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Iron in Soils and Clay Minerals 1988th ed.(Nato Science Series C: Vol.217) H XX, 894 p. 87

Stucki, J.W., Goodman, B.A., Schwertmann, U. 　著

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発行年月	1987年12月
出版社／提供元	Springer Netherlands
出版国	オランダ
言語	英語
媒体	冊子
装丁	hardcover
ページ数／巻数	XX, 894 p.
ジャンル	洋書／生命科学・医学／農学／農学
ISBN	9789027726131
商品コード	0208728340
本の性格	議事録
商品URL	https://kw.maruzen.co.jp/ims/itemDetail.html?itmCd=0208728340

内容

In order to understand fully the nature of one of Eath's most important natural resources, the soil, one must understand the behavior of iron. Why iron? Because it greatly influences many soil properties and processes. The various forms of iron in soils largely determine soil color, structure, fabric, electrical charge, and surface area; and are tied intimately to redox, laterization, and podzolization processes. Iron is thus a major force in determining soil fertility and the capacity of a soil to filterout pollutants that would otherwise find their way into underground waters. It has great influence on the movement of water, air, and roots. The purpose of this book is to discuss in depth the properties and behavior of iron in various soil minerals, andits role in soil forming processes. Also reviewed are the chemistry of iron, and methods for its separation, identification, and characterization in soils and sediments.

1. The Geobiochemical Cycle of Iron.- 1-1. Geochemical Characterization of Iron.- 1-2. Geochemical Behavior of Iron in the Weathering Environment.- 1-3. Iron in Organisms and Soil Organic Matter.- 1-3.1. Fe-Bearing Compounds in Organisms.- 1-3.2. Quantitative Relationships.- Literature Cited.- 2. An Introduction to Physical and Chemical Principles.- 2-1. Introduction.- 2-2. Nuclear Properties’and their Importance in Spectroscopy.- 2-3. Electronic Properties — Free Ions.- 2-4. Electronic Properties — Crystal Field Theory.- 2-5. Electronic Properties — Molecular Orbital Theory.- Literature Cited.- 3. Solubility and Redox Equilibria of Iron Compounds in Soils.- 3-1. Introduction.- 3-2. Equilibrium Reactions of Iron.- 3-3. Solubility of Iron(III) Oxides in Soils.- 3-4. Other Iron(III) Minerals.- 3-5. Hydrolysis of Iron(III).- 3-6. Other Iron(III) Complexes in Soils.- 3-7. Effect of Redox on Iron(II) Solubility.- 3-8. Effect of Redox on Total Iron Solubility.- 3-9. Electron Titration of Soils.- 3-10. Effect of Redox on Smectite Stability.- 3-11. Role of Chelation in Iron Solubility.- 3-11.1. Measuring Fe3+ Solubility in Soils.- 3-11.2. Role of Chelation in Iron Availability.- 3-12. Problems.- Literature Cited.- 4. Separation and Concentration of Iron-Containing Phases.- 4-1. Introduction.- 4-2. Physical Separation Procedures.- 4-2.1. Manual Separation of Iron-Rich Areas.- 4-2.2. Wet Sieving to Concentrate Iron-Rich Concretions.- 4-2.3. Particle Size Separation.- 4-2.4. Density Gradient Separation.- 4-2.5. Magnetic Separation.- Hand Magnet.- High Gradient Magnetic Separation.- 4-3. Chemical Separation Procedures.- 4-3.1. Dissolution of Aluminosilicates Using Strong Bases.- Acknowledgments.- Literature Cited.- 5. Phase Identification by Selective Dissolution Techniques.- 5-1. Introduction.- 5-1.1. Specificity and Selectivity.- 5-2. Dissolution Techniques.- 5-2.1. The Pyrophosphate Technique(s).- 5-2.2. The Oxalate Technique.- 5-2.3. The EDTA Technique.- 5-2.4. The Dithionite-Citrate-Bicarbonate Technique.- 5-3. Concluding Remarks.- Literature Cited.- 6. The Assay for Iron in Soils and Clay Minerals.- 6-1.Introduction.- 6-2. Preliminary Considerations.- 6-3. Sampling.- 6-4. Sample Preparation.- 6-5. Selective Dissolution.- 6-6. Total Dissolution.- 6-6.1.Hydrogen Peroxide.- 6-6.2. Acids.- 6-6.3. Ashing.- 6-6.4.Decomposition with Mineral Acids.- 6-6.5. Fusions.- 6-6.6.Resistant Minerals.- 6-6.7. Iron(II).- 6-7. The Determination of Iron.- 6-7.1. Titrimetry.- 6-7.2.Colorimetry.- 6-7.3.Electrical.- 6-7.4.Instrumental Analysis.- 6-8. Precision, Accuracy, and Reference Materials.- Acknowledgements.- Literature Cited.- 7. Introduction to Crystal Structures of Iron-Containing Minerals.- 7-1.Introduction.- 7-2. Chain Silicates.- 7-2.1. Olivine.- 7-2.2.Pyroxenes.- 7-2.3.Amphiboles.- 7-2.4.Garnet.- 7-3. Phyllosilicate Clay Minerals.- 7-4. Iron Oxides.- 7-3.1.Hematite.- 7-3.2.Umenite.- 7-3.3.Magnetite.- 7-3.4.Maghemite.- 7-3.5. Goethite.- 7-3.6.Lepidocrocite.- 7-3.7.Akaganéite.- 7-3.8.Ferrihydrite and Feroxyhite.- Acknowledgements.- Literature Cited.- 8. The Application of Micro-Beam Methods to Iron Minerals in Soils.- 8-1.Introduction.- 8-2. Diffraction Theory.- 8-3. X-ray Diffraction.- 8-3.1.Mineral Identification.- 8-3.2. Crystal Size Estimation.- 8-3.3.Unit Cell Dimensions.- 8-3.4.Examples.- Goethite.- Lepidocrocite.- Hisingerite.- Nontronite.- 8-4. Transmission Electron Microscopy.- 8-4.1. Electron Diffraction.- Selected Area Diffraction (SAD).- Single-Crystal Diffraction.- 8-4.2. Electron Imaging.- Bright Field.- Dark Field.- n-Beam Images — High Resolution TEM.- 8-4.3. Specimen Preparation.- Grain Mounts.- Ion Thinning.- Microtomed Sections.- 8-4.4. Examples.- Goethite.- Hisingerite.- Ferrihydrite.- Iron Mineral Formation in Weathering.- 8-4.5. Analytical Electron Microscopy.- Literature Cited.- 9. Some Properties of Soil and Synthetic Iron Oxides.- 9-1.Introduction.- 9-2. Color.- 9-3. Crystal Morphology and Size.- 9-3.1. General Morphology.- 9-3.2.Crystal Size and Morphological Variations.- Electron Microscopy.- X-ray Diffraction.- 9-3.3.Môssbauer Spectroscopy.- 9-4. Surface Area.- 9-4.1.Gas and Dipole Adsorption.- 9-4.2.Phosphate Adsorption.- 9-4.3. X-ray Diffraction Line Broadening.- 9-5. Isomorphous Substitution.- 9-5.1. Aluminum.- 9-5.2. Other Metals.- 9-6. Thermal Behavior.- 9-7. Dissolution Kinetics.- 9-9. Interactions with Clay Silicates.- 9-10. Future Work.- Literature Cited.- 10. Introduction to the Surface Charge Properties of Iron oxides and Oxidic Soils.- 10-1. Introduction.- 10-2. Charging Phenomena at Iron Oxide Interfaces.- 10-2.1. Charge Development in the Presence of Indifferent Electrolytes.- 10-2.2. Charge Development in the Presence of Specifically Adsorbed Ions.- 10-2. Surface Charge Characteristics of Highly Weathered Soils Rich in Oxides.- Literature Cited.- 11. Occurrence and Formation of Iron Oxides in Various Pedoenvironments.- 11-1. Introduction.- 11-1.1. Role of Iron(III) Oxides in Pedogenesis.- 11-1.2. Basic Reactions.- 11-1.3. Ways to Study the Relationship Between Iron(III) Oxides and Pedoenvironments.- 11-2. Pedoenvironments and Iron(III) Oxide Minerals.- 11-2.1. The Goethite-Hematite Pair.- Soil Temperature and Soil Water Activity.- Organic Matter.- Soil Acidity.- Aluminum.- Mechanism of Hematite and Goethite Formation from Ferrihydrite.- Conclusions.- 11-2.2. Lepidocrocite.- Occurrence in Various Soils.- The Lepidocrocite-Goethite Pair.- Conclusions.- 11-2.3. Ferrihydrite.- General Remarks.- Formation in Various Pedoenvironments.- Conclusions.- 11-2.4. Maghemite and Magnetite.- Maghemite.- Magnetite.- 11-3. Pedoenvironments and Aluminum Substitutions.- 11-3.1. General Remarks.- 11-3.2. Goethite.- 11-3.3. Hematite and Other Iron(III) Oxides 301.- 11-4. Conclusions and Future Work.- Literature Cited.- 12. Properties and Behavior of Iron Oxides as Determined by Mossbauer Spectroscopy.- 12-1. Principles of Mossbauer Spectroscopy.- 12-1.1 Introduction.- 12-1.2. Hyperfine Interactions.- 12-2. Effects of Magnetic Properties on Mossbauer Spectroscopy.- 12-2.1. The Neel Temperature and the Magnetic Hyperfine Field.- 12-2.2. The Quadrupole Interaction in Magnetically Ordered Materials.- 12-2.3. Nonideal Behavior: Superparamagnetic Relaxation and Related Phenomena.- 12-3. Variatons of the Magnetic Hyperfine Field in Crystalline Iron Oxides.- 12-3.1. Influence of A1 Substitution.- 12-3.2. Influence of Crystallinity.- 12-4. Magnetic Hyperfine Field Distributions.- 12-5. Selected Mineral Examples.- 12-5.1. Hematite.- Room-Temperature Spectra.- Low-Temperature Spectra.- 12-5.2. Goethite.- Room-Temperature Mossbauer Spectra.- Low-Temperature Spectra.- 12-5.3. Ferrihydrite.- Room-Temperature Mossbauer Spectra.- Low-Temperature Spectra.- 12-5.4. Magnetite and Maghemite.- 12-5.5. Transient Phases: The Green Rusts.- Acknowledgements.- Literature Cited.- 13. Iron Compounds as Indicators of Pedogenic Processes: Examples from the Southern Hemisphere.- 13-1. Introduction.- 13-2. Ferruginous Pedogenic Materials.- 13-2.1. Overall Occurrences: Some General Considerations.- Climatic Considerations.- Paleographic Considerations.- 13-2.2. Localized Occurrences: Some Specific Considerations.- Red and Yellow Ferruginous Soils With Varying Base Status.- Black Cracking Clays.- Ferruginous Duricrusts.- 13.3. Iron Compounds.- 13-3.1. Magnetic Iron Oxides.- Primary and Secondary Magnetic Iron Oxides.- Authigenic Magnetic Iron Oxides.- 13-3.2. Goethite.- 13-3.3. Hematite.- 13-3.4. Lepidocrocite.- 13-3.5. Ferrihydrite and Feroxyhite.- 13-3.6. Secondary Layer-Silicate Iron.- 13-3.7. Organically Complexed Iron.- 13-3.8. Other Iron Minerals.- 13-4. Pedogenic Linkages between the Ferruginous Pedogenic Materials and Iron Compounds.- 13-4.1. Continental Scale: Age, Parent Materials, and Climate.- Magnetic Fe-Oxides.- Ferrihydrite in Cryumbrepts (Afro-Alpine Soils) and Vertisols.- Goethite and Hematite in Oxisols, Ultisols, and Aridisols.- Al-Substituted Goethites and Hematites in Ferricretes and Red-Brown Hardpans.- Goethite-Hematite Ratio: Distribution of Red and Yellow Soils.- Al-Substituted Goethites and Hematites: An Indicator of Contemporary and Fossil Soil Formation.- Lepidocrocites: An Indicator of Certain Reductomorphic Pedogenic Environments in Humid Temperate Climates.- 13-4.2. Local Landscape Scale.- Effects of Altitude and Aspect on Goethite and Hematite Formation.- Effects of Slope and Hydrology on Goethite and Hematite Formation and Transformation.- Effects of Altitude, Aspect, Slope, and Hydrology on Maghemite Formation and Transformation.- Effects of Topography and Hydrology on the Forma tion and Transformation of Iron-Rich Smectites.- 13-4.3. Profile Scale.- Formation and Transformation of Goethite and Hematite at the Profile Scale.- Formation and Transformation of Magnetic Fe Oxides at the Profile Scale.- Formation and Transformation of Lepidocrocite at the Profile Scale.- 13-4.4. Micro-Pedological Scale.- Mottles and Ferricrete Fragments: Soil Matrix Comparisons.- Ferruginous Bauxite Nodules: Soil Matrix Comparisons.- Pipestems: Soil Matrix Comparisons.- Magnetic and Non-Magnetic Glaebules: Soil Matrix Comparisons.- influence of Heat From Forest Fires.- Placic Horizons: Soil Matrix Comparisons.- 13-5. Summary and Conclusions.- Acknowledgements.- Literature Cited.- 14. Magnetic Properties of Iron in Soil Iron Oxides and Clay Minerals.- 14-1. Introduction.- 14-2. Paramagnetism.- 14-2.1. Susceptibility and Magnetization of Iron(III).- 14-2.2. Susceptibility and Magnetization of Iron(II).- 14-3. Collective Magnetic Order.- 14-3.1. Ferromagnetic Interactions.- 14-3.2. Antiferromagnetic Interactions.- Antiferromagnetism.- Ferrimagnetism.- Speromagnetism.- 14-3.3. Ferromagnetic and Antiferromagnetic Interactions.- 14-3.4. Anisotropic and Antisymmetric Exchange.- 14-3.5. Chemical Disorder.- 14-3.6. Domain Effects.- 14-3.7. Fine Particle Effects.- Surface Spin Structures and Moments of Fine Particles.- Superparamagnetism.- 14-4. Experimental Techniques.- 14-4.1. Susceptibility.- 14-4.2. Magnetization.- 14-4.3. Natural Remanence.- 14-4.4. Hyper fine Interactions.- 14-4.5. Magnetic Structures.- 14-5. Iron Oxides.- 14-5.1. Hematite.- 14-5.2. Ilmenite.- 14-5.3. Magnetite.- 14-5.4. Maghemite.- Titanomaghemites.- Magnetic Soils.- 14-5.5. Goethite.- 14-5.6. Other Crystalline Ferric Hydroxides.- 14-5.7. Disordered and Amorphous Ferric Hydroxides.- 14-5.8. Other Minerals.- 14-6. Clay Minerals.- 14-6.1. Triocta’nedrai Iron(II) Minerals.- Mössbauer Spectra.- Magnetic Properties.- Neutron Diffraction.- Computer Experiments.- 14-6.2. Trioctahedral Iron(IIl) Minerals.- 14-6.3. Dioctahedral Minerals.- 14- 6.4. Summary.- Acknowledgements.- Appendix: Quantitites and Units.- Literature Cited.- 15. Structural Iron in Kaolinites and in Associated Ancillary Minerals.- 15-1. Introduction.- 15-2. Terminology and Crystal Structure.- 15-3. Deposits.- 15-4. General Properties.- 15-4.1. Shape and Size.- 15-4.2. Rheological Properties.- 15-5. Analysis and Mineralogy.- 15-5.1. Elemental Analysis.- 15-5.2. Mineralogical Analysis.- 15-5.3. Illustrative Analyses.- 15-5.4. Iron in the Kaolinite Structure.- 15-5.5. Iron Oxides and Oxyhydroxides.- 15-5.6. Iron in the Ancillary Minerals.- 15-5.7. Titanoferrous Impurities.- 15-6. Optical Properties.- 15-6.1. Introduction to Absorption and Scattering.- 15-6.2. Kubelka-Munk Equations.- 15-6.3. Significance of k and s.- 15-6.4. Measurement of k ands.- 15-6.5. Measurement of Reflectance and Brightness.- 15-6.6. Brightness Values.- 15-6.7. Experimental Values of k and s.- 15-6.8. The Scattering Coefficient 495 15-6.9. The Absorption Coefficient.- 15-6.10. Interpretation of Light Absorption.- 15-7. Ceramics.- 15-8. Commercial Production of Kaolin.- 15-8.1. Reactions with Sodium Dithionite.- 15-8.2. Magnetic Separation.- Principles.- Commercial Applications.- Research Applications.- 15- 8.3. Micromineral Separation.- Froth Flotation.- Selective Flocculation.- Selective Coagulation.- Acknowledgements.- Literature Cited.- 16. Role of Iron in Mica Weathering.- 16-1. Introduction.- 16-2. Status of Iron in Micas.- 16-2.1. Occurrence.- 16-2.2. Location.- 16-2.3. Determination.- 16-2.4. Variability.- 16-3. Naturally Weathered Micas.- 16-3.1. Theoretical Considerations.- 16-3.2. Changes Observed.- 16-4. Mica Dissolution.- 16-4.1. Principles.- 16-4.2. K Release.- 16-4.3. Hydrolysis and Precipitation.- 16-4.4. Complexation.- 16-4.5. General Aspects.- 16-5. Chemically Induced Redox Changes.- 16-5.1. Laboratory Conditions for Oxidation.- 16-5.2. Relevance of Mica Expansion.- 16-5.3. Br 2- and H2 O2 -Treated Mica.- 16-5.4. Structural Fe Reduction.- 16-6. Mica Alterations by Wet Redox Treatmemts.- 16-6.1. Visible Changes.- 16-6.2. Interlayer K.- 16-6.3. Chemical Composition.- 16-6.4. Structural Properties.- 16-7. Thermally Altered Micas.- 16-7.1. General Approach 59716-7.2. Macro Flakes.- 16-7.3. Structural Fe.- 16-7.4. Inter layer K.- Acknowledgements.- Literature Cited.- 17. Structural Iron in Smectites.- 17-1. Introduction.- 17-2. Composition and Origin of Iron-Bearing Smectites.- 17-2.1. Classification.- 17-2.2. Natural and Synthetic Formation.- 17-2.3. Site Occupancy of Iron.- 17-3. Methods of Characterization.- 17-3.1. Infrared Spectroscopy.- 17-3.2. Mossbauer Spectroscopy and Other Nuclear Techniques.- 17-3.3. UV-Visible Spectroscopy.- 17-4. Effects of Structural Iron on Smectite Properties.- 17-4.1. Surface Area.- 17-4.2. Layer Charge and Cation Exchange Capacity.- 17-4.3. Swelling in Water.- 17-4.4. Color.- 17-4.5. Crystallographic b-Dimension.- 17-4.6. Chemical Stability.- 17-5. Redox Processes and Mechanisms.- 17-5.1. Oxidation of Iron(II) Smectites.- 17-5.2. Reduction of Iron(III) Smectites.- Literature Cited.- 18. The Characterization of Iron Complexes with Soil Organic Matter.- 18-1. Introduction.- 18-2. The Bonding of Iron to Humic Substances.- 18-3. Bonding of Iron to Organic Matter in Soils.- Literature Cited.- 19. Chemistry of Iron in Calcareous Systems.- 19-1. Introduction.- 19-2. Iron Oxides in Calcareous Soils.- 19-3. Equilibrium Relations of CaC03.- 19-4. Equilibrium Relations of Iron in Calcareous Systems.- 19-5. Synthetic Systems for Studying the Reactions of Aqueous Iron with CaCO3.- 19-6. Reactions of Iron with CaC03.- 19-7. Iron Oxides Formed During the Reactions of Iron with CaC03.- 19-8. Iron Oxides and the Availability of Iron to Plants in Calcareous Systems.- 19-9. Influence of Soil Components on the Reactions of Iron in Calcareous Systems.- 19-10. Implications of Synthetic Studies to the Management of Iron in Calcareous Soils.- 19-11. Conclusions.- Acknowledgements.- Literature Cited.- 20. Microbiological Reactions of Iron in Soils.- 20-1. Introduction.- 20-2. Preliminary Note on the Iron(II)/Iron(III) Redox System.- 20-3. Oxidation of Iron(II).- 20-3.1. Thiobacillus Ferrooxidans.- 20-3.2. Mechanism of Oxidation.- 20-3.3. Biomass Yield of the Reaction.- 20-3.4. Other Acidophilic Fe Organisms.- 20-4. Neutral pH Iron Oxidizing Bacteria….- 20-5. Decomposition of Organic Iron(II) Complexes.- 20-6. Types of Iron(III) Oxides Formed by Bacteria.- 20-7. Reduction of Iron(III).- 20-7.1. Source of Electrons for Iron(III) Reduction.- 20-7.2. Mechanism of Iron(III) Reduction.- 20-8. Rate of Reduction.- 20-8.1. Methods for Determination of Reduction Rates.- 20-9. Factors Influencing the Rate of Reduction.- 20-9.1. Types of Microorganisms.- 20-9.2. Bacterial Activity.- 20-9.3. Types and Concentration of Iron(III) Oxides.- 20-9.4. Sinks for Iron(II).- 20-10. Alteration of Other Iron Minerals.- Literature Cited.- 21. The Fate of Iron During Soil Formation in Humid-Temperate Environments.- 21-1. Introduction.- 21-2. Weathering and Braunification.- 21-3. Lessivage.- 21-4. Podzolization.- 21-5. Processes of Reductomorphism.- 21-5.1. Surfacewater Soils.- 21-5.2. Groundwater Soils.- 21-5.3. Dry Reductomorphism.- 21-6. Lateral Translocation of Iron in Landscapes.- Acknowledgements.- Literature Cited.- 22. Laterites and Laterization Processes.- 22-1. Definition and Concepts.- 22-1.1. Laterites.- 22-1.2. Relative and Absolute Accumulation of Sesquioxides.- 22-2. A Sketch of a “Typical” Laterite Profile.- 22-3. Isovolumetric Chemical Balances.- 22-3.1. General Comments.- 22-3.2. Isovolumetric Chemical Balances in the Diouga Laterite.- 22-4. Absolute Accumulation of Iron — The Epi

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