Origin and Mineralogy of Clays

Springer-Verlag Berlin Heidelberg GmbH

B. Velde (Ed.)

Origin and Mineralogy of Clays Clays and the Environment

With 182 Figures and 7 Tables

, Springer

Dr. BRUCE VELDE

Laboratoire de Geologie Ecole Normale Superieure UA 1316 CNRS 24 rue Lhomond 75231 Paris France

ISBN 978-3-642·08195-8

Library of Congress Cataloging·in-Publication Data. Origin and mineralogy of cJays. p. cm. IncJudes bibliographical references and indexes. Contents: v. 1. Clay and the environmentl Bruce Velde [editor] ISBN 978-3-642-08195-8 ISBN 978-3-662-12648-6 (eBook) DOI 10.1007/978-3-662-12648-6 1. Clay minerals. 2. Clay. 3. Clay minerals-Environmental aspects. 4. Clay-Environmental aspects. 1. Velde, B. QE389.625.0n 1995 552'.5-dc20 95-24195

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Preface

The need for a solid understanding of the chemistry and physical processes of the solid, silicate-dominated surface environment is at present great and growing. Clay minerals, the most abundant and chemically active parts of the surface mineral world, are the key to understanding the links between nature (life), its substrate (sili­cates), and a mastery of the total eco-system by man, but unfortu­nately, the traditions of the study of clays have not always reached in this direction. Past professional interest has most often been bogged down in problems of taxonomy (mineral names), the study of physical and chemical properties without their natural context, and a general imprecision in the definition of interactions that are potentially useful to industrial processes. The growing needs of an industralized world were not considered. Clay mineralogists took their materials into the laboratory to better study them; agrono­mists simplified and then basically abandoned the identification of clays and their role in plant growth; and soil engineers abstracted the reality of the chemistry of clays to a neutral, physical use. The different fields of research dealing with the silicate surface environ­ment began to ignore each other.

Today there is an increased awareness that the surface envi­ronment is the key to the future of industrial survival, both city and rural. The lessons of the Eastern bloc nations cannot be ignored, nor can we continue to ignore the consequences of human activity on the biosphere; we are part of it, after all. In order to begin to understand the interdependence of the mineral world and the bio­sphere, it is necessary to understand clay minerals, an agent of exchange in the chemistry of life.

This book, then, attempts to lay the basis of understanding - it is hoped in an understandable way-the why and what of clay minerals. The origins of clays are described in their chemical and geographic context, while the cycle of geological dispersion and concentration is discussed with regard to the type of clays that can be formed and where they can be found. The change and eventual destruction of clay minerals in the cycle of sedimentation, burial, and rock-forming is described, and finally, an explanation is given

VI Preface

of the origin of clays which are useful to manufacturing (hydrothermal alteration). In this text, we hope to facilitate the discovery of the origin of clay minerals and their abundance in their various geological habitats. Of course, a brief explanation of the nomenclature and chemical differences between clays is given to start the beginner on his way.

With its five contributors, this book is obviously a group effort. These five people are friends as well as colleagues, and our com­mon interest in writing these chapters was to be as pertinent to present day needs as possible. Hence we have attempted to give readers a sort of introduction for environmentalists to the some­what confusing world of clay minerals and clay mineralogy. This, the first volume in the series, lays the foundations for a fuller understanding of the real problems of clays in the environment. The second volume then goes on to demonstrate the importance of clays in their different environments as they affect specific prob­lems of interaction between the inanimate and living world.

The volume editor would like to thank his friends and highly competent fellow clay mineralogists for contributing to the endeavor: the organization and conception of the different chap­ters and the assemblage benefited greatly from their patience and good will. Our publishing editor must also be thanked for his patience. Most of all, our gratitude is due to the home computer.

We hope that the volume will lead young scientists to under­stand and use this knowledge and to develop a better understand­ing of clay problems, the use of clays, and the potential they have in limiting the nefarious effects of other actors in the industrial or agricultural cycle. Knowledge is power, and a little prevention based upon some knowledge will certainly go a long way in avoid­ing much regret in the future.

Paris, July 1995 B. VELDE

Contents

1 Geology of Clays B. VELDE •••••.•••••••••••••••••••••••.•••.•. 1

1.1 Why Clays Form .............................. 1 1.2 Where Clays Form ............................ 3 1.3 Clay Formation: The Chemical Necessity ........ 5

2 Composition and Mineralogy of Clay Minerals B. VELDE ••••••.••••••..•••••••...•••••••.••• 8

2.1 Introduction ................................. 8 2.2 Physical Properties of Clays .................... 9 2.2.1 Particles and Shapes ........................... 9 2.2.1.1 Something About Clay Particles ................ 9 2.2.2 Clays and Water .............................. 11 2.2.3 Clays in Water ............................... 13 2.2.3.1 Mixtures of Water and Clays ................... 13 2.2.3.2 Clays in Water and Transport .................. 14 2.2.3.3 Exchange of Ionic Species (CEC) ............... 15 2.2.4 Summary .................................... 17 2.3 Crystallographic Structure of Clay Minerals ...... 17 2.3.1 Tetrahedra ................................... 18 2.3.2 Octahedra ................................... 19 2.3.3 Layer Structures Through Linkage .............. 19 2.3.3.1 Repeat Distances ............................. 20 2.3.4 Crystalline Water ............................. 22 2.3.5 Chemical Substitutions in the Structures ......... 23 2.3.5.1 Charge on the Unit Cell

for Different Layer Types ..................... 23 2.3.5.2 Charge on Ions in a Given Coordination Site ..... 23 2.3.5.3 Substitutional Types .......................... 24 2.3.6 Substitutions and Mineral Species ............... 27 2.4 Mineral Families ............................. 28 2.4.1 7 A Minerals

(One Octahedral + One Tetrahedral Sheet) ...... 29

VIII Contents

2.4.2

2.4.2.1 2.4.2.2

2.4.3 2.4.3.1 2.4.3.2 2.4.4

2.4.4.1 2.4.4.2 2.4.5 2.4.5.1 2.4.6 2.4.7 2.4.8 2.4.9

10 A Minerals (Two Tetrahedral and One Octahedral Layer) .. . Neutral Layer (Charge Almost Zero) .......... . High Charge Minerals: Mica-Like (Charge near 1, all Dioctahedral) .............. . Low Charge (Expanding) Minerals: Smectites ... . Dioctahedral Expanding Minerals ............. . Trioctahedral Expanding Minerals ............. . 14 A Chlorites (Two Octahedral + Two Tetrahedral Unit Layers, 2:1 + 1) ......... . Trioctahedral Chlorite Minerals ............... . Composition and Substitutions ................ . Mixed Layered Minerals ..................... . Mixed Layering Mineral Types ................ . Sepiolite-Palygorskite ....................... . Iron Oxides ................................. . Zeolites .................................... . Summary ................................... . Suggested Reading .......................... .

3 Origin of Clays by Rock Weathering and Soil Formation

29 30

30 31 31 32

33 33 34 35 36 37 38 39 41 41

D. RIGHI and A. MEUNIER. . . . . . . . . . . . . . . . . . . . . 43

3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.2 Weathered Rocks and Soils: The Major Factors

in Their Development. . . . . . . . . . . . . . . . . . . . . . . . . 44 3.2.1 General Organization:

Soil and Weathered Rock Domains............ 44 3.2.2 Basic Factors in Weathering

and Soil Formation .......................... 46 3.2.2.1 Climate and Water Regime

Within the Soil Mantle ....................... 47 3.2.2.2 Rock Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 3.2.2.3 Biological Factor:

Vegetation and Soil Organic Matter . . . . . . . . . . . . 52 3.2.2.4 Age and Soil History . . . . . . . . . . . . . . . . . . . . . . . . . 55 3.2.2.5 Topographic Effects: Translocations

and Accumulations .......................... 57 3.2.3 Distribution of Major Soil Types at the Surface

of the World ................................ 60 3.2.4 Structure of Weathered Rocks and Soils. . . . . . . . 62 3.2.4.1 Weathered Rocks:

Inheritance of the Rock Structure ............. 62

Contents IX

3.2.4.2 3.2.5 3.2.6

3.2.7

3.2.7.1 3.2.7.2 3.2.8 3.2.8.1 3.2.8.2 3.2.9

3.2.9.1 3.2.9.2 3.2.10 3.3 3.3.1

Soil Structures: Importance of Aggregation .... . Soil Structure-Porosity Relationship ........... . Changes in Rock Density and Mechanical Properties ................... . Water in Soils: Content and Chemical Potential .............. . Soil-Moisture Retention Curve ............... . Flow of Water in Soils and Weathered Rocks .. . Dissolution and Recrystallization Processes .... . General Statements ......................... . The Proton-Cation Exchange ................ . Basic Factors for Phase Relation Analysis in Rock Weathering ........................ . From Microsites to Microsystems ............. . Construction of Phase Diagrams .............. . Summary and Conclusions ................... . From Rock to Soil: The Granite Example ...... . Clay Formation in Weathered Granite Under Atlantic Climatic Conditions ........... .

3.3.1.1 Weathered Profiles on Granitic Rocks:

3.3.1.2 3.3.1.3 3.3.2

3.3.2.1 3.3.2.2 3.3.2.3 3.3.2.4

3.3.2.5 3.3.3 3.4 3.4.1 3.4.1.1 3.4.1.2 3.4.1.3 3.4.1.4 3.4.1.5 3.4.2 3.4.3 3.4.3.1 3.4.3.2 3.4.4 3.5

The First Stages of Weathering ............... . Construction of Phase Diagrams .............. . Summary .................................. . Soil Clays Developed on Granite Saprolite in the Temperate Zone ...................... . Methodology ............................... . Observations ............................... . Clay Genesis in Temperate Acid Soils ......... . Composition and Properties of the Subfractions .......................... . Conclusion ................................ . Summary of Weathering Effects .............. . Clays Formed During Rock Weathering ....... . Weathering of Basic and Ultrabasic Rocks ..... . Weathering Profiles ......................... . Weathered Macrocrystalline Basic Rocks ...... . Weathered Macrocrystalline Ultrabasic Rocks .. . Phase Diagrams ............................ . Weathered Serpentinite ..................... . Weathering of Basaltic Rocks ................ . Weathering of Clay-Bearing Rocks ........... . Weathering of Glauconitic Sandstones ......... . Weathering of Marls ........................ . Summary and Conclusions ................... . Clays Found in Soil Environments ............ .

62 66

67

69 70 70 73 73 76

78 78 81 84 87

88

88 93

101

102 102 104 107

107 114 114 115 115 115 116 117 119 124 126 129 129 131 133 134

X Contents

3.5.1

3.5.1.1 3.5.1.2

3.5.1.3

3.5.1.4

3.5.1.5 3.5.2

3.5.3

3.5.3.1

3.5.3.2 3.5.4

3.6

4

4.1 4.2

4.2.1 4.2.2 4.2.3 4.3

4.3.1 4.3.2 4.3.3 4.3.3.1 4.3.3.2 4.3.3.3 4.3.3.4 4.3.4 4.3.5

Clays in Soils from Cold and Temperate Climates ................................... . Nature and Rate of Clay Mineral Formation ... . Podzolization and Clay Mineral Evolution in the Temperate Zone: Influence of Organic Matter ... Clay Illuviation in Soils Developed from Glacial Loess Deposits: Movement by Transport of Solids ..................................... . Clays in Soils from Heavy Clay Rocks: Selective Transport of Clays ......................... . Summary ................................. . Clays in soils on Volcanic Rocks: The Short-Range-Ordered Minerals, Allophane and Imogolite .................... . Clays in Soils Formed Under Tropical Climate Conditions ................................. . Equatorial Wet Zone: Kaolinite and AI, Fe-Oxyhydroxides in Ferralsols ............... . Tropical Dry Zone: Smectites in Vertisols ..... . Arid and Semi-arid Zones: Palygorskite in Saline Soils and Calcareous Crust .......... . General Conclusions ........................ . References ................................ .

Erosion, Sedimentation and Sedimentary Origin of Clays S. HILLIER ................................. .

Introduction ............................... . Origins, Sources and Yields, and Global Fluxes of Clay Minerals ............................ . Origins of Clay Minerals in Sediments ......... . Sources and Yields ......................... . Global Fluxes .............................. . Erosion, Transport and Deposition of Clay Minerals ............................ . Transport by Rivers ......................... . Transport in the Sea and Ocean .............. . Deposition of Clay Minerals by Settling ....... . Salt Flocculation ........................... . Differential Flocculation and Settling .......... . Bio- and Organic Flocculation ................ . Properties of Aggregates and Flocs ........... . Erosion, Transport and Deposition by Wind ... . Erosion, Transport and Deposition by Ice ..... .

134 135

138

140

144 144

145

147

148 152

154 155 157

162

162

163 163 165 168

169 169 171 177 178 180 180 181 182 185

Contents XI

4.3.6 Modifications and Transformations

4.3.6.1 4.3.6.2 4.4

4.4.1 4.4.2 4.4.3 4.4.4 4.4.5 4.4.6

4.4.7 4.5 4.6 4.6.1 4.6.2

5

5.1 5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.5.1 5.1.5.2 5.2

5.2.1 5.2.2 5.2.3 5.2.4 5.3

5.3.1 5.3.2 5.3.3

5.3.4 5.4

During Transport and Deposition ............. . Ion Exchange and Fixation .................. . Pollutant Transport and Regulation ........... . Authigenic (in situ) Formation of Clay Minerals in Sediments ............................... . Continental Authigenic Smectite ............. . Marine Authigenic Smectites ................. . Marine Glauconite and Glauconite/Smectite ... . Celadonite and Celadonite/Smectite ........... . Non-Marine Glauconite and Ferric Illite ....... . Minerals Related to Chlorites and the Verdine Facies ...................... . Sepiolite and Palygorskite ................... . Mineralogical Patterns in the World Ocean .... . Environmental Interpretation of Clay Minerals .. Sedimentary Environments and Provenance ..... Palaeoclimatic Interpretation of Clay Minerals .. References ................................ .

Compaction and Diagenesis B. VELDE •••••••••.•••••••••.••••••••••••••.

The Geologic Structure of Diagenesis ......... . Compaction and Porosity .................... . Temperature ............................... . Sedimentation Rate ......................... . The Kinetics of Clay Transformations ......... . Chemically Driven Reaction in Clays .......... . Solution Transport .......................... . Chemical Equilibrium Among Clay Particle .... . Major Progressive Clay Mineral Reactions During Burial Diagenesis .................... . Mixed Layer Mineral Series .................. . Silica Polymorph Change During Diagenesis ... . Zeolite Mineralogy During Diagenesis ........ . Changes in Organic Matte ................... . Sequential Mineralogical Changes During Burial Diagenesis .................... . The First Kilometer ......................... . The Stability of Detrital Minerals ............. . Clay Mineral Assemblages in the Second Kilometer of Burial ............ . The Last Kilometers ........................ . Conclusions ................................ . Suggested Reading ......................... .

187 187 189

190 191 193 195 198 198

199 201 203 207 207 210 214

220

221 222 226 226 226 231 231 232

234 234 235 236 237

239 239 240

241 242 244 245

XII Contents

6 Hydrothermal Alteration by Veins A. MEUNIER.......... . . . . .......... . . . . . .... 247

6.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247 6.2 Structure of the Hydrothermal-Wall Rock

System..................................... 248 6.2.1 Central Deposit and Altered Wall Rocks ....... 248 6.2.2 Fluid Injection Vein Type .................... 249 6.2.3 Fluid Infiltration Vein Type .. . . . . . . . . . . . . . . . . . 251 6.2.4 Fluid Drainage Vein Type .................... 251 6.3 Alteration Mechanisms . . . . . . . . . . . . . . . . . . . . . . . 253 6.3.1 Zone Formation . . . . .. . . . . . . . . . . . . . . . . . . . . . . . 253 6.3.2 Zone Development .......................... 255 6.3.3 Kinetics of Zonation ......................... 256 6.3.4 Quantities of Fluids and Flow Regime

in Fractures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260 6.3.5 Successive Fluid Circulation . . . . . . . . . . . . . . . . . . . 262 6.4 Alteration of Pre-existing Clay Minerals ........ 263 6.4.1 Layer-Charge Control of Clay Hydrothermal

Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263 6.4.2 Polyphase Clay Mineral Assemblages .......... 265 6.5 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265

References ................................. 266

7 Formation of Clay Minerals in Hydrothermal Environments A. INOUE ................................... 268

7.1 Initial Statement ............................ 268 7.2 Definition of Hydrothermal Alteration ......... 269 7.3 Geologic Settings of Hydrothermal Systems. . . . . 270 7.4 Physico-chemical Nature

of Hydrothermal Systems ..................... 271 7.4.1 Temperature and Pressure. . . . . . . . . . . . . . . . . . . . 271 7.4.2 Fluid Compositions .......................... 273 7.5 Formation of Alteration Minerals

and Their Zoning . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277 7.6 Classification of Hydrothermal Alteration. . . . . . . 284 7.7 Distribution and Morphology

of Alteration Zones . . . . . . . . . . . . . . . . . . . . . . . . . . 288 7.8 Case Studies of Hydrothermal Alteration ....... 291 7.8.1 Acid-Type Alteration ........................ 291 7.8.2 Intermediate to Alkaline Types of Alteration ... 294 7.8.3 Deep Sea Hydrothermal Alteration. . . . . . . . . . . . 299 7.9 A Brief Summary on the Effect of Rock Type.. . 303

Contents XIII

7.10 Detailed Mineralogy of Selected Clay Mineral Types . . . . . . . . . . . . . . . . 304

7.10.1 Interstratified Illite/Smectite .................. 304 7.10.1.1 Structural Variation. . . . . . . . . . . . . . . . . . . . . . . . . . 305 7.10.1.2 Chemical Variation .......................... 307 7.10.1.3 Morphology Variation ....................... 309 7.10.1.4 Stability .................................... 311 7.10.2 Rectorite.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313 7.10.3 Dioctahedral Smectite ....................... 313 7.10.4 Sericite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314 7.10.5 Interstratified Trioctahedral

Chlorite/Smectite (C/S) . . . . . . . . . . . . . . . . . . . . . . . 315 7.10.5.1 Structural Variation. . . . . . . . . . . . . . . . . . . . . . . . . . 315 7.10.5.2 Chemical Variation317 7.10.5.3 Stability .................................... 318 7.10.6 Trioctahedral Chlorite

7.10.7 7.11

in Hydrothermal Deposits ................... . Aluminous Chlorite and Chlorite/Smectite ..... . Concluding Remarks ........................ . References ................................ .

318 320 320 321

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

List of Contributors

S. HILLIER

Macaulay Land Use Research Institute, Craigiebuckler, AB92QJ Aberdeen, Scotland

A. INOUE

Department of Earth Sciences, Faculty of Science, Chiba University, Chiba 263, Japan

A. MEUNIER

Laboratoire Argiles, Sols et Alterations UA 721 CNRS, Universite de Poitiers, 40 Ave Recteur Pineau, 86022 Poitiers, France

D. RIGHI

Laboratoire Argiles, Sols et Alterations UA721 CNRS, 40 Ave Recteur Pineau, 86022 Poitiers, France

B. VELDE

Laboratoire de Geologie UA 1316 CNRS, Ec10e Normale Superieure, 24 rue Lhomond, 75231 Paris, France