Bücher
Service
This book aims to help improve predictions of important properties of soils through a modern understanding of their highly reactive clay minerals as they are formed and occur in soils worldwide. It examines how clays occur in soils and the role of soil clays in disparate applications.
G. Jock Churchman is adjunct senior lecturer at the University of Adelaide (Australia) and adjunct
associate professor at the University of South Australia. Jock Churchman's clay interests began with
a PhD in chemistry on halloysite at the University of Otago in his native New Zealand, followed
by industrial ceramic research (1970-1971). He held a postdoctoral fellowship in soil science at the
University of Wisconsin-Madison (1971-1973) and was employed at the New Zealand Soil Bureau
(1973-89), then at CSIRO (1989-2003), the University of Adelaide (2003-2012) and the University
of South Australia (2013-2014). He has also held visiting fellowships in soil science for one year at
Reading University (UK) and for six months at the University of Western Australia. His research
has encompassed halloysite; acid dissolution of montmorillonite; dust transport; clay mineral genesis;
clay-organic complexes; the influence of clay mineralogy on soil physical properties; clays in
sodic soils; the characteriation of bentonites and their industrial and environmental applications;
and the philosophy of soil science.
He has published nearly 150 refereed papers and coedited four books, most recently The Soil
Underfoot: Infinite Possibilities for a Finite Resource (CRC Press, 2014) and Natural Mineral
Nanotubes (CRC Press, 2015). He is a former editor (now emeritus) of Applied Clay Science. He
has received awards from the New Zealand Society of Soil Science, Soil Science Australia, the
Association Internationale pour l'Étude des Argiles (AIPEA) and the Clay Minerals Society.
Bruce Velde is an emeritus researcher for the Centre Nationale de Recherche Scientifique at the
Ecole Normale Supérieure in Paris. He did his PhD at Montana State University (1962) under the
direction of John Hower, then he did a postdoctoral study at the Carnegie Geophysical Laboratory
in Washington DC (1962-1965) after which he joined the CNRS in Paris.
The initial research subjects treated were the evolution of clay minerals in sediments and sedimentary
rocks, and their stability under different laboratory conditions of pressure and temperature.
During the latter period, he published 237 refereed papers, authored and coauthored 8 books on
clays and their chemical relations in natural situations and advised 22 PhD theses on these subjects.
His books are Clays and Clay Minerals in Natural and Synthetic Systems (Springer, 1977);
Introduction to Clay Minerals: Chemistry, Uses and Environmental Significance (Chapman & Hall,
1992); Archaeological Ceramic Materials: Origin and Utilization (Springer, 1999); Clay Minerals:
A Physico-Chemical Explanation of Their Occurrence (Elsevier, 2000); Illite: Origins, Evolution
and Metamorphism (Springer, 2004); The Origin of Clay Minerals in Soils and Weathered Rocks
(Springer, 2008); Soils, Plants and Clay Minerals: Mineral and Biologic Interactions (Springer,
2009); Origin and Mineralogy of Clays: Clays and the Environment (edited) (Springer, 2013); and
Geochemistry at the Earth's Surface (2016).
The evolution of his work was to understand the chemical and physical reasons for the variety
and stability of clay mineral associations from depth towards the surface of the Earth. He also did
work on the formation of clay-associated structures (aggregates) and surface cracking using image
analysis.
Contents
Preface............................................................................................................................................ xiii
Authors............................................................................................................................................xvii
Chapter 1 Introduction and Definitions.........................................................................................1
1.1 Soil......................................................................................................................1
1.2 The Origin of Soils and Clays in Geological Time............................................2
1.3 Weathering as the Origin of (Most) Soils...........................................................3
1.4 From Rock to Soil: The Biological Factor in the Initial Stages of Rock
Alteration and Soil Formation............................................................................4
1.5 Soil Science........................................................................................................7
1.6 Clays...................................................................................................................8
1.7 Clay Mineral Formation.....................................................................................9
1.8 Soil Clay Mineralogy....................................................................................... 12
1.9 A New Approach to the Study of Soil Clays.................................................... 13
1.10 Soil Classification............................................................................................. 14
References................................................................................................................... 14
Chapter 2 Soil Clays: Mineralogy................................................................................................ 17
2.1 Basic Structures of Phyllosilicates................................................................... 17
2.2 Lattice Substitutions......................................................................................... 19
2.3 Oxidation-Reduction Effects............................................................................ 21
2.4 Residual Charge on 2:1 Structure Due to Ionic Substitutions and Site
Occupation ....................................................................................................... 21
2.4.1 Names for 2:1 Structure Minerals in Soils..........................................22
2.5 Charge Intensity and Interlayer Cation Complex Types...................................24
2.6 Cation Exchange in Interlayer Sites..................................................................24
2.7 Cation Exchange Sites on Clay Edges .............................................................26
2.8 Pertinent Principles of Cation Exchange..........................................................28
2.8.1 Cation-Water Interaction....................................................................28
2.8.1.1 Cation-Water Interaction: Summary...................................29
2.8.1.2 Selectivity among Ions in Solution: Summary....................30
2.8.1.3 Relations of Preference for Cations or Hydrogen Ions
(Cations): Summary.............................................................30
2.8.1.4 Types of Exchanged Cation in Layer Silicate
Interlayers: Summary..........................................................30
2.8.1.5 Cation Exchange on Edge Sites: Summary.........................30
2.8.2 Overall Effect of pH on Exchange (Capture or Loss) of Cations........ 31
2.9 Effect of Climate.............................................................................................. 32
2.10 Mixed-Layered Clays ...................................................................................... 32
2.11 Identification of Layer Silicate Clays (2:1 and 1:1 Structures) by X-Ray
Diffraction........................................................................................................ 33
2.12 Allophane and Imogolite..................................................................................34
2.13 Iron Oxides, Hydroxides and Oxyhydroxides.................................................. 35
2.13.1 Surface Reactions of Fe Oxides .........................................................36
2.14 Aluminium Oxides, Oxyhydroxides and Hydroxides......................................36
2.15 Manganese Oxides...........................................................................................36
2.16 Silicon Oxides.................................................................................................. 37
2.17 Titanium Oxides...............................................................................................37
2.18 Zirconium Minerals..........................................................................................37
References...................................................................................................................37
Chapter 3 Geology: Defining the Starting Point for Soil and Clay Formation............................ 41
3.1 The Geological Cycle....................................................................................... 41
3.2 Geology of the Continental Surfaces............................................................... 41
3.3 Primary Minerals in Rocks: Raw Material for Alteration............................... 42
3.3.1 Silicates............................................................................................... 42
3.3.2 Non-Silicates.......................................................................................44
3.3.3 The Initial Production of Clays in Weathering................................... 45
3.3.4 Geological Deposits, Rock Types and Clay Minerals......................... 47
3.3.4.1 Rocks................................................................................... 47
3.3.4.2 Sediments............................................................................ 47
3.3.4.3 Loess and Dust....................................................................48
References................................................................................................................... 51
Chapter 4 Primary Minerals and Their Alteration by Weathering.............................................. 53
4.1 Primary Minerals and Their Weathering Products ......................................... 53
4.1.1 Amphiboles, Pyroxenes and Olivines ................................................ 53
4.1.2 Serpentinites........................................................................................ 53
4.1.3 Volcanic Glass .................................................................................... 53
4.1.4 Feldspars .............................................................................................54
4.1.5 Micas ..................................................................................................54
4.1.6 Chlorites .............................................................................................54
4.1.7 Heterogeneity of Products................................................................... 55
4.2. Mechanisms of Alteration of Primary Minerals ............................................. 55
4.2.1 Oxidation............................................................................................. 55
4.2.2 Reaction Rates and Parameters Determining Alteration
as a Function of Time..........................................................................56
4.2.3 Effects of pH.......................................................................................56
References................................................................................................................... 57
Chapter 5 Driving Forces of Alteration....................................................................................... 59
5.1 Climate............................................................................................................. 59
5.2 Topography....................................................................................................... 59
5.2.1 Interaction at the Water-Rock Interface.............................................60
5.3 Geological Parameters......................................................................................63
5.3.1 Alteration Profile.................................................................................63
5.3.2 Rock Alteration by Pore Water............................................................64
5.3.3 Movement of Clays..............................................................................65
5.3.4 Geology and Alteration ......................................................................65
References...................................................................................................................68
Chapter 6 Chemistry of Alteration by Weathering......................................................................69
6.1 Alteration Context............................................................................................69
6.2 Chemical Forces...............................................................................................69
6.3 Chemistry of Elements and Mineral Stability.................................................. 70
6.4 Mechanisms of Alteration................................................................................ 71
6.4.1 Mineral Change: Loss of Mineralogical Identity ............................... 71
6.4.2 Dissolution........................................................................................... 72
6.4.3 Interaction by Diffusion and Ion Exchange........................................ 72
6.4.4 Oxidation............................................................................................. 74
6.5 Formation of New Clays................................................................................... 75
6.5.1 Crystal Growth.................................................................................... 75
6.5.2 Mineral Growth from Amorphous Materials..................................... 75
6.5.3 Mineral Transformation...................................................................... 76
References...................................................................................................................77
Chapter 7 Formation of Clays in the Soil Zone of Alteration...................................................... 79
7.1 Crystallisation from Incongruent Dissolution.................................................. 79
7.2 Crystal Growth from Elements in Solution......................................................80
7.2.1 Neogenesis...........................................................................................80
7.2.1.1 Thermodynamic Explanation of Stability of Minerals....... 81
7.2.2 Transformation of Minerals................................................................82
7.3 Effect of Plants on Soil Clay Assemblages......................................................85
7.3.1 Transformation in Temperate Climates...............................................86
7.3.2 Transformation of Pre-Existing Phyllosilicate Minerals of High
Temperature Origin.............................................................................86
7.3.3 Formation of Mixed-Layered 2:1 Clays .............................................87
7.3.4 Formation of Palygorskite and Sepiolite in Soils................................88
7.3.5 Formation and Transformation of 2:1 to 1:1 Mixed-Layer Clays........89
7.3.5.1 Interstratifications of Kaolinite and Smectite and
Their Evolution....................................................................89
7.3.5.2 Halloysite-Smectites............................................................90
7.3.5.3 Interstratification of Kaolins with Other 2:1 Minerals........90
7.3.6 Crystallisation of 1:1 Clays in Soils....................................................90
7.3.7 Formation of Oxyhydroxide Al- and Fe-Dominated Soil Clay
Assemblages .......................................................................................92
7.3.8 Formation of Other Oxides.................................................................93
7.3.9 Formation of Other Compounds in Soils............................................94
7.3.10 Biology and Its Effect on Clays and Clay Associations in Soils ........94
7.3.10.1 Soil Structure.......................................................................95
References...................................................................................................................95
Chapter 8 Nature and Origin of Surface Soil Clays.................................................................. 103
8.1 Illites (2:1)....................................................................................................... 103
8.2 Vermiculites (2:1)........................................................................................... 103
8.3 Smectites (2:1)................................................................................................. 108
8.4 Mixed-Layered 2:1 Minerals.......................................................................... 108
8.5 Kaolin-Smectites Interstratified (1:1-2:1)....................................................... 113
8.6 Kaolinite (1:1)................................................................................................. 116
8.7 Halloysite (1:1)................................................................................................ 116
8.8 Allophane (1:2 to 1:1) and Imogolite (1:2)...................................................... 121
8.9 Palygorskite and Sepiolite (2:1 Si:Mg)........................................................... 123
8.10 Oxides and Rarer Minerals............................................................................ 125
References................................................................................................................. 126
Chapter 9 The Importance of Climate in the Formation of Soil Clays..................................... 133
9.1 Cold and Cool Zones...................................................................................... 134
9.2 Warm Zone..................................................................................................... 135
9.3 Hot Zone......................................................................................................... 136
9.4 Mechanisms of Change.................................................................................. 138
References................................................................................................................. 139
Chapter 10 Associations of Soil Clays......................................................................................... 143
10.1 Organic Matter............................................................................................... 143
10.2 Charges on Clay Particles............................................................................... 144
10.3 Organo-Mineral Interactions.......................................................................... 146
10.4 Combined Indications on Links between Minerals and SOM....................... 152
10.5 Formation and Stabilisation of Microaggregates........................................... 153
10.6 Clay and Organic Aggregation and Soil Structure......................................... 156
10.6.1 Organic Particle Size and Fixation on Different Clay-Sized
Particles (OM Content and Clay-Size Fraction)................................ 156
10.6.2 Formation of Macroaggregates ........................................................ 157
10.6.3 Evolution of Aggregates with Rainfall Episodes
(Wetting and Drying)........................................................................ 158
10.6.4 Macroaggregates and Soil Structure: The Formation of Fractures.........158
10.6.5 Change of Structure with Depth: Aggregation and Fractures.......... 159
10.6.6 Organic Matter and Clay Structures and Retention
of Capillary Water............................................................................. 159
References................................................................................................................. 160
Chapter 11 Occurrence and Extraction of Soil Clays ................................................................. 167
11.1 Clay Associations........................................................................................... 167
11.2 Extraction of Soil Clays.................................................................................. 170
11.3 Recommended Procedures............................................................................. 174
References................................................................................................................. 175
Chapter 12 Identification and Quantification of Clay Minerals in Soils..................................... 177
12.1 Identification of Soil Clays by X-Ray Diffraction.......................................... 177
12.2 Identification and Analyses of Soil Clays by Chemical Extractions.............. 177
12.3 Identification of Soil Clays by Infrared Spectroscopy................................... 179
12.4 Identification of Soil Clays by Thermal Analyses.......................................... 179
12.5 Identification of Soil Clays by Electron Microscopy..................................... 179
12.6 Analysis of Soil Clays by Other Techniques.................................................. 180
12.7 Quantitative Analyses..................................................................................... 180
References................................................................................................................. 181
Chapter 13 Surfaces, Surface Reactions and Particle Size Effects.............................................. 185
13.1 Soil Clays and Surface Areas......................................................................... 185
13.2 Effect of Associations of Clays on Surface Areas.......................................... 186
13.2.1 Effect of Organic Matter on Surface Areas...................................... 186
13.2.2 Effect of Oxides, Oxyhydroxides and Hydroxides
on Surface Areas............................................................................... 187
13.3 Charges on Soils and Soil Clays..................................................................... 187
13.4 Effect of Associations upon Charges on Soils and Soil Clays....................... 187
13.5 Effects of Particle Size................................................................................... 190
13.6 Integration: Importance of Phenomena; Limitations of Measurements......... 191
References................................................................................................................. 192
Chapter 14 Role of Soil Clays in Agriculture, the Environment and Society ............................ 195
14.1 Plant Nutrition................................................................................................ 195
14.2 Soil Structure and Water Holding and Supply............................................... 196
14.3 Formation and Stabilisation of Pores............................................................. 198
14.4 Aggregation, Pores and Soil Quality..............................................................200
14.5 Bulk Soil Physical Properties......................................................................... 201
14.6 Carbon Sequestration.....................................................................................208
14.7 Pollution and Its Remediation........................................................................ 210
14.8 Medicine......................................................................................................... 212
14.9 Forensics......................................................................................................... 213
14.10 Archaeology and Environmental History...................................................... 214
References................................................................................................................. 215
Chapter 15 Summary................................................................................................................... 221
15.1 Soils (From Chapter 1)................................................................................... 221
15.2 Clays (From Chapter 2).................................................................................. 221
15.3 Formation of Clays in Soils (From Chapters 3-7).........................................222
15.4 Types of Clays and Their Origins (From Chapters 8 and 9)..........................224
15.5 Associations of Clays in Soils (From Chapter 10).........................................226
15.6 Extraction of Clays from Soil, and Their Identification and
Quantification (From Chapters 11 and 12).....................................................228
15.7 Surfaces, Surface Reactions and Particle Size Effects (From Chapter 13).........229
15.8 Role of Soil Clays in Applications in Agriculture, the Environment and
Society (From Chapter 14).............................................................................229
15.9 Résumé........................................................................................................... 231
Bibliography.............................................................................................................. 232
Annex: Simplified Methods for the Interpretation of X-Ray Diffraction
Diagrams of Soil Clay Assemblages............................................................................................... 233
Index...............................................................................................................................................245
