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Alpers C.N., Jambor J.L., Nordstrom D.K. (eds.) Sulfate Minerals. Crystallography, Geochemistry, and Environmental Significance

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Alpers C.N., Jambor J.L., Nordstrom D.K. (eds.) Sulfate Minerals. Crystallography, Geochemistry, and Environmental Significance
Reviews in Mineralogy & Geochemistry. Volume 40. — Washington: Mineralogical Society of America, 2000. — 608 p. — ISBN 0-939950-52-9.

The review chapters in this volume were the basis for a short course on sulfate minerals sponsored by the Mineralogical Society of America (MSA) November 11-12, 2000 in Tahoe City, California, prior to the Annual Meeting of MSA, the Geological Society of America, and other associated societies in nearby Reno, Nevada. The conveners of the course (and editors of this volume of Reviews in Mineralogy and Geochemistry), Charles Alpers, John Jambor, and Kirk Nordstrom, also organized related topical sessions at the GSA meeting on sulfate minerals in both hydrothermal and low-temperature environments. A special issue of a journal yet to be identified is being planned for the publication of research articles based on several of these presentations. Taken together, the MSA short course and the related GSA sessions represent the most comprehensive grouping of technical meetings ever devoted to sulfate minerals.

The Crystal Chemistry of Sulfate Minerals
Introduction
Chemical Bonding
Stereochemistry of Sulfate Tetrahedra in Minerals
Variation in (S–Ø) distances
Variation in S–O distances
General polyhedral distortion in sulfate minerals
S6+ ↔ Tn+ substitution in minerals and its influence on (S,T)–O distances
Hydrogen bonding in sulfate minerals
Stereochemistry of Thiosulfate Tetrahedra
Variation in (S–Ø) distances
Variation in S–O distances
The formal valences of S in the thiosulfate group
Stereochemistry of Fluorosulfate Tetrahedra
Variation in S–Ø distances
Molecular-Orbital Studies of SO4 Polyhedra
The role of 3d-orbitals in bonding in sulfates
Stability of the (SO4)2– tetrahedron
(H2SO4) and (H2S2O7) clusters: prediction of equilibrium geometry
Bond angles in (SO4)2– tetrahedra
Alkali metal-sulfate clusters
Experimental studies of electron density
Theoretical studies of electron densities
Models of chemical bonding
Hierarchical Organization of Crystal Structures
Polymerization of SO4 and Other TØ4 Tetrahedra
A Structural Hierarchy for Sulfate Minerals
Structures Based on Sulfate Tetrahedra and Divalent and/or Trivalent Cation Octahedra
Graphical representation of octahedral-tetrahedral structures
Structures with unconnected SO4 groups
Structures with finite clusters of polyhedra
Structures with infinite chains
Structures with infinite sheets
Structures with infinite frameworks
Structures with Non-Octahedral Cation-Coordination Polyhedra
Calcium-sulfate minerals
Alkali-metal- and NH4-sulfate minerals
Apatite-like structures
Sulfates with the barite structure
Pb4(SO4)(CO3)2(OH)2 polymorphs
Uranyl sulfates
Sulfates with non-sulfate tetrahedral sheets or frameworks
Basic sulfates of Sb3+ and Bi3+
Miscellaneous sulfates
Structures with Anion-Centered Tetrahedra
Thiosulfate Minerals
Sulfite Minerals
Fluorosulfate Minerals
Acknowledgments
Appendix: Index of mineral names and the table numbers in which they appear
References
X-ray and Vibrational Spectroscopy of Sulfate in Earth Materials
Introduction
X-ray Spectroscopy
X-ray absorption spectroscopy (XAS)
X-ray absorption spectroscopy at the sulfur L-edge
X-ray photoelectron spectroscopy
X-ray imaging and spectromicroscopy
Vibrational Spectroscopy
Symmetry and vibrational modes of sulfate and its complexes
Data collection and analysis
Vibrational spectra of sulfate in solids
Vibrational spectra of sulfate in aqueous solutions
Vibrational spectra of sulfate at the interfaces
Spectromicroscopy of sulfates
Complementary Spectroscopic Methods
Scattering methods
Infrared emission spectroscopy
Optical spectroscopy
Summary and Future Directions
Acknowledgments
References
Sulfate Minerals in Evaporite Deposits
Solubility Controls on Mineral Precipitation and Paths of Evaporation
Solubility of Na-K-Ca-Mg-bearing sulfate minerals
Chemical divides in the system Ca2+–SO42––HCO3
Precipitation sequences of Na-K-Mg-bearing sulfates
Radium
Fluid inclusions
Barite in Submarine Volcanic Hydrothermal Systems
Sulfide-poor barite deposits of Archean age
Volcanic-hosted massive sulfide (VHMS) deposits
Modem submarine hydrothermal barite
Sedimentary Exhalative (Sedex) Deposits of Barite
Proterozoic barite
Phanerozoic convergent continental margins
Ordovician-Devonian Roberts Mountain allochthon, Nevada
Cenozoic strike-slip margins
Sedex barite deposits in active marine evaporite settings
The question of metal-bearing and metal-free bedded barite deposits
Cenozoic Pelagic Barite and Dispersed Barite in Deep Sea Sediments
Barite in seawater
Mode(s) of precipitation of pelagic barite
Fate of barite in the water column
Barite in deep-sea sediments
Epigenetic Barite Deposits and Evaporites
Carbonate-hosted barite deposits
Continental rifts
Barite in late-stage thrust belts
Dispersed cements and nodules of barite
Barite of Continental Igneous and Igneous-Hydrothermal Origin
Carbonatites
Other magmatic examples
Hydrothermal barite in the Cordilleran of the western United States
Barite from outer space
Behavior of Barite during Weathering, Diagenesis, and Metamorphism
Formation of barite in soil environments
Subaerial weathering of barite
Solution and reprecipitation of barite in diagenetic redox fronts
Behavior of barite during metamorphism
Celestine in Sedimentary Environments
Pelagic celestine
Carbonate sediments
Celestine in coastal carbonate-evaporite sequences
Environmental Aspects
Barium in potable water supplies
Barite and the uranium industry
Problems related to oil and gas production
An example of a «bad rap» for barite
Concluding Remarks
Acknowledgments
References
Evaporation paths and mineralogy of marine evaporites
Evaporation paths and mineralogy of non-marine evaporites
Mineral Textures and Fabrics
Criteria for syndepositional features
Criteria for burial alteration features
Ambiguous features
Summary
References
Barite-Celestine Geochemistry and Environments of Formation
Introduction
Geological significance of barite and celestine
Economic importance
Some conventions and terms used in this chapter
Physical Chemistry
Crystal chemistry and solid-phase relations
Solubility of barite and celestine in aqueous solutions
Stability ranges in multicomponent systems
Ba, Sr, and S in Crustal Rocks and Natural Waters
Crustal abundance and controls on the distribution of Ba and Sr
Sulfate geochemistry
Waters in sedimentary basins
Meteoric groundwaters
Seawater
River and estuarine waters
Waters in crystalline rocks
Continental rifts
Seafloor hydrothermal vents
Review of controls on Sr/Ba ratios in natural waters
Environments of Formation of Barite and Celestine: An Overview
Mechanisms for the precipitation of barite and celestine
Relation of barite and celestine occurrences to global tectonics and regional hydrogeology
Relation of barite and celestine occurrences to the secular evolution of sedimentary rock types
Marine versus continental barite
Chemical and Isotopic Composition of Barite and Celestine: An Overview
Frequency distribution of compositions in the barite-celestine series
Ba-Sr zoning in barite-celestine
Other cations
Strontium isotopic composition
Sulfur isotopic composition
Oxygen isotopic composition
Precipitation and Dissolution of Alkaline Earth Sulfates: Kinetics and Surface Energy
Introduction
Driving Forces for Growth and Dissolution
Supersaturation
Definition and Determination of Growth Rate
Rate determination
Crystallization and Dissolution Kinetics
Homogeneous nucleation
Heterogeneous nucleation
Determination of interfacial free energy
Interfacial energies between minerals and aqueous solutions
Contact-Angle Method
Surface-tension component theory
Contact-angle measurement and thin-layer wicking
Conclusions
Nomenclature
Symbols
Subscripts and superscripts
References
Metal-sulfate Salts from Sulfide Mineral Oxidation
Compositions and Crystal Chemistry of Hydrated Metal Salts
Divalent cations
Trivalent cations
Mixed divalent-trivalent salts
Other minerals
Processes of Formation, Transformation and Dissolution
Pyrite oxidation
Field studies
Dissolution during rainfall events
Laboratory studies
Solubilities and stability relationships
Paragenesis
Acknowledgments
References
Iron and Aluminum Hydroxysulfates from Acid Sulfate Waters
Introduction to Acid Sulfate Environments
Mine drainage
Residues from mineral extraction and ore processing
Rock weathering
Acid sulfate soils (cat clays)
Formation of Acid Sulfate Waters and Associated Weathering Products of Fe and Al
The Fe system
The Al system
Fe and AI Hydroxysulfates of Low Crystallinity
Schwertmannite [Fe8O8(OH)6SO4•nH2O]
Hydroxysulfates of Al
Formation and Decomposition of Fe- and Al-Hydroxysulfates of Low Crystallinity
Biological influences on mineral formation
Geochemical Controls on Mineral Formation
The Fe System
The AI system
Environmental Implications of Trace Element Sorption
Sorption of metal cations
Sorption of oxyanions
Mineral instability and possible affects on sorbed species
Summary
References
Jarosites and Their Application in Hydrometallurgy
Introduction
Synthesized Members of the Jarosite Subgroup
Occurrences of the Jarosite Subgroup
Oxidized sulfide deposits and pyritiferous rocks
Nodules and disseminations in clays
Acid soils
Hypogene jarosite
Alteration of minerals of the jarosite subgroup
Conditions Affecting the Syntheses of the Jarosite Subgroup
Sodium, potassium, and ammonium jarosites
Jarosite Precipitation in the Zinc Industry
Outline of the jarosite process
Metallurgical problems and environmental concerns
Kinetics of Jarosite Precipitation
Flowsheets
Impurity Incorporation in Synthetic Jarosites
Monovalent substitutions
Divalent substitutions
Trivalent substitutions
Higher valency substitutions
Cell Dimensions of the Subgroup
Conclusions and Future Trends
References
Alunite-Jarosite Crystallography, Thermodynamics, and Geochronology
Crystallographic Data
Unit-cell parameters
Thermodynamic Data
Alunite and natroalunite
Jarosite and natrojarosite
Other minerals in the alunite-jarosite supergroup
Mixing relations
Geochemistry and Occurrences
Alunite and natroalunite
Jarosite and natrojarosite
Geochronology Using Alunite and Jarosite
References
Solid-Solution Solubilities and Thermodynamics: Sulfates, Carbonates and Halides
Introduction
Definitions and Representation of Thermodynamic States
Thermodynamic equilibrium states
Primary saturation states
Stoichiometric saturation states
Comparison of Solid-Solution and Pure-Phase Solubilities
Stoichiometric saturation solubilities
Primary saturation and thermodynamic equilibrium solubilities
Estimation of Thermodynamic Mixing Parameters
Miscibility-gap data
Spinodal-gap data
Critical mixing-point data
Distribution coefficient measurements
Stoichiometric saturation solubilities
Thermodynamic equilibrium solubilities
Excess-free-energy data for selected sulfate, carbonate and halide solid solutions
Multicomponent solid-solution systems
Summary and Conclusions
Acknowledgments
References
Predicting Sulfate-Mineral Solubility in Concentrated Waters
Introduction
Background
Compositions of concentrated waters
Modeling approaches
Model Description
Summary of model formulation
Internal consistency of model data-sets
Model Development to Predict Sulfate-Mineral Solubility
Sulfate-mineral formation in the system Na-Ca-Mg-K-Cl-SO4-H2O
Formation of Ba, Sr, and Rb sulfates
Formation of metal sulfates
Formation of sulfates in acid systems
Formation of sulfates in basic systems
Application of the Ion-Interaction Approach to Field Settings
Results of the applications
Conclusions
References
Stable Isotope Systematics of Sulfate Minerals
Introduction
Fundamental Aspects of Stable Isotope Geochemistry
Analytical Methods
Reference Reservoirs
Factors that Control Stable Isotope Fractionation
Equilibrium Fractionation Factors
Sulfur
Oxygen
Hydrogen
Geothermometry
Processes that Cause Stable Isotopic Variations
Kinetics of isotope exchange reactions
Sulfate reduction, sulfide oxidation, and associated processes
Mechanisms of precipitation and dissolution of sulfate minerals
Geochemical Environments
Secular variations in seawater sulfate isotopic compositions
Seafloor hydrothermal systems
Magmatic systems
Continental hydrothermal systems
Metamorphism of sulfate minerals
Surficial environments
Summary
Acknowledgments
References
Index
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