Table Of ContentS. Yariv . H. Cross
Geochemistry
of Colloid Systems
For Earth Scientists
With 86 Figures
Springer-Verlag
Berlin Heidelberg New York 1979
Dr. SHMUEL YARIV
The Hebrew University of Jerusalem, Israel
Dr. HAROLD CROSS
Israel Patent Office, Jerusalem, Israel
ISBN-13: 978-3-642-67043-5 e-ISBN-13: 978-3-642-67041-1
DOl: 10.1007/978-3-642-67041-1
Library of Congress Cataloging in Publication Data. Yariv, Shmuel,
1934--. Geochemistry of colloid systems for earth scientists. Bibliography: p.
Includes index. 1. Colloids. 2. Geochemistry. I. Cross, Harold, 1930-, joint
author. II. Title. QE515.Y37. 551.9. 78-11407
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© by Springer-Verlag Berlin Heidelberg 1979.
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Preface
Colloid science has been applied by soil chemists and clay mineral
ogists for many years, and some of the most important studies on
the behavior of colloids have been contributed by them. Barring a
few notable exceptions, only in the last decade have geochemists
applied colloid science in their research and in this period much work
has been published.
It seemed to the authors that it would be useful at this stage to
attempt to summarize the progress made and to try to examine what
colloid science has contributed and can further contribute to geo
chemistry.
This book is based partly on a course of the same title given to
graduate students by one of the authors (S. Y) between 1972 and
1977 at the Department of Geology at the Hebrew University of
Jerusalem. Consequently many fundamental concepts of the subject
are included that will be of use to graduate students in geology, geo
chemistry, soil science, and oceanography.
So that specialists interested in certain sections may find their
subjects comprehensively covered, a few topics are dealt with in more
than one chapter so that readers may ignore sections not especially
of interest to them. However the chapters more fully treating certain
topics are cross-referenced. In such cases the subjects are treated
from different viewpoints and the citations used represent these dif
fering viewpoints.
Since this branch of geochemistry is in its infancy, a few of the
conclusions are still speculative and some of these are even highly
speculative. In those cases where conclusions were regarded by us as
speculative, allusion was made to this fact. However, in our five years
of accumulating the literature it has been seen that conclusions once
regarded as highly speculative have been shown to be solidly based,
and it is probable that the conclusions now regarded as speculative
will also in time be shown to be correct.
We would like to acknowledge the invaluable advice and encour
agement of Professor V. G. Gabriel of New York given during the
entire gestation period of the manuscript and for his careful review
of the work in progress.
The various chapters were critically reviewed by experts in the
fields involved, many of whom supplied us with unpublished data,
pointed ou t further sources in the literature, and corrected errors and
VI Preface
misconceptions. We are grateful to the following, in alphabetical
order, for this generous and invaluable contribution: Miss. N. Agron,
Geological Survey of Israel, Jerusalem; Z. Aizenshtat, Hebrew Uni
versity of Jerusalem; F. Bartoli, Centre National de la Recherche
Scientifique, Vandoeuvre, France; Mrs. L. Ben-Dor, Hebrew Univer
sity of Jerusalem; A. Ben-Nairn, Hebrew University of Jerusalem;
Miss M. Bielsky, Hebrew University of Jerusalem; G. P. Briner, Divi
sion of Agricultural Chemistry at the Department of Agriculture,
Victoria, Melbourne; A. E. Foscolos, Geological Survey of Canada,
Calgary; Z. Garfunkel, Hebrew University of Jerusalem; Mrs. L.
Heller-Kallai, Hebrew University of Jerusalem; W. H. Huang, Texas
A & M University, College Station; W. D. Keller, University of Mis
souri, Columbia; B. Kohn, Ben-Gurion University of the Negev, Beer
Sheva; N. Lahav, Hebrew University, Rehovot;A.A. Levinson, The
University of Calgary; B. Luz, Hebrew University of Jerusalem; E.
Mendelovici, Instituto Venezolano de Investigaciones Cientificas,
Caracas; U. Mingelgrin, Agricultural Research Organization - The
Volcani Center, Bet-Dagan; B. D. Mitchell, The Macaulay Institute
for Soil Research, Aberdeen; M. M. Mortland, Michigan State Uni
versity, East Lansing; A.M. Posner, The University of Western Aus
tralia, Nedlands; I. Rozenson,Hebrew University of Jerusalem; Mrs.
S. Saltzman, Agricultural Research Organization-The Volcani Cen
ter, Bet-Dagan; E. Sass, Hebrew University of Jerusalem; A. Singer,
Hebrew University, Rehovot; B. Spiro, Hebrew University of Jeru
salem; E. Vansant, University of Antwerp; D.H. Yaalon, Hebrew
University of Jerusalem.
We are grateful to the authors and publishers who granted us
permission to reproduce illustrations from their books, articles, and
journals. These sources are noted in the legends of the figures.
Thanks are also due to Mr. Peter Grossman for the preparation
of some of the illustrations, to Messrs. Shlomo Shoval, Eli Yariv, and
Shalom Yariv for their help in preparing the typescript, to the librari
ans of the Department of Geology, Hebrew University, Miss Yon a
Metzger and Mrs. Zelda Kolodner for their help in collecting the
literature and lastly to our wives for their forbearance during the
long period of the book's preparation.
During the final preparation of the book, one of us (S. Y.) spent
a sabbatical at the Instituto Venezolano de Investigaciones Cienti
ficas (I. V.I.C.). He would like to acknowledge the contribution of
discussions he had with colleagues from the Institute, and the secre
tarial help of Mrs. Barbara Kamal, Mrs. Paula Morales and Mrs.
Monica Sanhueza.
October, 1978 S. Yariv
H. Cross
Contents
Introduction . . . . . . . . . . . . . . . . . . . . ........... .
1. What is Colloid Science? ...................... 1
2. Classification of Colloid Systems ................ 2
2.1 Based on States of Matter .................. 2
2.2 Based on Chemical Properties of the Components .. 3
3. Crystal Chemistry of Silicates . . . . . . . . . . . . . . . . . . . 5
3.1 Island Structure . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2 Chain and Ribbon Structures ................ 8
3.3 Layer Structure ... . . . . . . . . . . . . . . . . . . . . . . 9
3.4 Three-dimensional Network .. . . . . . . . . . . . . . .. 11
4. Water .................................. 12
4.1 Fine Structure of Water ................... 13
4.2 Fine Structure of Aqueous Inorganic Salt Solutions. 16
4.3 Fine Structure of Aqueous Solutions of Small Non-
polar Molecules and Radicals ................ 17
4.4 Liquid Boundary Layer . . . . . . . . . . . . . . . . . . .. 17
4.5 Aqueous Solutions of Hydrophilic Colloids . . . . . .. 19
References ................................. 22
Chapter 1
Some Geologic Colloid Systems 23
1. Mineralogy of Colloids in the Sedimentary Cycle ...... 23
1.1 Structure of the Common Clay Minerals . . . . . . . .. 23
1.2 Hydrous Oxides of Aluminum and Iron ......... 30
2. Soils and Sediments as Colloid Systems ............ 32
2.1 Solid Fraction in Soils and Sediments .......... 34
2.2 Water in Soils and Sediments ................ 36
2.3 Gases in Soils and Sediments ................ 37
2.4 Organic Matter in Soils and Sediments .......... 38
3. Fluidized Beds ............................ 41
4. Magma as a Colloid System .................... 44
4.1 Magmaphilic Polymeric Structures ............ 45
4.2 Magmaphobic Colloids .................... 52
4.3 Emulsions of Immiscible Liquids ............. 54
4.4 Foam of Volatiles ....................... 55
VIII Contents
5. Colloid Systems in Volcanic Eruptions . . . . . . . . . . . .. 56
5.1 Lava ................................ 58
5.2 Volcanic Smokes ........................ 59
6. The Ocean as a Colloid System ...... . . . . . . . . . . .. 62
6.1 Air-Water Interface ...................... 63
6.2 Gas Bubbles in the Ocean .................. 64
6.3 Suspended Inorganic Solids in the Ocean ........ 65
6.4 Organic Compounds in the Ocean ............. 73
7. The Atmosphere as a Colloid System ... . . . . . . . . . .. 77
7.1 Tropospheric Aerosols .................... 79
7.2 Stratospheric Aerosols .................... 85
References ................................. 86
Chapter 2
Physical Chemistry of Surfaces 93
1. Thermodynamics of Heterogeneous Systems . . . . . . . .. 94
1.1 Thermodynamic Properties and Quantities of the Inter-
face. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 95
1.2 Pressure Dependence of Chemical Potential and of
Water Migration in Compacting Sediments ....... 101
1.3 Surface Tension, the Strength of Intermolecular
Forces and Cleavage of Mineral Crystals ......... 102
1.4 Capillary Pressure ....................... 104
1.5 Contact Angle of a Liquid at a Boundary of Three
Phases and the Wetting Process . . . . . . . . . . . . . .. 108
2. Liquid Surface ............................ 111
2.1 Liquid Surface Tension .................... 111
2.2 Evaporation ........................... 116
3. Sorption ................................ 118
3.1 Sorption of Gases and Vapors by Solids ......... 120
3.2 Sorption by Solids from Solutions ............ 122
3.3 Sorption onto a Liquid-Gas Interface . . . . . . . . . .. 123
3.4 Gas Exchange Across a Gas-Liquid Interface ...... 124
3.5 Ion Exchange .......................... 130
3.6 Sorption and Surface Tension. . . . . . . . . . . . . . .. 134
4. Electrochemistry of Heterogeneous Systems ......... 135
4.1 Electric Double Layer at a Solid-Liquid Interface . .. 136
4.2 Electrokinetic Phenomena . . . . . . . . . . . . . . . . .. 143
4.3 Theory of Electrokinetic Phenomena . . . . . . . . . .. 146
4.4 Electric Properties of Dust Storms ............ 151
References ................................. 152
Contents IX
Chapter 3
Fonnation of Aqueous Solutions and Suspensions of Hydro-
phobic Colloids .............................. 157
1. Condensation Process (Formation of New Phases) ..... 157
1.1 Chemistry of Aluminum in Natural Waters ....... 161
1.2 Chemistry of Iron and Manganese in Natural Waters . 172
2. Dispersion Process .......................... 183
2.1 Physical Weathering ...................... 183
2.2 Chemical Weathering ..................... 186
2.3 Detachment of Particles Caused by Rainfall ...... 194
2.4 Peptization .. . . . . . . . . . . . . . . . . . . . . . . . . .. 196
References ................................. 201
Chapter 4
Surface Coatings on Rocks and Grains of Minerals 207
1. Incongruent Dissolution of Silicates .............. 207
2. Sorption from Aqueous Solutions onto Mineral Surfaces . 210
2.1 Sorption by Long-range Interactions ........... 210
2.2 Sorption by Short-range Interactions .. . . . . . . . .. 213
3. Alteration of Minerals by Abrasion ............... 219
3.1 Abrasion of Silica and Silicate Minerals ......... 219
3.2 Abrasion of Calcite 223
3.3 Abrasion pH Values of Minerals .............. 224
4. Surface Structures of Gibbsite and Goethite ......... 226
References ................................. 227
Chapter 5
Kinetic Properties of Colloid Solutions 231
1. Kinetic Properties of Particles Dispersed in Still Fluids .. 231
1.1 Brownian Movement ..................... 231
1.2 Diffusion ............................. 231
1.3 Sedimentation ........................ " 235
2. Kinetic Properties of Particles in Flowing Fluids ...... 237
2.1 Laminar and Turbulent Flow ................ 237
2.2 Fluid Drag ............................ 238
2.3 Dispersion of Particles in a Turbulent System ..... 241
2.4 Entrainment of Sediment .................. 242
References ................................. 244
x Contents
Chapter 6
Colloid Geochemistry of Silica 247
1. Surface Chemistry of Silica .................... 248
1.1 Functional Groups on Silica . . . . . . . . . . . . . . . .. 248
1.2 Functional Groups on Silica-Alumina .......... 259
1.3 Opals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 262
2. Silica in Aqueous Solutions .................... 264
2.1 Polymerization and Depolymerization of Silicic Acid . 264
2.2 Solubility of Silica ....................... 266
2.3 Silica Sorption by Minerals ................. 273
2.4 Silica in Natural Waters . . . . . . . . . . . . . . . . . . .. 276
References ................................. 282
Chapter 7
Colloid Geochemistry of Clay Minerals 287
1. Functional Groups on Clay Minerals and Ion Exchange
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 287
1.1 "Broken-bond" Surfaces ................... 287
1.2 Interlayer Space of 2: I-Type Clay Minerals . . . . . .. 293
1.3 The Flat Oxygen and Hydroxyl Planes .......... 300
2. Interaction Between Clay Minerals and Organic
Compounds .............................. 302
2.1 Sorption of Organic Ions by Clay Minerals ....... 302
2.2 Sorption of Organic Polar Molecules by Clay Minerals 307
2.3 Organic Reactions Catalyzed by Clay Minerals . . . .. 312
3. Solubility of Clay Minerals .................... 313
4. Environmental Effects on Clay Mineralogy .......... 318
4.1 Origin of Primary-stage (Neoformation) Clay Minerals
and Their Related Environment .............. 321
4.2 Environmental Relationships ofN + 1 Stage Clay
Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 326
References ................................. 327
Chapter 8
Interaction Between Solid Particles Dispersed in Colloid
Systems ....... . . . . . . . . . . . . . . . . . . . . . . . . . . .. 335
1. Interaction Between Solid Particles Dispersed in a Gaseous
Phase. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 335
1.1 Van Der Waals-London Forces Between Disperse
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 336
1.2 Electrostatic Forces Between Disperse Particles .... 337
Contents XI
1.3 Effect of Adsorbed Water Monolayer on Desert
Varnish .............................. 337
2. Aggregation of Particulate Matter in the Hydrosphere . .. 337
2.1 Interactions Between Solid Particles Dispersed in a
Liquid Medium ......................... 337
2.2 Stability of Aqueous Hydrophobic Colloid Solutions
and Suspensions ........................ 343
2.3 Coagulation in Natural Waters ............... 349
3. Soil Aggregates ............................ 353
3.1 Interaction Between Clay Particles ............ 355
3.2 Interaction Between Sand Grains ............. 360
3.3 Reactions of Humic Substances with Mineral Soil
Components ........................... 363
3.4 Pore Space in Soils . . . . . . . . . . . . . . . . . . . . . .. 369
3.5 Stability of Aqueous Soil Dispersions and the Migra-
tion of Soil Constituents ................... 369
References ................................. 373
Chapter 9
Rheology of Colloid Systems ..................... 379
1. Flow Behavior of Suspensions .................. 379
2. Rheology of Dispersions in the Hydrosphere ......... 383
2.1 Rheology of Dilute Dispersions .............. 384
2.2 Rheology of Concentrated Dispersions and Muds ... 388
3. Rheology of Sediments of Silicate Minerals . . . . . . . . .. 391
3.1 Wet Sediments of Sand Grains ............... 394
3.2 Argillaceous Sediments .................... 395
4. Viscosity of Magmas . . . . . . . . . . . . . . . . . . . . . . . .. 397
References ................................. 399
Chapter 10
Colloid Geochemistry of ArgiI1aceous Sediments ........ 401
1. Microstructure of Argillaceous Sediments ........... 404
1.1 Microstructure of Fresh Sediments ............ 405
1.2 Microstructure of Compacted Sediments ........ 406
2. Aging and Diagenetic Alteration of Smectites in Argil-
laceous Sediments .......................... 408
3. Surface Chemistry of Solutes Flow Through Argillaceous
Sediments ............................... 413
3.1 Nature of Pores in Shales. . . . . . . . . . . . . . . . . .. 414
3.2 Effect of Migrating Water on the Migration of Solutes 415
