Isotopic Constraints on Earth System Processes

1 Cover

2 Series Page

3 Title Page

4 Copyright Page

5 List of Contributors

6 Preface PART I: HIGH‐TEMPERATURE/DEEP EARTH PROCESSES PART II: LOW‐TEMPERATURE/SHALLOW EARTH PROCESSES REFERENCES

7 About the Companion Website

8 Dedication Page

9 Part I: High‐Temperature/Deep Earth Processes 1 High‐Temperature Kinetic Isotope Fractionation of Silicate Materials 1.1. INTRODUCTION 1.2. DIFFUSION IN MULTI‐COMPONENT CONDENSED SYSTEMS: THEORY AND DEFINITIONS 1.3. KINETIC ISOTOPE FRACTIONATION DURING DIFFUSION BETWEEN NATURAL MELTS 1.4. ISOTOPE FRACTIONATION BY SORET DIFFUSION 1.5. ISOTOPE FRACTIONATION BY DIFFUSION IN SILICATE MINERALS 1.6. ISOTOPE FRACTIONATION BY EVAPORATION FROM SILICATE MELTS 1.7. SUMMARY 1.8. THOUGHTS ON FURTHER RESEARCH REFERENCES 2 Ca and K Isotope Fractionation by Diffusion in Molten Silicates 2.1. INTRODUCTION 2.2. METHODS 2.3. RESULTS 2.4. DISCUSSION 2.5. MODELING 2.6. CONCLUSIONS AND POSSIBLE FUTURE APPLICATIONS APPENDIX LINEAR VERSUS EXPONENTIAL DEPENDENCE OF ACTIVITY ON SIO 2 ACKNOWLEDGMENTS REFERENCES 3 Calcium Isotope Constraints on Recycled Carbonates in Subduction‐Related Magmas 3.1. INTRODUCTION 3.2. ANALYTICAL METHODS AND SAMPLES 3.3. RESULTS 3.4. DISCUSSION 3.5. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 4 Reassessing the Role of Continental Lithospheric Mantle in Cenozoic Magmatism, Southwestern North America 4.1. INTRODUCTION 4.2. GEOLOGIC BACKGROUND & GENERAL TERMINOLOGY 4.3. METHODS/DATA 4.4. RESULTS 4.5. DISCUSSION 4.6. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES 5 Rhyolite Ignimbrite Generation in the Northern Andes 5.1. INTRODUCTION 5.2. GEOLOGICAL SETTING AND AGE OF THE CHALUPAS CALDERA 5.3. GEOCHEMICAL RESULTS 5.4. EVOLUTION OF THE CHALUPAS MAGMATIC SYSTEM 5.5. CRUSTAL STRUCTURE, MAGMA SUPPLY, AND TRANSPORT 5.6. CHALUPAS ERUPTION VOLUME AND MAGMA SUPPLY 5.7. SUMMARY AND CONCLUSIONS APPENDIX 5A Appendix APPENDIX 5B MINERAL CHEMISTRY AND PETROGRAPHIC DESCRIPTIONS APPENDIX 5C MODELS FOR CRYSTAL FRACTIONATION, ASSIMILATION-FRACTIONAL CRYSTALLIZATION, AND MAGMA FLUXES ACKNOWLEDGMENTS REFERENCES 6 Xenolith Constraints on “Self‐Assimilation” and the Origin of Low δ 18O Values in Mauna Kea Basalts 6.1. INTRODUCTION 6.2. SAMPLES AND ANALYTICAL METHODS 6.3. RESULTS 6.4. DISCUSSION 6.5. CONCLUSIONS ACKNOWLEDGMENTS REFERENCES SUPPLEMENTAL DATA 7 Monitoring Volcanic Activity Through Combined Measurements of CO 2Efflux and ( 222Rn) and ( 220Rn) in Soil Gas 7.1. INTRODUCTION 7.2. BACKGROUND 7.3. SAMPLING STRATEGY AND ANALYTICAL METHODS 7.4. SYNOPSIS OF THIS STUDY’S RESULTS 7.5. THE SOIL GAS DISEQUILIBRIUM INDEX (SGDI) 7.6. RELATIONSHIP BETWEEN FILTERED SGDI DATA AND VOLCANIC ACTIVITY OF MT. ETNA 7.7. SUMMARY APPENDIX STATISTICAL TREATMENT OF SGDI DATA ACKNOWLEDGMENTS REFERENCES

10 Part II: Low‐Temperature/Shallow Earth Processes 8 The Carbon Isotope Record and Earth Surface Oxygenation 8.1. INTRODUCTION 8.2. THE CARBON ISOTOPE BUDGET 8.3. f orgAND THE OXYGEN BUDGET 8.4. OXYGEN SINKS IN A LOW‐OXYGEN WORLD 8.5. RESOLVING THE pO 2– f orgPARADOX 8.6. PREDICTIONS OF THE AUTHIGENIC FEEDBACK HYPOTHESIS 8.7. CONCLUSIONS REFERENCES 9 Detrital Garnet Geochronology 9.1. INTRODUCTION AND MOTIVATION 9.2. THEORETICAL FEASIBILITY OF DETRITAL GARNET GEOCHRONOLOGY 9.3. DETAILED METHODOLOGY 9.4. CASE STUDIES 9.5. CONCLUSION ACKNOWLEDGMENTS REFERENCES 10 A Review of the Development of Cr, Se, U, Sb, and Te Isotopes as Indicators of Redox Reactions, Contaminant Fate, and Contaminant Transport in Aqueous Systems 10.1. INTRODUCTION 10.2. MASS SPECTROMETRY AND SAMPLE PREPARATION METHODS 10.3. CURRENT UNDERSTANDING OF ISOTOPIC FRACTIONATION 10.4. APPLICATIONS OF CR, U, AND SE ISOTOPE MEASUREMENTS 10.5. REACTIVE TRANSPORT MODELS: AN ESSENTIAL PART OF THE SCIENCE 10.6. CONCLUSIONS AND OUTLOOK APPENDIX ACKNOWLEDGMENTS REFERENCES 11 The Effects of Reactive Transport on Sulfur Isotopic Compositions in Natural Environments 11.1. MOTIVATION 11.2. SULFUR ISOTOPE INTRODUCTION 11.3. REACTIVE TRANSPORT EFFECTS ON SULFUR ISOTOPE‐SIGNATURES 11.4. SUMMARY REFERENCES 12 A Reactive Transport Framework Describing Covariation in the Isotopic Ratios of Multiple Elements in Natural Systems 12.1. MOTIVATION 12.2. A SYNTHETIC MODEL STUDY OF PAIRED ISOTOPE SIGNATURES 12.3. SUMMARY REFERENCES 13 Stable Ca Isotope Fractionation in Cenozoic Marine Mammals 13.1. INTRODUCTION 13.2. BACKGROUND 13.3. METHODS 13.4. RESULTS 13.5. DISCUSSION 13.6 CONCLUSIONS APPENDIX 13A MARINE MAMMAL BONE ANALYSIS APPENDIX 13B BALEEN ANALYSIS I APPENDIX 13C BALEEN ANALYSIS II ACKNOWLEDGMENTS REFERENCES

11 Index

12 End User License Agreement

1 Chapter 1 Table 1.1 Summary of the exponents β from laboratory diffusion exper...

2 Chapter 2 Table 2.1 Major element composition of starting materials (fused glasses) m... Table 2.2 Summary of isotopic results.

3 Chapter 3 Table 3.1 Mass‐dependent calcium isotope compositions of igneous rocks and ... Table 3.2 Difference between igneous rocks used to estimate δ 44Ca of BSE an...

4 Chapter 4Table 4.1 Whole rock trace element compositions from the Cretaceous Slidero...Table 4.2 Whole rock Nd and Sr isotopic data from Sliderock Mountain Volcan...

5 Chapter 5Table 5.1 Major and trace element data for samples from the Chalupas calder...Table 5.2 Isotopic analyses of samples from the Chalupas volcanic system.Table 5.3 Major and trace element data for metamorphic basement rocks.Table 5.4 Isotopic analyses of metamorphic basement rocks.Table 5.5 Summary of analytical data resulting from incremental heating exp...Table 5.6 Representative electron microprobe analyses of Chalupas samples....Table 5.7 Major element composition of Chalupas AFT and calculated glass co...Table 5.8 Inputs for finite difference‐AFC modeling.

6 Chapter 6Table 6.1 Mineral Sr‐, Nd‐, Pb‐, and O‐isotope compositions of Mauna Kea xe...Table 6.2 Average clinopyroxene major and trace element compositionsTable 6.3 Average mineral major element data (plagioclase, olivine, orthopy...Table S6.1 Clinopyroxene Major and Trace Element CompositionsTable S6.2 Olivine major element compositionsTable S6.3 Orthopyroxene major element compositionsTable S6.4 Plagioclase major element compositionsTable S6.5 Spinel major element compositions

7 Chapter 7Table 7.1a Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.1b Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.1c Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.1d Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.2a Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.2b Values of soil CO 2efflux (g/m 2/d) and soil activities of 222Rn a...Table 7.3 Schematic summary of the occurrence of SGDI anomalies divided by ...Table 7.4 Values of SGDI (in dimensionless units) for the sites of the ZE‐S...Table 7.5 Values of SGDI (in dimensionless units) for the sites of the PAT ...Table 7.6 Correlation matrix for filtered SGDI values and corresponding atm...Table 7.7 Correlation matrix for filtered SGDI values and corresponding atm...

8 Chapter 9Table 9.1 Isotope ratios and age results from preliminary detrital garnet a...Table 9.2 Isotope ratios and age results for both case studies utilizing ga...Table 9.3 Isotope ratios and age results from detrital garnet dating attemp...

9 Chapter 10Table 10.1 Naturally occurring redox states of Cr, Se, U, Sb and Te, with e...Table 10.2 Interferences encountered during Se isotope measurement by MC‐IC...Table 10.3 Summary of Cr isotopic fractionation factors for Cr(VI) reductio...Table 10.4 Se isotope fractionations associated with various reduction reac...Table 10.5 U isotopic fractionation observed for U(VI) reduction in laborat...Table 10.6 Cr isotope fractionation induced by various oxidation reactions....