussed successively. Chapter
2 gives an overview of natural isotope variations of 47 elements; Rb, Zr, and Nd,
Eu and the HREE have been added in the new edition. Special emphasis has been
given to studies that have been published over the last three years, while still
summarizing the important discoveries made before that time.
As in earlier editions, the third part discusses natural variations of isotope
compositionsinthecontextoftheclassicgeochemical“spheres”.Newsubsections
have been added such as: Meteorite-Earth relationships, volatile elements on the
Moon, magnesium and iron relationships in magmatic rocks, subduction-zone
metamorphism, metal isotope variations in ore deposits and in the ocean, and
carbon isotope stratigraphy. Chapter 3 ends with two new subtitles: (i) forensic
isotope geochemistryand(ii)medicalinvestigations.Averylong listofreferences
withmanynewcitationsenablesaquickaccesstotheexponentiallygrowingrecent
v
vi Preface
literature, although I have neglected a number of recent references, because the
citation list encompasses already about 30% of the book.
Ilya Bindeman, Daniel Herwartz and Franck Poitrasson have reviewed the
manuscript; to all three of them I owe my deepest thanks. Andreas Pack and Jens
Fiebig helped me with some figures. Special thanks to Annett Büttner for support
during final preparation of the manuscript.
In summary, I hope the new enlarged edition gives a timely overview of the
recent progress in stable isotope geochemistry; for any shortcoming that remains I
take responsibility.
Göttingen, Germany Jochen Hoefs
Contents
1 Theoretical and Experimental Principles . . . . . . . . . . . . . . . . . . . . . 1
1.1 General Characteristics of Isotopes . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Isotope Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Isotope Fractionation Processes . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.3.1 Isotope Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.3.1.1 Fractionation Factor (a). . . . . . . . . . . . . . . 7
1.3.1.2 The Delta Value (d) . . . . . . . . . . . . . . . . . 8
1.3.1.3 Evaporation–Condensation Processes . . . . . 9
1.3.2 Kinetic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.3 Mass-Dependent and Mass-Independent Isotope
Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.3.3.1 Mass Dependent Effects. . . . . . . . . . . . . . . 12
1.3.3.2 Mass Independent Effects . . . . . . . . . . . . . 13
1.3.4 Nuclear Volume and Magnetic Isotope Effects. . . . . . . 14
1.3.4.1 Nuclear Volume Effects. . . . . . . . . . . . . . . 14
1.3.4.2 Magnetic Isotope Effects . . . . . . . . . . . . . . 15
1.3.5 Multiply Substituted Isotopologues . . . . . . . . . . . . . . . 15
1.3.5.1 Position or Site-Specific Isotope
Fractionations . . . . . . . . . . . . . . . . . . . . . . 18
1.3.6 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.7 Other Factors Influencing Isotopic Fractionations . . . . . 21
1.3.8 Isotope Geothermometers . . . . . . . . . . . . . . . . . . . . . . 23
1.4 Basic Principles of Mass Spectrometry. . . . . . . . . . . . . . . . . . . . 28
1.4.1 Continuous Flow–Isotope Ratio Monitoring
Mass Spectrometers . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.4.2 General Remarks on Sample Preparation Methods
for Gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.4.3 Laser Extraction Techniques . . . . . . . . . . . . . . . . . . . . 33
1.4.4 High-Mass-Resolution Multiple-Collector IR Mass
Spectrometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.4.5 Infrared Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . 34
1.4.6 Nuclear Magnetic Resonance (NMR) Spectroscopy . . . 34
vii
viii Contents
1.5 Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.6 Microanalytical Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.6.1 Multicollector-ICP-Mass Spectrometry. . . . . . . . . . . . . 38
1.6.2 Secondary Ion Mass Spectrometry (SIMS). . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2 Isotope Fractionation Processes of Selected Elements . . . . . . . . . . . . 49
2.1 Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.1.1 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.1.2 Standards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.1.3 Fractionation Processes. . . . . . . . . . . . . . . . . . . . . . . . 53
2.1.3.1 Water Fractionations . . . . . . . . . . . . . . . . . 53
2.1.3.2 Equilibrium Reactions . . . . . . . . . . . . . . . . 55
2.1.3.3 Fractionations During Biosynthesis. . . . . . . 56
2.1.3.4 Other Fractionations . . . . . . . . . . . . . . . . . 57
2.2 Carbon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.2.1 Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.2.1.1 Standards . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.2.2 Fractionation Processes. . . . . . . . . . . . . . . . . . . . . . . . 59
2.2.2.1 Carbonate System . . . . . . . . . . . . . . . . . . . 59
2.2.2.2 Other Equilibrium Isotope
Fractionations . . . . . . . . . . . . . . . . . . . . . . 60
2.2.2.3 Organic Carbon System. . . . . . . . . . . . . . . 61
2.2.2.4 Interactions Between Carbonate-Carbon
and Organic Carbon . . . . . . . . . . . . . . . . . 62
2.3 Nitrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.1 Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.2 Biological Nitrogen Isotope Fractionations. . . . . . . . . . 65
2.3.3 Trophic Level Indicator . . . . . . . . . . . . . . . . . . . . . . . 67
2.3.4 Nitrogen Isotopes in the Mantle and Crust. . . . . . . . . . 67
2.3.5 Nitrogen in the Ocean and in Sediments . . . . . . . . . . . 68
2.4 Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4.1 Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4.1.1 Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.4.1.2 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . 71
2.4.1.3 Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.4.1.4 Phosphates . . . . . . . . . . . . . . . . . . . . . . . . 73
2.4.1.5 Sulfates. . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.4.1.6 Nitrates. . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.4.2 Standards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.4.3 Fractionation Processes. . . . . . . . . . . . . . . . . . . . . . . . 74
Contents ix
2.4.3.1 Fractionation of Water. . . . . . . . . . . . . . . . 74
2.4.3.2 CO –H O System . . . . . . . . . . . . . . . . . . . 76
2 2
2.4.3.3 Mineral Fractionations. . . . . . . . . . . . . . . . 77
2.4.4 Triple Oxygen Isotope Compositions. . . . . . . . . . . . . . 79
2.4.5 Fluid-Rock Interactions. . . . . . . . . . . . . . . . . . . . . . . . 80
2.5 Sulfur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.5.1 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2.5.2 Fractionation Mechanisms. . . . . . . . . . . . . . . . . . . . . . 85
2.5.2.1 Equilibrium Reactions . . . . . . . . . . . . . . . . 85
2.5.2.2 Dissimilatory Sulfate Reduction . . . . . . . . . 86
2.5.2.3 Thermochemical Reduction of Sulfate . . . . 89
2.5.3 Quadruple Sulfur Isotopes. . . . . . . . . . . . . . . . . . . . . . 90
2.6 Lithium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
2.6.1 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.6.2 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
2.6.3 Magmatic Rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
2.6.4 Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2.6.5 Ocean Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
2.6.6 Meteoric Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2.7 Boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
2.7.1 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2.7.2 Isotope Fractionation Mechanism . . . . . . . . . . . . . . . . 101
2.7.3 Fractionations at High Temperatures . . . . . . . . . . . . . . 103
2.7.4 Weathering Environment . . . . . . . . . . . . . . . . . . . . . . 104
2.7.5 Tourmaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.8 Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.8.1 Calculated Isotope Fractionations . . . . . . . . . . . . . . . . 106
2.8.1.1 Mantle Rocks . . . . . . . . . . . . . . . . . . . . . . 107
2.8.1.2 Continental Crust . . . . . . . . . . . . . . . . . . . 108
2.8.2 Fractionations During Weathering . . . . . . . . . . . . . . . . 108
2.8.3 Ocean Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2.8.4 Carbonates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
2.8.5 Plants and Animals. . . . . . . . . . . . . . . . . . . . . . . . . . . 110
2.9 Calcium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2.9.1 Analytical Techniques . . . . . . . . . . . . . . . . . . . . . . . . 111
2.9.2 High Temperature Fractionations. . . . . . . . . . . . . . . . . 112
2.9.3 Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
2.9.4 Fractionations During Carbonate Precipitation . . . . . . . 114
2.9.5 Variations of Ocean Water with Geologic Time. . . . . . 115
2.9.6 Plants, Animals and Humans. . . . . . . . . . . . . . . . . . . . 116