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Группа авторов. Magma Redox Geochemistry
Table of Contents
List of Tables
List of Illustrations
Guide
Pages
Geophysical Monograph Series
Geophysical Monograph 266. Magma Redox Geochemistry
LIST OF CONTRIBUTORS
PREFACE
1 Redox Equilibria: From Basic Concepts to the Magmatic Realm
ABSTRACT
1.1. GENERAL ASPECTS AND RATIONALE. 1.1.1. Oxidation Number, Electron Transfer, and Half‐Reactions
1.1.2. The Redox Potential in Solutions and the Ligand Role
1.2. OXYGEN FUGACITY: THE CENTRALITY OF AN ELUSIVE PARAMETER
1.3. CONCLUDING REMARKS AND PERSPECTIVES
ACKNOWLEDGMENTS
REFERENCES
2 Redox Processes Before, During, and After Earth’s Accretion Affecting the Deep Carbon Cycle
ABSTRACT
2.1. THE REDOX STATE OF PLANETARY INTERIORS AND THE SPECIATION OF CARBON IN THE EARTH
2.2. OXIDATION STATE OF EARTH’S BUILDING BLOCKS AND EARLY DIFFERENTIATION
2.2.1. The Solar Nebula Redox State. The fO2 of Chondrites
The fO2 of Planetesimals and the Role of Volatiles
The Oxidation State of Earth’s Interior, Other Planets, and Meteorites
2.3. MANTLE OXIDATION STATE OVER TIME AND ITS EFFECT ON THE C–O–H VOLATILE SPECIATION
2.3.1. The Redox State of the Upper Mantle and the Mobilization of Deep C
2.3.2. Is the fO2 of the Transition Zone and Lower Mantle Recorded by Sublithospheric Diamonds?
2.3.3. Temporal and Spatial Evolution of the Redox State of the Asthenospheric Mantle
2.4. THE MANTLE GREAT OXIDATION EVENT: FACT OR ARTEFACT?
ACKNOWLEDGMENTS
REFERENCES
3 Oxygen Fugacity Across Tectonic Settings
ABSTRACT
3.1. INTRODUCTION
3.1.1. Theoretical Background
3.1.2. Fe‐Based Oxybarometry
3.1.3. Trace‐Element Oxybarometry
3.1.4. Other Oxybarometers
3.2. SAMPLE SELECTION, METHODOLOGY, AND DESIGN OF THIS STUDY
3.3. RESULTS
3.3.1. Fe‐Based Oxybarometry. Mid‐Ocean Ridges
Arcs and Back Arcs
Plumes
3.3.2. V/Yb Concentrations
3.4. DISCUSSION
3.4.1. Linking the fO2 of Volcanics and Mantle Lithologies
Degassing
Crystal Fractionation
Inferences about Mantle fO2 as a Function of Tectonic Setting
3.5. CONCLUSIONS AND FUTURE DIRECTIONS
ACKNOWLEDGMENTS
METHODS APPENDIX
REFERENCES
4 Redox Variables and Mechanisms in Subduction Magmatism and Volcanism
ABSTRACT
4.1. INTRODUCTION
4.2. REDOX VARIABLES. 4.2.1. Intensive and Extensive Redox Variables
4.2.2. Uses of Redox‐Sensitive Elements
4.2.3. Measurement Techniques
4.3. MECHANISMS
4.3.1. Processes Affecting the Slab Prior to Subduction
A Note of Caution
4.3.2. Devolatilization of the Slab
Mantle Lithosphere
Oceanic Crust
Sediments
4.3.3. Fluid/Melt Transfer and Mantle Metasomatism – Is the Sub‐Arc Mantle More Oxidized than Mantle Elsewhere?
Yes
No
4.3.4. Formation of Primary Magmas in the Sub‐Arc Mantle
Role of Volatiles
Role of Refertilization
4.3.5. Modification of Primary Magmas
Differentiation
Degassing
Redox Aspects of Ore Deposit Formation Associated with Arc Magmas
4.4. DISCUSSION. 4.4.1. Temporal Variation
4.4.2. Opportunities
4.4.3. Synthesis
ACKNOWLEDGMENTS
REFERENCES
5 Redox Melting in the Mantle
ABSTRACT
5.1. INTRODUCTION
5.2. MANTLE MELTING WITH VOLATILE COMPONENTS
5.3. REDOX MELTING. 5.3.1. Development of the Concept
5.3.2. Redox Melting Mechanisms
5.4. COMPOSITIONS OF MELTS FORMED BY REDOX MELTING
5.5. THE OXIDATION STATE IN THE MANTLE LITHOSPHERE, ASTHENOSPHERE, AND SUBDUCTION ZONES
5.6. DISCUSSION
5.6.1. Spatial Variations in Oxidation State on the Modern Earth. Lower Cratonic Lithosphere
The Subduction Environment and Recycled Blocks
5.6.2. The Evolution of Mantle Oxidation States through Earth History
Redox State of the Mantle in the Archean
Evolution of Alkaline Melt Types as a Sensor of the Evolving Incipient Melting Regime
Subduction Before the Great Oxidation Event (GOE)
Redox Melting Before the Cratons
5.7. CLOSING COMMENTS
ACKNOWLEDGMENTS
REFERENCES
6 Ionic Syntax and Equilibrium Approach to Redox Exchanges in Melts: Basic Concepts and the Case of Iron and Sulfur in Degassing Magmas
ABSTRACT
6.1. INTRODUCTION
6.2. IONIC SYNTAX, SPECIATION STATE AND THE MELT/GLASS NETWORK: STATE OF THE ART AND CONCEPTUAL FRAMEWORK
6.2.1. The Effect of Melt Composition on Iron and Sulfur Oxidation State
6.2.2. Fe–S Mutual Interactions
6.3. REDOX EVOLUTION AND MAGMATIC DEGASSING
6.3.1. Mechanisms of Sulfur Release on Magma Rise
6.3.2. Application to Real Cases
6.4. DISCUSSION. 6.4.1. Who Controls What: the Composition/Polymerization/Acid–Base/Redox Connection
6.4.2. Magma Degassing: Oxygen as a Perfectly Mobile Component and the Role of Gas Redox Buffers
6.5. CONCLUSIONS
CODE AVAILABILITY
ACKNOWLEDGMENTS
REFERENCES
7 The Petrological Consequences of the Estimated Oxidation State of Primitive MORB Glass
ABSTRACT
7.1. INTRODUCTION
7.2. MODELING METHODS AND SAMPLE SELECTION. 7.2.1. Simple Model
7.2.2. PRIMELT3
7.2.3. pMELTS and rhyoliteMELTS
7.2.4. Choice of Reference Samples
7.3. RESULTS. 7.3.1. PRIMELT3, Potential Temperature, and Host‐Phenocryst‐Inclusion Equilibrium
7.3.2. pMELTS, Potential Temperature, and Typical Oceanic Crustal Thickness
7.3.3. rhyoliteMELTS and Implications for Origin of Oceanic Lower Crust
7.4. SUMMARY AND PROSPECTS
ACKNOWLEDGMENTS
REFERENCES
8 Oxygen Content, Oxygen Fugacity, the Oxidation State of Iron, and Mid‐Ocean Ridge Basalts
ABSTRACT
8.1. OXYGEN CONTENT, OXYGEN FUGACITY, AND THE OXIDATION STATE OF IRON
8.2. MID‐OCEAN RIDGE BASALTS
ACKNOWLEDGMENTS
REFERENCES
9 Chromium Redox Systematics in Basaltic Liquids and Olivine
ABSTRACT
9.1. INTRODUCTION
9.1.1. Some Applications of Cr‐Redox Systematics to Petrologic Problems
9.1.2. Overview of Chapter Content
9.2. MEASURING CR VALENCE IN GEOLOGIC MATERIALS WITH CR‐K EDGE XANES SPECTROSCOPY
9.2.1. Quench Modification of Cr2+/∑Cr in Fe‐bearing Glasses
9.2.2. XANES Anisotropy in Non‐Isometric Silicate Minerals
9.3. CR‐REDOX SYSTEMATICS IN SILICATE LIQUIDS: WHAT WE KNOW AND DON’T KNOW
9.3.1. The First Direct Measurements of Cr Valence in Quenched Liquids
9.3.2. Indirect Studies of Cr Valence using Cr‐Spinel Buffered Basaltic Liquids
9.3.3. XANES Studies of Cr Valence in CMAS and Basaltic Liquids
9.3.4. Existing Knowledge Gaps and Future Directions
9.4. CR‐VALENCE SYSTEMATICS IN EQUILIBRIUM LIQUID‐OLIVINE PAIRS
9.4.1. Existing Knowledge Gaps and Future Directions
9.5. CONCLUDING REMARKS
ACKNOWLEDGMENTS
REFERENCES
10 The Thermodynamic Controls on Sulfide Saturation in Silicate Melts with Application to Ocean Floor Basalts
ABSTRACT
10.1. INTRODUCTION
10.2. SULFIDE CAPACITY
10.2.1. The Experimental Sulfur Solubility Minimum
10.3. THE THERMODYNAMIC MEANING OF THE SULFIDE CAPACITY
10.3.1. The Fe3+ Problem
10.3.2. Sulfate Capacities,
10.3.3. Other Capacities for Anions and Anion Complexes in Silicate Melts
10.4. A NEW PARAMETERIZATION OF SULFIDE CAPACITY FOR BASALTIC MELTS
10.4.1. Temperature Dependence of
10.5. SULFIDE CONTENT AT SULFIDE SATURATION (SCSS)
10.5.1. Fitting the Experimental Data on SCSS on Anhydrous Compositions
10.5.2. The Effect of Pressure on SCSS
10.5.3. The Dependence of SCSS on FeO
10.5.4. The Effect of H2O
10.6. APPLICATION TO MID‐OCEAN RIDGE AND SIMILAR BASALTS
10.6.1. Sensitivity analysis
10.6.2. Is Neglecting H2O in OFB Glasses Justified?
10.6.3. Comparison with Previous Models
10.6.4. Application to Other OFB Glass Datasets
10.6.5. Siqueiros OFB Olivine‐Hosted Melt Inclusions
10.7. THE SULFUR FUGACITY (f S2) OF OCEAN FLOOR BASALTS
10.8. CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
11 Redox State of Volatiles and Their Relationships with Iron in Silicate Melts: Implications for Magma Degassing
ABSTRACT
11.1. INTRODUCTION
11.2. WATER CONCENTRATION IN MELT AND ITS EFFECT ON REDOX
11.3. THE SULFUR SPECIES AND THE REDOX (FE3+/∑FE Ratio) OF SILICATE MELTS. 11.3.1. Sulfur Speciation in Natural Magmas
11.3.2. Improvement of the Spectroscopic Methods to Probe the Sulfur Valence States in Silicate Melts
11.3.3. The Sulfur Minimum
11.3.4. Sulfur Concentration and Redox as a Function of fO2
11.3.5. The Sulfide–Sulfate Transition
11.3.6. The Sulfide–Sulfate Transition and its Key Role on the Sulfur Behavior During Magma Evolution and Decompression
11.3.7. Fluid‐Melt Partitioning of Sulfur
11.4. NATURAL SYSTEMS: MAGMA DEGASSING AND REDOX
11.4.1. Basaltic Systems
11.4.2. Intermediate to Silicic Systems
11.5. CONCLUDING REMARKS
ACKNOWLEDGMENTS
REFERENCES
12 Iron in Silicate Glasses and Melts: Implications for Volcanological Processes
ABSTRACT
12.1. INTRODUCTION
12.2. IRON DISTRIBUTION IN THE DIFFERENT TERRESTRIAL ENVELOPES
12.3. REDOX EQUILIBRIUM IN MELTS
12.3.1. Temperature, Oxygen Fugacity, and Pressure Effects
12.3.2. Influence of the Melt Structure and Composition. Introductory Remarks about the Structure of Silicate Melts and Glasses
Iron Environment in Melts and Glasses
Melt Composition and Iron Oxidation State
12.4. PHYSICAL PROPERTIES: HIGHLIGHTS ON DENSITY AND VISCOSITY
12.4.1. Influence of Iron Content and Redox on the Density of Melts
12.4.2. Iron and the Viscosity of Silicate Melts
12.5. INFLUENCES ON CRYSTALLIZATION AND DEGASSING IN MAGMATIC SYSTEMS
12.6. CONCLUDING REMARKS
ACKNOWLEDGMENTS
REFERENCES
13 How to Measure the Oxidation State of Multivalent Elements in Minerals, Glasses, and Melts?
ABSTRACT
13.1. INTRODUCTION
13.2. WET‐CHEMICAL ANALYSES
Advantages, drawbacks, accuracy
13.3. ELECTRONIC MICROPROBE
Advantages, drawbacks, accuracy
13.4. MÖSSBAUER SPECTROSCOPY
Advantages, drawbacks, accuracy
13.5. OPTICAL ABSORPTION SPECTROSCOPY
Advantages, drawbacks, accuracy
13.6. X‐RAY ABSORPTION SPECTROSCOPY
13.6.1. K‐edge XANES Spectra of 3d Transition Elements
13.6.2. Extracting Information from XANES Spectra
Advantages, drawbacks, accuracy
13.7. RAMAN SPECTROSCOPY
13.7.1. Spectrometer, Technical Designs, Acquisition Parameters
13.7.2. Raman Spectra
13.7.3. Spectral Pre‐Treatment: Background Subtraction and Normalization
13.7.4. Details on Raman Spectra of Silicate Glasses
13.7.5. Raman Spectra of Iron Silicate Glass
Advantages, drawbacks, accuracy
13.8. IN SITU REDOX DETERMINATION AT HIGH TEMPERATURE OR AT HIGH PRESSURE
13.9. CONCLUSION
ACKNOWLEDGMENTS
REFERENCES
Notes
14 Oxidation State, Coordination, and Covalency Controls on Iron Isotopic Fractionation in Earth’s Mantle and Crust: Insights from First‐Principles Calculations and NRIXS Spectroscopy
ABSTRACT
14.1. INTRODUCTION
14.2. THEORY: EQUILIBRIUM ISOTOPIC FRACTIONATION FROM VIBRATIONAL PROPERTIES
14.3. CALCULATION OF VIBRATIONAL PROPERTIES. 14.3.1. First‐Principles Calculations
14.3.2. NRIXS Spectroscopy
14.4. IRON ISOTOPE STUDIES BASED ON NRIXS OR DFT
14.5. COMPARISON OF EQUILIBRIUM FRACTIONATION FACTORS DERIVED FROM VARIOUS TECHNIQUES
14.6. PARAMETERS CONTROLLING EQUILIBRIUM FRACTIONATION FACTORS
14.7. SELECTED APPLICATIONS TO THE INTERPRETATION OF IRON ISOTOPIC VARIATIONS IN IGNEOUS ROCKS
14.7.1. Mineral‐Melt Fractionation and the Heavy Fe Isotopic Composition of the Crust
14.7.2. Isotopic Fractionation During Magmatic Differentiation
14.7.3. Isotopic Fractionation in Arc Lavas
14.8. CONCLUSIONS AND PERSPECTIVES
ACKNOWLEDGMENTS
REFERENCES
15 The Role of Redox Processes in Determining the Iron Isotope Compositions of Minerals, Melts, and Fluids
ABSTRACT
15.1. INTRODUCTION
15.2. PRINCIPLES AND NOMENCLATURE
15.3. METHODS FOR THE CALIBRATION OF IRON ISOTOPE FRACTIONATION FACTORS
15.3.1. Theoretical
15.3.2. Experimental
15.3.3. Spectroscopic
15.4. FUNDAMENTAL CONTROLS ON ISOTOPIC FRACTIONATION BETWEEN MINERALS, MELTS, AND FLUIDS
15.4.1. Minerals
15.4.2. Melts
15.4.3. Fluids
15.5. EFFECT OF REDOX PROCESSES IN INFLUENCING IRON ISOTOPE FRACTIONATION IN NATURAL SYSTEMS
15.5.1. Magmatic Processes
Partial Melting
Differentiation
15.5.2. Fluid Transfer from Mantle to Crust
Altered Oceanic Lithosphere
Subducted Oceanic Lithosphere
Iron Bearing Fluids Transferred to the Mantle Wedge
15.6. CONCLUSION
ACKNOWLEDGMENTS
REFERENCES
Notes
16 Zinc and Copper Isotopes as Tracers of Redox Processes
ABSTRACT
16.1. INTRODUCTION
16.2. THE DETERMINATION OF CU AND ZN ISOTOPE RATIOS
16.3. THEORETICAL AND EXPERIMENTAL CONSTRAINTS ON CU AND ZN ISOTOPE BEHAVIOR IN RELATION TO REDOX PROCESSES
16.4. APPLICATION OF CU AND ZN TO TRACE REDOX PROCESSES IN NATURAL SYSTEMS. 16.4.1. Hydrothermal Systems
Early Studies
Porphyry Systems
Magmatic Systems
16.4.2. Tracers of Fluid Rock Reactions and Subduction Zone Mass Transfer
16.5. SUMMARY AND CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
17 Mineral‐Melt Partitioning of Redox‐Sensitive Elements
ABSTRACT
17.1. INTRODUCTION
17.2. THEORETICAL BACKGROUND
17.2.1. Homogeneous Equilibria
17.2.2. Heterogeneous Equilibria
17.2.3. Mineral/Melt Partitioning as a Function of fO2
17.3. TRANSITION METALS (Fe, Cr, Ti, V)
17.3.1. Iron (Fe)
17.3.2. Chromium (Cr)
17.3.3. Titanium (Ti)
17.3.4. Vanadium (V)
17.4. RARE EARTHS (Ce, Eu)
17.5. URANIUM (U)
17.6. SIDEROPHILE ELEMENTS (Mo, W, Re, Pt GROUP ELEMENTS)
17.6.1. Molybdenum (Mo), Tungsten (W), and Rhenium (Re)
17.6.2. Platinum Group Elements (Ru, Rh, Pd, Os, Ir, Pt)
17.7. CONCLUDING REMARKS
ACKNOWLEDGMENTS
REFERENCES
Note
18 Titanomagnetite – Silicate Melt Oxybarometry
ABSTRACT
18.1. INTRODUCTION
18.2. OXYBAROMETERS RELATED TO TITANOMAGNETITE
18.3. OXYBAROMETERS BASED ON MINERAL EQUILIBRIA INVOLVING TITANOMAGNETITE
18.4. OXYBAROMETERS BASED ON ELEMENT PARTITIONING BETWEEN TITANOMAGNETITE AND SILICATE MELT
18.4.1. Vanadium Partitioning Oxybarometry
18.4.2. FeTiMM
18.5. APPLICATION OF TITANOMAGNETITE‐BASED OXYBAROMETERS TO NATURAL SILICIC ROCKS
18.6. CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
SUPPLEMENTARY REFERENCES
19 The Redox Behavior of Rare Earth Elements
ABSTRACT
19.1. INTRODUCTION
19.1.1. Trace Elements
19.1.2. Lanthanides
19.2. GEOCHEMISTRY OF RARE EARTH ELEMENTS
19.3. MULTIVALENT RARE EARTH ELEMENTS
19.3.1. Europium
19.3.2. Cerium
19.3.3. Influence of Other Elements: Mutual Interactions
Fe‐Eu Mutual Interactions
19.3.4 Other Multivalent Rare Earth Elements
19.4. CONCLUSIONS AND PERSPECTIVES
ACKNOWLEDGMENTS
REFERENCES
Notes
INDEX
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