Minerals in Soil Environment

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Title Page
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CONTENTS
DEDICATION
FOREWORD
PREFACE
CONTRIBUTORS
Chapter 1
Chapter 1: An Introduction to Soil Mineralogy
I. Chemical and Structural Classification of Minerals
A. Halide, Sulfate, and Carbonate Minerals
B. Sulfides
C. Oxides, Hydroxides, and Oxyhydroxides
D. Silicates
II. Phyllosilicate Minerals in Soils
A. Basic Structural Concepts
B. Structure and Properties of Phyllosilicate Minerals Common in Soils
III. Aluminosilicate Minerals with Short-Range Order: Allophane and Imogolite
IV. Some Crystallographic Concepts
A. Periodicity in Crystals
B. The Unit Cell
C. Miller Indices
D. X-ray Diffraction
V. Summary
VI. Problems and Exercises
Acknowledgments
References
Chapter 2
Chapter 2: Surface Chemistry of Soil Minerals
I. Nature of Mineral Surfaces
A. Diffuse Double-layer Model of Permanent-charge Minerals
B. Structure of the Layer Silicate-Solution Interface
C. Point of Zero Charge Concept for Variable-charge Minerals
D. Diffuse Double-layer Model of Variable-charge Minerals
E. Discrete-site Bonding Model of Variable-charge Minerals
F. Specifically Adsorbed Ions on Variable-charge Minerals
II. Processes at Mineral Surfaces
A. Ion Exchange Equations and the Problem of Surface Activity
B. A Statistical Mechanical Description of Ion Exchange
C. Difficulties with Ion Exchange Models
D. General Rules of Cation Exchange
E. Chemisorption of Cations and Anions
F. Clay Surface Acidity
G. Electron Transfer
H. Clay Swelling Behavior
I. The Covolume Model of Particle Interaction
III. Summary
IV. Appendix
References
Chapter 3
Chapter 3: An Introduction to Organic Matter in Mineral Soils
I. The Nature of Organic Substances
A. Plant Materials
B. Humic Materials
C. Nonhumic Substances-Carbohydrates
D. Microbial Biomass
II. The Persistence of Organic Substances
A. The Use of 14C as a Tracer
B. Dating Techniques for Organic Matter
III. Reactions of Well-Defined Chemicals with Clays
A. Small Molecules
B. Macromolecules or Polymers
C. Predicted Behavior of Biopolymers in Soils
IV. Natural Organo-Mineral Associations
A. Density Fractionations
B. Fractionations by Sedimentation
C. Physical Disaggregation of Soils
D. Associations of Organic Matter with Hydrous Oxides
V. Conclusions
VI. Acknowledgements
VII. Problems and Exercises
VIII. Supplemental Reading-Texts on Organic Matter
References
Chapter 4
Chapter 4: Mineral Equilibria and the Soil System
I. Fundamentals of Mineral Equilibria
A. Phase Rule¹
B. Enthalpy, Entropy, and Free Energy
C. Thermochemical Data Base
D. Role of Solubility Measurements in Understanding the Soil System
II. Use of Thermochemical Data in Understanding Soil Mineral Equilibria
A. Soil Mineral Weathering Sequences
B. Mechanisms That Control Aqueous Concentrations
C. Geochemical Groundwater Modeling
D. Selection of Appropriate Experiments or Experimental Parameters
III. Past, Present, and Future
IV. Study Problems
References
Chapter 5
Chapter 5: Mineral Occurrence in Soil Environments
I. Soil Taxonomy: Soil Mineralogy Relationships
A. Orders
B. Suborders
C. Great Groups
D. Subgroups
E. Families
F. Series
II. Quartz and Other Silica Materials
III. Feldspars
IV. Olivine, Amphiboles, Pyroxenes
A. Olivine
B. Amphiboles
C. Pyroxenes
V. Micas
A. Biotite
B. Muscovite
C. Clay Mica
VI. Vermiculite
VII. Chlorite
VIII. Smectite
A. Inheritance
B. Formation by Pedogenesis and Alteration
C. Alteration to Other Minerals
D. Distribution
IX. Talc and Pyrophyllite
X. Kaolinite and Halloysite
A. Kaolinite
B. Halloysite
XI. Serpentine
XII. Palygorskite and Sepiolite
XIII. Zeolites
XIV. Allophane and Imogolite
A. Allophane
B. Imogolite
XV. Carbonates, Sulfates. Sulfides. and Chlorides
A. Carbonates
B. Sulfates
C. Sulfides
D. Chlorides
XVI. Aluminum Oxides
XVII. Iron Oxides
A. Magnetite and Ilmenite
B. Goethite
C. Lepidocrocite and Akaganeite
D. Hematite
E. Maghemite
F. Ferrihydrite
G. Iron Oxides and Soil Families
XVIII. Manganese Oxides
XIX. Titanium and Zirconium Minerals
XX. Phosphate Minerals
XXI. Summary
XXII. Problems and Exercises
References
Chapter 6
Chapter 6: Carbonate, Halide, Sulfate, and Sulfide Minerals
I. Calcite. Magnesium-Calcite, and Dolomite
A. Natural Occurrence
B. Crystallography
C. Formation and Stability
D. Identification
E. Impact on Soils
II. Gypsum and Other Moderately Soluble Sulfates
A. Natural Occurrence
B. Crystallography
C. Formation and Stability
D. Identification
E. Impact on Soils
III. Pyrite and Jarosite
A. Natural Occurrence
B. Crystallography
C. Formation and Stability
D. Identification
E. Impact on Soils
IV. Soluble Minerals
A. Natural Occurrence
B. Crystallography
C. Formation and Stability
D. Identification
E. Impact on Soil
V. Summary
VI. Problems and Exercises
References
Chapter 7
Chapter 7: Aluminum Hydroxides and Oxyhydroxides
I. Nomenclature and Structural Properties
II. Methods of Identification and Determination
A. X-ray Diffraction Analysis
B. Thermal Analysis
C. Infrared Absorption Analysis
D. Selective Dissolution
III. Mechanism of Aluminum Hydroxide Formation
A. Composition and Structure of OH-Al Polymers
B. Hydrolysis and Polymerization
C. Crystallization of Aluminum Hydroxides
D. Polymorphs of Aluminum Hydroxides
IV. Gibbsite in Soils
A. Occurrence
B. Genesis of Gibbsite in Soils
V. Formation of Aluminum Oxyhydroxides in Soils
VI. Reactions of Aluminum "Hydroxide" in Soils
A. Reaction with Anions
B. Adsorption of Cations
C. Stabilization of Soil Aggregates
VII. Problems and Exercises
References
Chapter 8
Chapter 8: Iron Oxides
I. Forms and Characteristics of Soil Iron Oxides
A. General
B. Goethite
C. Hematite
D. Lepidocrocite
E. Magnetite and Maghemite
F. Ferrihydrite
G. Other Minerals
II. Occurrence and Formation of Iron Oxides
A. General Processes
B. Thermodynamic Stability vs. Kinetics
C. Occurrence and Modes of Formation in Soils
III. Properties Relevant to Soils
A. Surface Structure
B. Surface Charge
C. Ion Adsorption
D. Adsorption of Organics
E. Aggregation and Cementation
IV. Iron Oxides and Microorganisms
A. Reduction of Iron-Oxides by Microorganisms
B. Biotic Formation of Iron Oxides
V. Determination
A. General
B. Goethite
C. Hematite
D. Lepidocrocite
E. Maghemite-Magnetite
F. Ferrihydrite-Feroxyhite
VI. Acknowledgment
VII. Problems and Exercises
VIII. Supplementary Reading
References
Chapter 9
Chapter 9: Manganese Oxides and Hydroxides
I. The Manganese-Oxide Minerals
A. Tunnel Structures
B. Layer Structures
C. The Lower Oxides
D. Relation Between Tunnel and Layer Structures
II. Mineral Identification
A. X-ray Diffraction
B. Infrared Spectroscopy
III. Occurrence of the Minerals in Soils
IV. Oxidation of Manganese and Growth of Nodules
V. Formation of Manganese Minerals in Soils
VI. Chemical Properties
A. Chemical Composition
B. Surface Charge
C. Adsorption
VII. Summary
VIII. Problems and Exercises
References
Chapter 10
Chapter 10: Kaolin and Serpentine Group Minerals
I. Structural Properties of Kaolin Minerals
A. Kaolinite
B. Halloysite
II. Morphological Characteristics of Kaolinite and Halloysite
A. Kaolinite
B. Halloysite
III. Formation of Kaolin
A. Rapid Synthesis of Kaolinite
B. Equilibrium Environment and Conditions for Synthesis
C. Kaolinite Formation Induced by Plant Growth
D. Kaolinite Formation From Hydroxy-Al Interlayered Montmorillonite
E. Isotopic Composition of Kaolins formed at Different Temperatures
F. Summary
IV. Occurrence of Kaolin Minerals in Soils, Rocks, and Sediments
A. Stability of Kaolinite in Weathering Environments
B. Kaolinite in Young Soils
C. Soils with Abundant Kaolinite Content
D. Rocks Containing Abundant Kaolinite
E. Formation and Distribution of Halloysite in Soils
F. Soil Kaolinite-A Major Source of Ocean Sediments
V. Order-Disorder in Kaolins
VI. Interstratification of Kaolinite and 2:1 Minerals
VII. Isomorphous Substitution in Kaolinite and Halloysite
VIII. Chemical Properties of Kaolinite
A. Cation Exchange
B. Anion Exchange
C. Flocculation and Dispersion
IX. Physical Properties of Kaolinite and Halloysite
X. Identification of Kaolinite and Halloysite
XI. Quantitative Analysis of Kaolinite and Halloysite
XII. Serpentine Minerals
A. Structure
B. Composition
C. Morphological Properties
D. Thermal Properties
E. Stability and Weathering
F. Synthesis
XIII. Problems and Exercises
XIV. Supplemental Reading
References
Chapter 11
Chapter 11: The Pyrophyllite-Talc Group
I. Structural Properties and Mineral Identification
A. Structures and Formulas
B. X-ray Diffraction
C. Thermal Analysis
D. Infrared Analysis
E. Optical Properties
II. Natural Occurrences
A. Geologic Extent
B. Soil Environment
III. Equilibrium Environment and Conditions for Synthesis
IV. Chemical Properties
V. Physical Properties
VI. Quantitative Determinations
VII. Problems and Exercises
References
Chapter 12
Chapter 12: Micas
I. Structural Properties and Mineral Identification
A. Structures, Formulas, and Nomenclature
B. X-Ray Diffraction (XRD)
C. Differential Thermal Analysis (DTA)
D. Thermogravimetry (TG)
E. Infrared Spectroscopy (IR)
F. Electron Microscopy
G. Mössbauer Spectroscopy
H. Nuclear Magnetic Resonance (NMR)
II. Weathering and Synthesis Relationships
A. General Principles
B. Physical Weathering
C. Simple Transformation to Expansible 2:1 Minerals
D. Mica-Vermiculite-Kaolinite Stability Diagram and Complex Transformations
E. Pedogenic Mica
F. Illitization in Geologic Columns
G. Glauconite Formation and Weathering
III. Natural Occurrence
A. Occurrence in Soil Parent Materials
B. Occurrence in Soils
IV. Chemical Properties
A. Properties Related to Ion Exchange
B. Chemical Composition
V. Physical Properties
VI. Quantitative Determination
VII. Conclusions
VIII. Acknowledgments
IX. Problems and Exercises
X. Supplemental Reading
References
Chapter 13
Chapter 13: Vermiculites¹
I. Distribution in Soils
II. Structure and Composition
III. Formation of Vermiculite
A. Release of Potassium
B. Oxidation of Iron
C. Hydroxyl Orientation
D. Total Charge
E. Stability of Vermiculites
IV. Identification of Vermiculites
A. X-ray Diffraction
B. Infrared Spectroscopy
C. Thermal Analysis
D. Electron Microscopy
E. Total Charge
F. Quantitative Determination of Vermiculite
V. Ion Exchange
A. Cation Exchange Capacity
B. Cation Exchange
C. Ion Fixation
VI. The Soil-Clay-Vermiculite Problem
VII. Problems and Exercises
References
Chapter 14
Chapter 14: Smectites
I. Structural Properties and Mineral Identification.
A. X-Ray Diffraction (XRD)
B. Electron Optical Properties (TEM & SEM)
C. Thermal Analysis
D. Infrared (IR) Spectroscopy
E. Elemental Analysis (EA)
F. Selective Dissolution Analysis (SDA)
G. Mössbauer Spectroscopy (MS)
H. Other Methods of Smectite Identification
II. Natural Occurrence
A. Geographic Extent
B. Soil Environment
C. Sedimentary Occurrence
III. Equilibrium Environment and Conditions for Synthesis
A. Conditions for Laboratory Synthesis
B. Transformation and Formation in Soils
C. Smectite Weathering
IV. Chemical Properties.
A. Cation Exchange
B. Anion Exchange
C. Reaction Kinetics
D. Molecular Sorption
E. Other Chemical Properties
F. Smectites and Soil Fertility
V. Physical Properties
A. Shrink-Swell
B. Water Retention
C. Cohesion and Adhesion
D. Particle Size Distribution
VI. Quantitative Determination
A. X-Ray Diffraction Methods
B. Surface Area Methods
C. Cation Exchange Capacity Methods
D. Other Methods of Quantitative Determination
VII. Conclusions
VIII. Problems and Exercises
IX. Supplementary Reading
References
Chapter 15
Chapter 15: Chlorites and Hydroxy-Interlayered Vermiculite and Smectite
I. Origin and Sources of Chlorite
II. Structural Properties and Mineral Identification of Chlorite
A. Idealized Structures
B. X-ray Diffraction Properties
C. Chemical Properties
D. Thermal Properties
E. Infrared and Mössbauer Properties
III. Weathering of Chlorite Minerals
IV. Structural Properties and Mineral Identification of Hydroxy-Interlayered Vermiculite (HIV) and Smectite (HIS)
A. Idealized Structure and Generalizations
B. Identification by X-ray Diffraction (XRD)
C. Identification by Thermal Analysis
D. Identification by Infrared Analysis
E. Characterization of Hydroxy-interlayer Materials by Conductometric and Potentiometric Titrimetry
V. Origin, Sources, Distribution, and Weathering of Hydroxy Interlayered Minerals
A. Origin and Sources
B. Distribution and Weathering
VI. Physicochemical Properties of Hydroxy-Interlayered Vermiculite (HIV) and Hydroxy-Interlayered Smectite (HIS)
A. Physical Properties
B. Chemical Properties
C. Removal of Hydroxy Interlayers
VII. Laboratory Synthesis of Hydroxy-Interlayered Vermiculite (HIV) and Smectite (HIS)
A. Synthesis Methodology
B. Type of Clay Mineral Structure.
C. Nature of Hydroxy-Interlayer Material
D. Comparison of Synthetic and Naturally Interlayered Clays
VIII. Problems and Exercises.
Acknowledgments
References
Chapter 16
Chapter 16: Interstratification in Layer Silicates
I. Regular Interstratification
A. Characterization of Regularly Interstratified Layers
B. Examples of Regularly Interstratified Minerals and Interpretation of Their X-Ray Diffraction Patterns
II. Random Interstratification
A. Characterization of Randomly Interstratified Layers
B. Examples of Randomly Interstratified Minerals and Interpretation of Their XRD Patterns
III. Formation of Interstratified Minerals
A. Mica-Vermiculite
B. Mica-Smectite
C. Mechanism of Regular Interstratification
IV. Recent Developments
V. Summary
VI. Appendix
Sample Calculation for Complete One-Dimensional Diffraction Profile
References
Chapter 17
Chapter 17: Palygorskite and Sepiolite Group Minerals
I. Basic Characteristics
A. Structure
B. Chemical Composition
C. Morphology
D. Surface Properties
II. Mineral Identification
A. Field and Optical Identification
B. X-ray Identification
C. Thermal Analysis
D. Transmission- and Scanning-Electron Microscopy (TEM and SEM)
E. Infrared and Mössbauer Spectroscopy
III. Formation of Palygorskite and Sepiolite.
A. Synthesis
B. Equilibrium Conditions
C. Environments of Occurrence
D. Pedogenic Formation of Palygorskite
IV. Problems and Exercises
References
Chapter 18
Chapter 18: Zeolites in Soils
I. Structure and Composition
A. Definition
B. Composition
C. Crystal Structure
II. Properties and Applications
A. Mineralogical Properties
B, Cation-exchange Properties
C. Adsorption and Molecular Sieving Properties
III. Natural Occurrences
A. Geologic Occurrences
B. Pedogenic Occurrences
IV. Formation of Zeolites
A. Equilibrium Environments and Conditions for Formation
B. Synthesis under Hydrothermal Conditions
V. Mineral Identification
A. X-ray Diffraction
B. Morphology
C. Optical Microscopy
D. Thermal Analyses
E. Elemental Analysis
F. Other Analytical Methods
VI. Quantitative Determinations
A. X-ray Diffraction Methods
B. Cation-Exchange Methods
C. Adsorption Methods
VII. Problems and Exercises
VIII. Acknowledgments
IX. Supplemental Reading
References
Chapter 19
Chapter 19: Silica in Soils: Quartz and Disordered Silica Polymorphs
I. Structure and Chemical Composition
A. Crystal Structure
B. Chemical Composition
II. Mineral Identification
A. Physical Properties
B. Light Optical Properties
C. X-ray Diffraction
D. Thermal Properties
E. Infrared Spectroscopy
III. Quantitative Determination
A. Quartz
B. Opal-CT and Cristobalite
C. Opal-A
IV. Formation and Solubility of Silica Minerals
A. Formation of Silica Minerals
B. Solubility of Silica Minerals
C. Soil Factors Influencing Dissolution Kinetics
V. Natural Occurrence
A. Quartz
B. Opal-CT and Cristobalite
C. Opal-A
VI. Pedological Implications
A. Impact on Soil Properties
B. Quartz as a Stable Reference Mineral
C. Silica as an Indicator of Provenance
D. Silica as an Index of Environmental History
VII. Problems and Exercises
References
Chapter 20
Chapter 20: Feldspars, Olivines, Pyroxenes, and Amphiboles¹
I. Structural Properties and Mineral Identification
A. Feldspars
B. Olivines, Pyroxenes, and Amphiboles
II. Natural Occurrence and Equilibrium Environment
A. Feldspars
B. Olivines, Pyroxenes, and Amphiboles
III. Physicochemical Properties
A. Feldspars
B. Olivines, Pyroxenes, and Amphiboles
IV. Quantitative Determination
A. Feldspars
B Olivines, Pyroxenes, and Amphiboles
V. Summary and Conclusions
VI. Problems and Exercises
VII. Supplementary Reading
References
Chapter 21
Chapter 21: Allophane and Imogolite
I. Structural Properties and Mineral Identification
A. X-ray Diffraction
B. Electron Microscopy
C. Electron Diffraction
D. Chemical Analyses
E. Infrared Spectroscopy
F. X-ray Fluorescence Spectroscopy
G. Nuclear Magnetic Resonance Spectroscopy
H. Thermal Analyses
I. Density and Surface-Area Measurement
J. Structure Models
II. Natural Occurrence
A. Geographic Extent
B. Soil Environment
C. Sedimentary Occurrence
III. Equilibrium Environment and Conditions for Synthesis
IV. Chemical Properties
A. Ion Exchange
B. Surface Acidity
C. Specific Adsorption of Cations and Anions
D. Interaction with Organic Compounds
V. Physical and Engineering Properties
VI. Quantitative Determination
VII. Conclusion
VIII. Problems and Exercises
References
Chapter 22
Chapter 22: Phosphate Minerals
I. Classification and Structure of Phosphate Minerals
II. Occurrence of Phosphate Minerals in Soils
A. Naturally Occurring Phosphate Minerals in Soils
B. Reaction Products of Phosphate Fertilizers in Soils
C. Surface Reactions of Phosphate on Soil Minerals
III. Phosphate Mineral Equilibria in Soils
A. Phosphate Species in Soil Solution
B. A Unified Phosphate Solubility Diagram
C. Effect of Redox on Phosphate Stability
D, Polyphosphate Equilibria in Soil
E. Equilibria of Trace Element Phosphates
IV. Physical Characterization of Phosphate Minerals in Soils
V. Conclusions
VI. Problems and Exercises
References
Chapter 23
Chapter 23: Titanium and Zirconium Minerals
I. Geological and Geochemical Background: Titanium and Zirconium in Parent Materials
A. Titanium
B. Zirconium
II. Forms and Occurrence of Titanium and Zirconium in Soils
A. Residual Minerals
B. Minerals Formed Through Weathering or Alteration
C. Authigenic Minerals
III. Chemical and Physical Properties of the Minerals Commonly Reported in Soils
A. Crystal Structures and Chemistry
B. Stability Relationships
C. Charge Characteristics
D. Magnetic Properties
E. Techniques of Identification
F. Influence on Soil Structure and Induration
IV. Formation and Weatherability of the Minerals
A. Evidence for Titanium and Zirconium Mobility
B. Synthesis of the Minerals
C. Use of Titanium and Zirconium in Studies of Soil Formation
V. Problems and Exercises
Acknowledgments
References
Topic Index
SUBJECT INDEX