books sssabookseries mineralsinsoile frontmatter
TRANSCRIPT
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Soil Science Society
o
merica Book Series
Books in the series are available from the Soil Science Society ofAmerica
677 South
Segoe
Road Madison WI 53711 USA.
1.
MINERALS N SOIL ENVIRONMENTS. Second Edition. 1989.
J. B Dixon and
S.
B Weed
editors
R. C Dinauer
m n ging editor
2.
PESTICIDES
N
THE SOIL ENVIRONMENT: PROCESSES IMPACTS
AND MODELING.
1990.
H.
H. Cheng
editor
S.
H. Mickelson
m n ging editor
3. SOIL TESTING AND PLANT ANALYSIS. Third Edition. 1990.
R. L Westerman editor S. H. Mickelson m n ging editor
4. MICRONUTRIENTS IN AGRICULTURE. Second Edition. 1991.
J. J. Mortvedt et aI. editors S. H. Mickelson m n ging editor
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Copyright © 1989 by the Soil Science Society of America, Inc.
ALL RIGHTS RESERVED
UNDER THE
U.S. COPYRIGHT
LAW OF 1978 (P.L. 94-553)
Any and all uses beyond the fair use provision of the law require
written permission from the publishers and/or author(s); not ap
plicable to contributions prepared by officers or employees
of
the
U.S. Government as part
of
their official duties.
Second Printing 1992
Soil Science Society
of
America, Inc.
677 South Segoe Road, Madison, Wisconsin 53711 USA
Library o Congress Cataloging in Publication Data
Minerals in soil environments.
(SSSA Book Series; no.
1
Includes bibliographies and index.
1. Soil mineralogy.
I
Dixon, Joe Boris.
II. Weed, S.
B.
(Sterling
Barg)
III. Dinauer,
Richard C.
S592.55.M56 1989 549 88-34929
ISBN 0-89118-787-1
Printed in the United States of America
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CONTENTS
Page
DEDICAnON
XVll
FOREWORD
xix
PREFACE xxi
CONTRIBUTORS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XXlll
PERIODIC TABLE
OF
THE
ELEMENTS XXVI
Chapter
An
Introduction
to
Soil Mineralogy
1
D.
G
SCHULZE
I Chemical and Structural Classification of Minerals. . . . . . . . . . . . . . . I
A Halide Sulfate and Carbonate Minerals 3
B Su l f i d e s 3
C
Oxides Hydroxides and Oxyhydroxides 4
D. Silicates 6
II. Phyllosilicate Minerals in Soils 6
A Basic Structural Concepts 9
B Structure and Properties of Phyllosilicate Minerals Common in
So i l s
16
III. Aluminosilicate Minerals with Short-Range Order: Allophane and
Imogolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
IV Some Crystallographic Concepts 25
A Periodicity in Crystals 25
B
The Unit
Cell
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
26
C Miller Indices
27
D. X-ray Diffraction 29
V S umma r y 33
VI
Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
ACKNOWLEDGMENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
REFERENCES 34
Chapter 2 Surface Chemistry of Soil Minerals
5
M B
MC
BRIDE
I
Nature
of
Mineral Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
A Diffuse Double-layer Model
of
Permanent-charge Minerals. . . . . 35
B
Structure
of
the Layer Silicate-Solution Interface
40
C Point of Zero Charge Concept for Variable-charge Minerals . . . 44
D Diffuse Double-layer Model
of
Variable-charge Minerals. . . . . . . 47
E Discrete-site Bonding Model
of
Variable-charge Minerals
49
F
Specifically Adsorbed Ions on Variable-charge Minerals
53
II. Processes at Mineral Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
A Ion Exchange Equations and the Problem
of
Surface Activity 55
B
A Statistical Mechanical Description
of
Ion Exchange 59
C Difficulties with Ion Exchange Models 63
D
General Rules
of
Cation Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . 65
E
Chemisorption of Cations and Anions 67
F Clay Surface Acidity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
G. Electron Transfer
72
H
Clay Swelling Behavior 75
I The Covolume Model
of
Particle Interaction. . . . . . . . . . . . . . . . . 80
III. S umma r y 81
IV
Appe nd i x
82
REFERENCES 84
v
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vi
CONTENTS
Chapter 3
An
Introduction to Organic Matter in Mineral Soils 89
J. M OADES
I
The Nature of Organic Substances
92
A Plant Materials
92
B
Humic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
C
Nonhumic Substances-Carbohydrates
107
D
Microbial Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
II. The Persistence of Organic Substances. . . . . . . . . . . . . . . . . . . . . . . . . 118
A
The Use of
4C
as a Tracer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
B Dating Techniques for Organic Matter . . . . . . . . . . . . . . . . . . . . 123
III. Reactions of Well-Defined Chemicals with Clays
127
A Small Molecules .
128
B
Macromolecules or Polymers 131
C Predicted Behavior of Biopolymers in Soils . . . . . . . . . . . . . . . . . 134
IV Natural Organo-Mineral Associations. . . . . . . . . . . . . . . . . . . . . . . . . . 135
A Density Fractionations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
135
B
Fractionations by Sedimentation
137
C Physical Disaggregation of Soils . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
D Associations of Organic Matter with Hydrous Oxides
145
V
Conc lu s ion s
lSI
VI Acknowledgments
152
VII. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
152
VIII. Supplemental Reading-Texts on Organic Matter . . . . . . . . . . . . . . . .
152
REFERENCES
153
Chapter 4 Mineral Equilibria and the Soil System 161
DHANPAT RAI AND JAMES
A
KITTRICK
I Fundamentals of Mineral Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . .
163
A Phase Rule . . . . . . . . .
163
B
Enthalpy Entropy and Free Energy
167
C
Thermochemical Data Base
173
D Role of Solubility Measurements in Understanding the Soil
Sy s t em 177
II. Use of Thermochemical Data in Understanding Soil Mineral
Equilibria. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
A Soil Mineral Weathering Sequences. . . . . . . . . . . . . . . . . . . . . . . . .
179
B
Mechanisms That Control Aqueous Concentrations . . . . . . . . . . . 185
C Geochemical Groundwater Modeling . 189
D
Selection
of
Appropriate Experiments or Experimental
Parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
III. Past Present and Future
191
IV Study Problems
192
REFERENCES
194
Chapter 5 Mineral Occurrence in Soil Environments 199
B L.
ALLEN AND
B
F HAJEK
I
Soil Taxonomy: Soil Mineralogy Relationships. . . . . . . . . . . . . . . . . .
200
A
Orders
201
B Subo rde r s 201
C
Great Groups
204
D Subgroups 205
E Families . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
F
Series 209
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II. Quartz and Other Silica Minerals 209
III. Fe ld s p a r s 210
IV Olivine Amphiboles Pyroxenes 213
A Ol i v i n e 213
B
Amph i b o l e s 214
C Pyroxenes 215
V Mi c a s
215
A Biotite 216
B
Muscovite 217
C Clay Mi c a 218
VI. Vermiculite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
VII. Chlorite 225
VIII.
Smec t i t e
228
A Inheritance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
B
Formation by Pedogenesis and Alteration 229
C
Alteration to Other Minerals
231
D
Distribution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
231
IX. Talc and Pyrophyllite 232
X
Kaolinite and Halloysite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
A Kaolinite 233
B Ha l l o y s i t e
236
XI. Serpentine 239
XII. Palygorskite and Sepiol ite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
XIII. Zeolites 242
XIV. Allophane and Imogolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
A Allophane 244
B
Imogolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
XV. Carbonates Sulfates. Sulfides. and Chlorides. . . . . . . . . . . . . . . . . . . . 246
A Carbonates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
B Su l f a t e s
247
C Su l f i d e s
249
D
Chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
XVI. Aluminum Oxides 250
XVII. Iron Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
A
Magnetite and Ilmenite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
B
Goe t h i t e 253
C Lepidocrocite and Akaganeite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
D
Hematite
255
E
Magh em i t e
256
F
Ferrihydrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
G. Iron Oxides and Soil Families 256
XVIII. Manganese
Oxides
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
XIX. Titanium and Zirconium Minerals 258
XX. Phosphate Minerals 260
XXI. S umma r y
261
XXII. Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
REFERENCES 264
Chapter 6 Carbonate Halide Sulfate and Sulfide Minerals 279
HARVEY
E
DONER AND WARREN C LYNN
I Calcite. Magneisum-Calcite. and Dolomite 279
A Natural Occurrence 280
B
Crys t a l l og raphy 285
C Formation and Stability 287
D
Identif ication. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 294
E Impact on Soils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
II. Gypsum and Other Moderately Soluble Sulfates. . . . . . . . . . . . . . . . . 296
A Natural Occurrence 296
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B Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
C.
Formation and Stability 297
D Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
E
Impact on Soils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
III. Pyrite and Jarosite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302
A
Natural Occurrence 303
B
Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
C Formation and Stability 305
D
Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
307
E
Impact on Soils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
IV Soluble Minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
A
Natural Occurrence 309
B Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
C
Formation and Stability 314
D Identification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
E Impact on Soil 320
V S umma r y
320
VI
Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
REFERENCES 324
Chapter 7 Aluminum Oxides
and
Oxyhydroxides 33
PA HO HSU
I
Nomenclature and Structural Properties. . . . . . . . . . . . . . . . . .
331
II. Methods
of
Identification and Determination
338
A
X-ray Diffraction Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
338
B Thermal Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
C Infrared Absorption Analysis 343
D Selective Dissolution 345
III. Mechanism
of
Aluminum Hydroxide Formation 346
A
Composition and Structure of OH-AI
Polymers
. . . . . . . . . . . . . 347
B Hydrolysis and Polymerization 351
C
Crystallization of Aluminum Hydroxides. . . . . . . . . . . . . . . . . . . . 353
D Polymorphs of Aluminum Hydroxides . . . . . . . . . . . . . . . . . . . . 357
IV Gibbsite in Soils. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
A Occurrence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
B Genesis
of
Gibbsite in Soils 359
V Formation
of
Aluminum Oxyhydroxides in Soils . . . . . . . . . . . . . . . . 362
VI
Reactions of Aluminum Hydroxide in Soils
363
A
Reaction with Anions 364
B
Adsorption of Cations
366
C
Stabilization
of
Soil Aggregates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
VII. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
REFERENCES 371
Chapter 8
Iron
Oxides 79
U
SCHWERTMANN AND R M TAYLOR
I Forms and Characteristics of Soil Iron Oxides 380
A
General 380
B Goethite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
C Hematite 387
D Lepidocrocite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
E
Magnetite and Maghemite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
F. Ferrihydrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
G
Other Minerals 394
II. Occurrence and Formation of Iron Oxides. . . . . . . . . . . . . . . . . . . . . .
395
A General Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
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B
Thermodynamic Stability
vs
Kinetics 396
C Occurrence and Modes of Formation in Soils 398
III. Properties Relevant to Soils 407
A Surface Structure 407
B
Surface Charge 407
C Ion Adsorption 408
D Adsorption
of
Organics 415
E Aggregation and Cementation. . . . . . . . . . . . . . . . . . . . . . . .. . . . . . 416
IV
Iron Oxides and Microorganisms 419
A Reduction
of
Iron Oxides by Microorganisms. . . . . . . . . . . . . . . . 419
B
Biotic Formation of Iron Oxides 420
V Determination
421
A General 421
B Goe t h i t e
423
C Hematite 424
D
Lepidocrocite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
E Maghemite Magnetite 425
F Ferr ihyd ri te Ferox yhite . . . . . . . . . . .. . . . . .. . . . . . .. . . . . . .. . . .
426
VI Acknowledgment 426
VII. Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
VIII. Supplemental Reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
REFERENCES 427
Chapter 9 Manganese Oxides and Hydroxides 439
R M
MC KENZIE
I
The Manganese Oxide Minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 439
A Tunnel Structures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 440
B
Layer Structures 444
C
The Lower Oxides 446
D
Relation Between Tunnel and Layer Structures. . . . . . . . . . . . . . . 447
II. Mineral Identification 449
A X ray Diffraction 449
B
Infrared Spectroscopy 449
III. Occurrence of the Minerals in Soils 451
IV
Oxidation
of
Manganese and Growth
of Nodules.
. . . . . . . . . . . . . . . 452
V Formation of Manganese Minerals in Soils 455
VI
Chemical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
A
Chemical Composition 456
B Surface Charge 457
C
Adso rp t i o n
457
VII.
S umma r y
460
VIII. Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 460
REFERENCES 461
Chapter 10 Kaolin and Serpentine Group Minerals 467
J
B
DIXON
I
Structural Properties
of
Kaolin Minerals 468
A Kaolinite 468
B
Ha l loy s i t e 474
II. Morphological Characteristics
of
Kaolinite and Halloysite 474
A
Kaolinite 474
B Ha l loy s i t e 477
III. Formation of Kaolin
481
A Rapid Synthesis of Kaolinite
481
B Equilibrium Environment and Conditions for Synthesis 482
C Kaolinite Formation Induced by Plant
Growth.
. . . . . . . . . . . . . . 485
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D Kaolinite Formation from Hydroxy-AI-Interlayered
Montmorillonite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
E Isotopic Composition of Kaolins Formed at Different
Temperatures 486
F.
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 486
IV Occurrence
of
Kaolin Minerals in Soils Rocks and Sediments 486
A
Stability
of
Kaolinite in Weathering Environments. . . . . . . . . . . . 486
B Kaolinite in Young
Soils
. . . . . . . . . . . . . . . . . . . . . . . 487
C Soils with Abundant Kaolinite Content 488
D Rocks Containing Abundant Kaolinite 489
E
Formation and Distribution
of
Halloysite in Soils 489
F. Soil Kaolinite-A Major Source
of
Ocean Sediments 493
V Order-Disorder in Kaolins . . . . . . . . . . . . . . . . . . . . . . 495
VI Interstratification
of
Kaolinite and 2: 1 Minerals 496
VII. Isomorphous Substitution in Kaolinite and Halloysite . . . . . . . . . . . . 497
VIII. Chemical Properties
of
Kaolinite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
A Cation Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
B
Anion Exchange
501
C
Flocculation and Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503
IX. Physical Properties
of
Kaolinite and Halloysite . . . . . . . . . . . . . . . . . . 506
X
Identification
of
Kaolinite and Halloysite . . . . . . . . . . . . . . . . . . . . . . . 508
XI. Quantitative Analysis of Kaolinite and Halloysite 510
XII. Serpentine Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
511
A
Structure 511
B Compos i t i o n 512
C Morphological Properties 512
D
Thermal Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
E
Stability and Weathering. . . . . . . . . . . . . . . . . . . . . . . . . .
515
F. Synthesis
517
XIII. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
XIV. Supplemental Reading. . . . . . . . . . . . . . . . . . . . . . . . . . . 518
REFERENCES 519
Chapter The Pyrophyllite-Talc Group 527
L
W
ZELAZNY AND
G
N. WHITE
I Structural Properties and Mineral Identification 527
A
Structures and Formulas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
B X-ray Diffraction 531
C
Thermal Analysis
533
D Infrared Analysis 537
E
Optical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
II. Natural Occurrences 539
A
Geologic Extent
539
B
Soil Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 542
III. Equilibrium Environment and Conditions for Synthesis 543
IV Chemical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
545
V Physical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
VI Quantitative Determinations 546
VII. Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 546
REFERENCES 547
Chapter
12
Micas 551
DELVIN S FANNING VISSARION
Z
KERAMIDAS AND
MOHAMED A EL-DESOKY
I Structural Properties and Mineral Identification 552
A Structures Formulas and Nomenclature 552
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xi
B
X-Ray Diffraction
XRD)
.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 567
C
Differential Thermal Analysis DTA)
571
D. Thermogravimetry TG) 577
E
Infrared Spectroscopy IR) 578
F
Electron Microscopy 580
G. Mossbauer
Spectroscopy.
. . . . . . . . . . . . . . . . . . . . . . . . .
. .
. . . . . .
581
H. Nuclear Magnetic Resonance
NMR)
582
II. Weathering
and
Synthesis Relationships. . . . . . . . . . . . . . . . . . . . . . . . 583
A
General Principles 583
B
Physical
Weathering.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
C
Simple Transformation to Expansible
2:
I Minerals 584
D. Mica-Vermiculite-Kaolinite Stability Diagram
and
Complex
Transformat ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
E Pedogenic Mica. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
F
Illitization in Geologic
Columns
603
G. Glauconite Formation
and Weathering.
. . . . . . . . . . . . . . . . . . . . . 605
III. Natural Occurrence 608
A
Occurrence in Soil Parent Materials 608
B
Occurrence in Soils 609
IV. Chemical
Properties.
. . . . . . . . . . . . . . . .
. .
. . . . . . .
. .
. . . . . . . . . . . . .
611
A
Properties Related to Ion Exchange. . . . . . . . . . . . . . . . . . . . . . . . .
611
B
Chemical Composit ion 618
V
Physical
Properties.
. . . . . . . . . . . . . . . . . .
. .
. . . . . . .
. .
.
. .
. . . . . . . . . 618
VI.
Quantitative
Determination 619
VII.
Conc l u s i o n s
620
VIII. Acknowledgments 622
IX. Problems
and
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 622
X. Supplemental
Reading.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623
REF ERENCES
624
Chapter 3 Vermiculites
635
LOWELL
A DOUGLAS
I
Distr ibut ion in Soils 635
II. Structure and Composition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
III. Formation
of Vermiculite.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
A
Release
of
Potassium .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
B
Oxidation
of
Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 646
C. Hydroxyl
Orientation.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
D. Total Charge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
E
Stability of Vermiculites 650
IV. Identification
of
Vermiculites.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 652
A
X-ray Diffraction 653
B
Infrared Spectroscopy 657
C
Thermal Analysis 658
D. Electron Microscopy 659
E
Total
Charge.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
F.
Quantitative
Determination
of
Vermiculite
661
V Ion Exchange 662
A
Cation Exchange
Capacity.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
B
Cation
Exchange.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
C
Ion Fixation 664
VI.
The
Soil-Clay-Vermiculite Problem. . . . . . . . . . . . . . . . . . .
. .
. . . . . . 667
VII. Problems
and
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
REFERENCES 668
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Chapter 14 Smectites
CONTENTS
675
GLENN BORCHARDT
I.
Structural Properties and Mineral Identification. . . . . . . . . . . . . . . . . 675
A.
X-Ray Diffraction XRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
B Electron Optical Properties TEM SEM) 679
C
Thermal Analysis 682
D.
Infrared IR) Spectroscopy 683
E
Elemental Analysis
EA) 685
F. Selective Dissolution Analysis SDA) 686
G. M6ssbauer Spectroscopy MS) 687
H. Other Methods
of
Smectite Identification. . . . . . . . . . . . . . . . . . . . 687
II
Natural Occurrence 689
A.
Geographic Extent 689
B Soil Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 691
C Sedimentary Occurrence 694
III
Equilibrium Environment and Conditions for Synthesis 697
A.
Conditions for Laboratory Synthesis. . . . . . . . . . . . . . . . . . . . . . . . 697
B
Transformation and Formation in Soils . . . . . . . . . . . . . . . . . . 697
C Smectite Weathering 701
IV. Chemical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
703
A.
Cation Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
703
B Anion Exchange 707
C Reaction Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 707
D.
Molecular Sorption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
708
E
Other Chemical Properties 708
F. Smectites and Soil Fertility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 708
V.
Physical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
A. Shrink-Swell
709
B
Water
Retention
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
711
C Cohesion and Adhesion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
D. Particle Size Distribution 713
VI. Quantitative Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
713
A.
X-Ray Diffraction Methods
713
B. Surface Area Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 714
C Cation Exchange Capacity Methods 715
D. Other Methods
of
Quantitative Determination 715
VII. Conc l u s i o n s 716
VIII. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 716
IX. Supplementary Reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 718
REFERENCES 718
Chapter 15 Chlorites
and
Hydroxy Interlayered Vermiculite
and
Smectite 729
RICHARD
I.
BARNHISEL AND PAUL
M.
BERTSCH
I.
Origin and Sources of Chlorite. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
II. Structural Properties and Mineral Identification of Chlorite 731
A.
Idealized Structures
731
B
X-ray Diffraction Properties 733
C Chemical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 736
D. Thermal Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
E
Infrared and M6ssbauer Properties 740
III
Weathering
of
Chlorite Minerals 742
IV. Structural Properties and Mineral Identification
of
Hydroxy-
Interlayered Vermiculite HIV) and Smectite HIS) 744
A.
Idealized Structure and Generalizations 744
B Identification by X-ray Diffraction XRD) . . . . . . . . . . . . . . . . . 746
C Identification by Thermal Analysis
748
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D. Identification by Infrared Analysis. . . . . . . . . . . . . . . . . . . . . . . . . .
749
E
Characterization of Hydroxy-interlayer Materials by
Conductometric
and
Potentiometric Titr imet ry . . . . . . . . . . . . . . . 749
V
Origin, Sources, Distribution,
and
Weathering
of
Hydroxy
Interlayered Materials
750
A
Origin
and Sources.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
750
B
Distribution
and
Weathering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
VI. Physicochemical Properties of Hydroxy-Interlayered Vermiculite
HIV)
and
Hydroxy-Interlayered Smectite HIS) . . . . . . . . . . . . . . . . .
756
A
Physical
Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
756
B
Chemical
Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
757
C
Removal
of
Hydroxy Interlayers
. . . . . . . . . . . . . . . . . . . . . . . . . . . 761
VII. Laboratory Synthesis of Hydroxy-Interlayered Vermiculite HIV)
and Smectite HIS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
763
A
Synthesis Methodology
764
B Type of Clay Mineral Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . .
769
C
Nature
of
Hydroxy-Interlayer
Material.
. . . . . . . . . . . . . . . . . . . . .
771
D Comparison of Synthetic
and
Naturally Interlayered Clays. . . . . 774
VIII. Problems
and
Exerc ises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
ACKNOWLEDGMENTS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
778
REFERENCES 779
Chapter 16 Interstratification in Layer Silicates 789
BRI1
1 SAWHNEY
I
Regular Interstratification
789
A
Characterization
of
Regularly Interstratified Layers
. . . . . . . . . . .
790
B Examples of Regularly Interstratified Minerals and
Interpretation
of
Their X-ray Diffraction Patterns . . . . . . . . . . . . 790
II.
Random
Interstratification
797
A
Characterization
of
Randomly Interstratified Layers. . . . . . . . . . .
797
B Examples of Randomly Interstratified Minerals and
Interpretation of Their XRD Patterns. . . . . . . . . . . . . . . . . . . . . . . 807
III. Formation ofInterstratified M ine ra l s . . . . . . . . . . . . . . . . . . . . .. . . . . 812
A M ica V erm icul i te . . . . . . . . . . . .. . . . . .. . . . . .. . . . . . .. . . . . .. . .
812
B
M ica Sm ec t i t e . . . . . . . . .. . . . .. . . . .. . . . .. . . .. . . . .. . . . .. . 813
C
Mechanism of Regular Interstratification . . . . . . . . . . . . . . . . . . . . 815
IV. Recent
D ev e lo pm en ts . . . . . . . . .. . . . . . .. . . . . . . .. . . . . . .. . . . . . .. 816
V S um m ary . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . . .. . . . . . . . . . .. . . . . . . 819
VI.
Appendix Sample
Calculation for One-Dimensional Diffraction
Profile 820
REFERENCES 824
Chapter 17 Palygorskite and Sepiolite Group Minerals 829
ARIEH
SINGER
I
Basic Characteristics
830
A
Structure
. . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . .
830
B
Chemical Composition
832
C M or ph olo gy . . . . . .. . . . .. . . . . .. . . . . .. . . . .. . . . . .. . . . .. . . . . .
835
D. Surface
Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 838
II. Mineral Identification 843
A
Field
and
Optical Identification 843
B X-ray Identification 843
C
Thermal Analysis
845
D
Transmission-
and
Scanning-Electron Microscopy TEM
and
SEM) 846
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E Infrared and Mossbauer Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . 847
III. Formation of Palygorskite and Sepiolite. . . . . . . . . . . . . . . . . . . . . . . . 849
A Synthesis 849
B
Equilibrium Conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852
C
Environments of Occurrence 854
D Pedogenic Formation
of
Palygorskite 860
IV
Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 866
REFERENCES
866
Chapter 18 Zeolites in Soils 873
DOUGLAS
W
MING AND FREDERICK
A
MUMPTON
I Structure and Composition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 874
A Definition 874
B
Composition 874
C
Crystal Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
875
II. Properties and Applications
879
A Mineralogical Properties 879
B
Cation-exchange Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 880
C
Adsorption and Molecular Sieving Properties 882
III. Natural Occurrences 883
A Geologic Occurrences. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883
B Pedogenic Occurrences 887
IV
Formation of Zeolites 890
A Equilibrium Environments and Conditions for Formation 890
B Synthesis under Hydrothermal Condit ions. . . . . . . . . . . . . . . . . . . 892
V
Mineral Identification
893
A X-ray Diffraction 893
B
Morpho logy
895
C
Optical Microscopy 896
D
Thermal Analyses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 900
E Elemental Analysis . . . . . . . 901
F. Other Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 902
VI Quantitative Determinations 904
A X-ray Diffraction Methods 904
B
Cation-Exchange Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 904
C
Adsorption Methods 905
VII. Problems and Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
906
VIII. Acknowledgments
906
IX. Supplemental Reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
906
REFERENCES 907
Chapter 19 Silica in Soils: Quartz and Disordered Silica Polymorphs 913
L
RICHARD DREES LARRY P WILDING NEIL E SMECK AND
ABU L SENKA YI
I
Structure and Chemical
Composition
. . . . . . . 914
A Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
B
Chemical Composition 918
II. Mineral Identification 921
A Physical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
B
Light Optical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 932
C
X-ray Diffraction 934
D Thermal Properties.. . . . . . . . . 937
E Infrared Spectroscopy 939
III. Quantitative Determination 941
A Quartz 941
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B
Opal CT and Cristobalite .
C
Opal-A .
IV.
Formation
and Solubility
of
Silica Minera ls .
A Formation of
Silica Minera ls .
B
Solubility of Silica Minera ls .
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 Feldspars Olivines Pyroxenes
and
Amphiboles
P. M.
HUANG
x
942
943
943
943
948
950
954
954
956
957
959
959
961
961
963
964
965
975
I Structural Properties and Mineral Identification 976
A Feldspars 976
B
Olivines Pyroxenes
and Amphiboles.
. . . . . . . . . . . . . . . . . . . . . . 997
II. Natural Occurrence and Equilibrium Environment 1003
A
Feldspars 1003
B Olivines Pyroxenes and Amphiboles. . . . . . . . . . . . . . . . . . . . . . . 1013
III. Physicochemical
Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1016
A F e l d s p a r s
1016
B Olivines Pyroxenes
and Amphiboles.
. . . . . . . . . . . . . . . . . . . . . . 1029
IV.
Quantitative Determination
1034
A Feldspars 1034
B
Olivines Pyroxenes and Amphiboles. . . . . . . . . . . . . . . . . . . . . . . 1037
V Summary and Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1038
VI. Problems
and Exercises.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1038
VII. Supplementary
Reading.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
REFERENCES 1039
Chapter
21
Allophane
and
Imogolite
1 51
KOJI WADA
I Structural Properties
and
Mineral Identification 1052
A X-ray Diffraction 1052
B Electron Microscopy 1053
C. Electron Diffraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1054
D.
Chemical Analyses.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1056
E Infrared
Spectroscopy 1059
F
X-ray Fluorescence
Spectroscopy.
. . . . . . . . . . . . . . . . . . . . . . . . . . 1060
G. Nuclear Magnetic Resonance Spectroscopy 1060
H.
Thermal
Analyses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1061
I
Density
and
Surface-Area
Measurement.
. . . . . . . . . . . . . . . . . . . . 1062
1
Structure Models 1062
II.
Natural
Occurrence 1064
A Geographic Extent 1064
B
Soil
Environment.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1064
C. Sedimentary Occurrence. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1068
III. Equilibrium Environment and Conditions for Synthesis 1068
IV.
Chemical Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070
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A Ion Exchange. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1070
B
Surface Acidity 1072
C Specific Adsorption of Cations and Anions 1073
D. Interaction with Organic Compounds
. . . . . . . . . . . . . . . . . . . . . 1076
V Physical and Engineering Properties 1077
VI. Quantitative Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1080
VII. Conclusion 1080
VIII. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1081
REF ERENCES 1081
Chapter 22 Phosphate Minerals 1089
WILLARD
L
LINDSAY PAUL
L
G. VLEK AND SEN H. CHIEN
I
Classification
and
Structure
of
Phosphate Minerals 1089
II. Occurrence
of Phosphate Minerals in Soils 1102
A Naturally Occurring Phosphate Minerals in Soils 1103
B Reaction Products of Phosphate Fertilizers in Soils
11
03
C Surface Reactions
of
Phosphate on Soil Minerals 1107
III. Phosphate Mineral Equilibria in Soils . . . . . . . . . . . . . . . . . . . . . . . . . 1109
A
Phosphate Species in Soil Solution 1109
B
A Unified Phosphate Solubility Diagram 1111
C Effect of Redox on Phosphate Stability . . . . . . . . . . . . . . . . . . . . . 1114
D. Polyphosphate Equilibria in Soil 1115
E Equilibria
of
Trace Element Phosphates . . . . . . . . . . . . . . . . . . . . . 1115
IV. Physical Characterization of Phosphate Minerals in Soils 1117
V
Conc l u s i o n s
1124
VI. Problems and Exercises. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1125
REFERENCES 1126
Chapter 23 Titanium and Zirconium Minerals 1131
A
R
MILNES
AND R W
FITZPATRICK
I Geological and Geochemical Background: Titanium and Zirconium
in Parent Materials 1132
A Titanium 1132
B
Zirconium 1140
II. Forms
and
Occurrence
of
Titanium and Zirconium in Soils. 1144
A Residual Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1147
B
Minerals Formed Through Weathering or Alteration . 1153
C
Authigenic Minerals . . . . . . . 1157
III. Chemical
and
Physical Properties
of
the Minerals Commonly
Reported in Soils 1162
A Crystal Structures and Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . 1162
B Stability Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1166
C Charge Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167
D. Magnetic Properties 1171
E
Techniques of Identification 1174
F Influence on Soil Structure and Induration 1180
IV. Formation and Weathering
of
the
Minerals
. . . . . . . . . . . . . . . . . . . . 1183
A Evidence for Titanium and Zirconium Mobility . . . . . . . . . . . . 1183
B Synthesis of the Minerals 1186
C Use
of
Titanium
and
Zirconium in Studies of Soil Formation 1190
V
Problems
and
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1194
ACKNOWLEDGMENTS 1194
REFERENCES 1194
SUbject Index 1207
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DEDICATION
Dr
Marion
L
Jackson
Emeritus Professor of Soil Science
Department of Soil Science
University of Wisconsin
Madison Wisconsin
It is very fitting that Minerals n
Soil Environments. 2nd edition be ded
icated to Professor Marion L Jackson
because
of
his important contributions
to the fledgling science
of
soil miner
alogy during his long and distinguished
career.
Marion Leroy Jackson was born in
Reynolds ebraska 14 ovember
1914 He received the B S degree max
ima cum laude with high distinction
in
1936 and the
M S
degree in 1937 from
the University of Nebraska. He began
his career in soil science working as a
land classification aide with the USDA
in Nebraska. He
was
granted the Ph.D.
in soil science at the University ofWis
consin
in 1939
Early in his career Dr.
Jackson
was
a soil chemist at Purdue
University and then
he
returned to the
University of Wisconsin. Dr. Jackson
progressed through the professional
ranks at the University
of
Wisconsin
and
he was
selected Franklin Hiram
King Professor in 1974. He was awarded an honorary Doctor of Science degree
in 1974 from the University of Nebraska.
In
1986 Professor Jackson was eJected
to the National Academy of Sciences.
Through his research Professor Jackson developed the leading weathering
sequence for clay minerals and a widely used set of methods for soil mineral
analysis. He made many other contributions to the understanding
of
soil minerals
their chemical properties and their roles
in
the environment. His scientific con
tributions are documented in 241 scientific publications including two books Soil
Chemical Analysis and Soil Chemical Analysis Advanced Course and
14
chapters
in
other books on soil chemistry soil mineralogy and other topics.
Dr. Jackson trained
59
Ph.D. and
18 M S
students who occupy numerous
positions of importance
in
clay and soil science
in
industry and
in
academia
throughout the world. Also he advised 37 postdoctoral research associates during
his tenure
as
a researcher and scholar.
Professor Jackson served as president of the Soil Science Society of America
and of the Clay Minerals Society. He was on the organizing committee of the
first edition
of
Minerals n Soil Environments. He contributed to the National
Research Council report on disposal of radioactive wastes and the U.S.S.R.-U.S A
xvii
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xviii DEDICATION
cooperative monograph on soils and climate. He contributed to the International
Conference on Clays in Environmental Sciences and lectured in medical schools
on trace substances in environmental health.
Professor Jackson has given many distinguished lectures at scientific meetings
including the Pioneer in Clay Science Lecture and the George W. Brindley Lecture
for the Clay Minerals Society. He has addressed the National Academy Sinica in
Nanking and Peking China and the European Academy o Sciences and Medicine
in West Germany. The latter lecture was on the geochemistry
o
elements as
related to health.
Throughout his career Professor Jackson has had the generous support o his
lovely wife Chrystie. She and Professor Jackson have four children.
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FOREWOR
A thorough knowledge and appreciation o the minerals in soils is critical to
our understanding and use
o soils for the betterment o mankind while protecting
our fragile environment. Scientists from many disciplines use this knowledge in
fundamental and adaptive research on soil erosion weathering classification
fertility physics chemistry and biochemistry as well as in the engineering aspects
o
soils. A critical new use is the application
o
this knowledge to waste-related
environmental problems including toxic waste cleanup and landfill siting.
The need for additional information on specific mineral groups as well as
the availability o additional significant research results led to a series o symposia
sponsored by Division
S 9
o
SSSA in 1984 and 1985 and a complete revising
o Minerals n Soil Environments This revision has much new material and
greatly expanded coverage
o
surface chemistry mineral equilibria soil organic
matter and numerous minerals. The editors have done a remarkable job
o
or
ganizing the book and providing the direction for a readable and usable volume.
The authors are world renowned and all have contributed state-of-the-art chapters.
This book will be the first number in the newly established SSSA Book Series.
Finally it is so very fitting that this book be dedicated to Professor M. L
Jackson. He is one o the truly great soil scientists
o
this century and it has been
my personal privilege to have received the benefits
o
his wisdom during my
career at the University o Wisconsin.
xix
D. R. KEENEY
president
Soil Science Society o America
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PREF CE
Like its predecessor the second edition o Minerals in Soil Environments was
developed by Division
S-9 o
the Soil Science Society
o
America. Symposia on
Recent Developments in Soil Mineralogy were held in 1984 and 1985 where
materials were presented for 14 o the chapters. Due to the growth
o
research
results and the need to develop
full
chapters on mineral groups that had been
aggregated in the first edition, chapters on methods, shrink-swell, and interactions
o organic compounds with minerals were eliminated. These subjects are covered
in other publications-those dealing with mineralogical methods o analysis are
covered in the second edition
o Methods o Soil Analysis Part 1
(1986). The
new edition has been reorganized to better serve
as
a graduate text and
as
a
reference for mineralogy o soils.
Chapters from the first edition o
Minerals in Soil Environments
have been
rewritten and several new chapters have been added. The first five chapters pro
vide general coverage
o
introductory mineralogy, surface chemistry, mineral
equilibria, soil organic matter, and mineral occurrence. The remaining 18 chapters
are devoted to minerals in various chemical and structural groups. The authors
were selected,
as
in the first edition, from among scientists
who
have particular
interest in and experience with their subject matter. Thus, the book has an in
ternational selection o
38
authors. The 23 chapters contain nearly 400 figures
140
tables, problems and exercises, and
key
references for study.
The introductory chapter by
D.
G. Schulze is entirely new and contains 13
new illustrations. A new chapter
by
M. B. McBride addresses the surface chemistry
o minerals in a modern analytical way. A new chapter on organic matter by J.
M. Oades is included because o the ubiquitous occurrence o this important soil
component in association with minerals in surface horizons. Coverage
o
soil
organic matter is more thorough and information from new methods
o
organic
matter analysis are discussed. The chapter on mineral equilibria
by
D. Rai and
J.
A. Kittrick is more rigorous and detailed than in the previous edition. Also,
it includes new material on mineral equilibria in relation to radioactive elements
in the soil environment. B. L Allen and B F. Hajek have completely rewritten
the chapter that interfaces mineralogy with soil taxonomy. Their chapter is a
valuable reference on mineral occurrence in soils
o
the world.
A new chapter on pyrophyllite and talc has been written
by L W.
Zelazny
and
G.
N. White to introduce these minerals early in the book where they are
usually taught to students. A new chapter on palygorskite and sepiolite has been
written by
A.
Singer reflecting the author s experience in the Middle East where
these minerals frequently occur. A significant new chapter on zeolites in soils has
been written by D. W. Ming and F. A. Mumpton. A comprehensive new chapter
on titanium and zirconium minerals has been written by A. R. Milnes and R.
W. Fitpatrick o Australia. Each o the other chapters has been rewritten and
xxi
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xxii
PREFACE
updated to keep it current with the recent literature. Thus the second edition
o
Minerals in Soil Environments
has a vast amount
o
new information.
During the preparation
o
such a large volume there have been many un-
named scientists students and editors who have contributed to the final volume
and
we
are grateful for their generous help.
J. B.
DIXON
co-editor
Department ofSoil
and
Crop Sciences
Texas
A M
University
College Station Texas
S.
B.
WEED co-editor
Department of Soil Science
North Carolina State University
Raleigh North Carolina
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B. L. Allen
R. I Barnhisel
Paul
M
Bertsch
Glenn Borchardt
Sen H Chien
J B. Dixon
Harvey E. Doner
Lowell A. Douglas
L. Richard Drees
M A.
EI-Desoky
D. S. Fanning
R.
W. Fitzpatrick
Ben F. Hajek
Pa Ho
Hsu
P. M Huang
V. Z. Keramidas
James A. Kittrick
Willard L. Lindsay
Warren C. Lynn
M B. McBride
CONTRI UTORS
Professor
of
Soils, Plant and Soil Science Department, Texas
Tech University, Lubbock, Texas
Professor
of
Agronomy and Geology, Department
of
Agronomy,
University
of
Kentucky, Lexington, Kentucky
Assistant Professor, Savannah River Ecology Laboratory, Uni
versity
of
Georgia, Aiken, South Carolina
Soil Mineralogist, California Division
of
Mines and Geology,
San Francisco, California
Soil Chemist, Agro-Economic Division, International Fertilizer
Development Center, Muscle Shoals, Alabama
Professor of Soil Mineralogy, Department
of
Soil and Crop Sci
ences, Texas A M University, College Station, Texas
Professor
of
Soil Chemistry, Department
of
Plant and Soil Bi
ology, University of California, Berkeley, California
Professor of Soil Mineralogy, Department of Soils and Crops,
Cook College, Rutgers University, New Brunswick, New Jersey
Associate Research Scientist, Department of Soil and Crop Sci
ences, Texas A M University and Texas Agricultural Experi
ment Station, College Station, Texas
Formerly Graduate Student, Department
of
Agronomy, Uni
versity
of
Maryland, College Park, Maryland. Now at Depart
ment ofSoil Science, College ofAgriculture, University ofAssiut,
Assiut, Egypt
Professor
of
Soil Science, Department
of
Agronomy, University
of
Maryland, College Park, Maryland
Principal Research Scientist, CSIRO Division
of
Soils, Glen Os
mond, South Australia
Professor ofSoil Science, Agronomy and Soils Department, Au
burn University, Auburn, Alabama
Professor
of
Soil Chemistry, Department
of
Soils and Crops,
Cook College, Rutgers University, New Brunswick, New Jersey
Professor
of
Soil Science, Department
of
Soil Science, University
of Saskatchewan, Saskatoon, Saskatchewan, Canada
Assistant Professor
of
Soil Science, Laboratory
of
Soil Science,
School
of
Agriculture, Aristotelian University, Thessaloniki,
Greece
Professor of Soil Science, Department of Agronomy and Soils,
Washington State University, Pullman, Washington
Professor, Department
of
Agronomy, Colorado State University,
Fort Collins, Colorado
Soil Scientist, Soil Conservation Service, U.S. Department
of
Agriculture, National Soil Survey Laboratory, Lincoln, Nebraska
Professor
of
Soil Chemistry, Department
of
Agronomy, Cornell
University, Ithaca, New York
xxiii
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xxiv
R. M. McKenzie
Douglas W.
Ming
A. R. Milnes
Frederick A. Mumptou
J.
M.
Oades
Dhanpat
Rai
Brij
L
Sawhney
Darrell G. Schulze
Udo Schwertmann
Abu L Senkayi
Arieh Singer
Neil
E.
Smeck
R. M. Taylor
Paul
L. G.
Vlek
Koji
Wada
G. N. White
Larry
P.
Wilding
Lucian W. Zelazny
CONTRIBUTORS
Formerly Senior Principal Research Scientist, CSIRO Division
of
Soils, Glen Osmond, South Australia. Now retired, Netherby,
South Australia
Space Scientist, National Aeronautics and Space Administration,
Lyndon
B
Johnson Space Center, Houston, Texas. Formerly
Graduate Research Assistant, Department of Soil and Crop Sci
ences, Texas A M University, College Station, Texas
Principal Research Scientist, CSIRO Division of Soils, Glen Os
mond, South Australia
Doctor, Department ofEarth Sciences, State University of New
York-College
at
Brockport, Brockport, New York
Professor, Department of Soil Science, Waite Agricultural Re
search Institute, University
of
Adelaide, Glen Osmond, South
Australia
Technical Leader, Geochemistry Section, Battelle, Pacific North
west Laboratories, Richland, Washington
Soil Chemist,
The
Connecticut Agricultural Experiment Station,
New Haven, Connecticut
Associate Professor of Agronomy, Department of Agronomy,
Purdue University, West Lafayette,
Indiana
Professor
of
Soil Science, Institut f r Bodenkunde, Technische
Universitat Miinchen, Freising-Weihenstephan, Federal Repub
lic of Germany
PRC Environmental Management, Inc.; 1 Dallas Center, 350 N
St. Paul Street; Suite 2600; Dallas, Texas 75201. Formerly Re
search Associate, Department
of
Soil
and
Crop Sciences, Texas
A M University, College Station, Texas
Professor of Soil Mineralogy, The Seagram Center for Soil and
Water Sciences, Faculty of Agriculture, Hebrew University of
Jerusalem, Rehovot, Israel
Professor of Agronomy, Department of Agronomy, The Ohio
State University, Columbus, Ohio
Doctor, CSIRO Division
of
Soils, Glen Osmond, South Australia
Inst.-Tropischen
Pflanzenbau
Grisebachstr.
6,
Goettingen
D3400, Germany. Formerly Division Director, International
Fertilizer Development Center-Africa, Lome, Togo
Professor of Soils, Department of Agricultural Chemistry, Fac
ulty
of
Agriculture, Kyushu University, Fukuoka, Japan
Formerly Graduate Research Assistant, Agronomy Department,
Virginia Polytechnic Institute and State University, Blacksburg,
Virginia.
Now
Research Associate, Department ofSoil and
Crop
Sciences, Texas A M University, College Station, Texas
Professor of Pedology, Department of Soil and Crop Sciences,
Texas A M University
and
Texas Agricultural Experiment Sta
tion, College Station, Texas
Professor of Agronomy, Agronomy Department, Virginia Pol
ytechnic Institute and State University, Blacksburg, Virginia
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xxvi
PERIODIC
T BLE
PERIODIC T BLE
O
THE ELEMENTS
Representative
elements Transition elements-d
I
Group IA
IIA IIIB
IVB VB VIB
VIIB
VIII
Valence
Period
shell
s s2
d
1
s
2
fx
d
2
s
2
d
3
s
2
§
dSs
§
d
S
s
2
d
6
s
2
§
1
n l
Is
1.008
3 4
n=
2s2p
Li
Be
6.941 9.012
12
n=3
3s3p
Na
Mg
22.99 24.31
19
20 21
22 23 24 25
26
n=4
4s3d4p K
Ca
Sc
Ti
V Cr Mn
Fe
39.10 40.08
44.96 47.90
50.94 52.00 54.94
55.85
37 38
39 40 41 42 43
44
n=5
5s4d5p
Rb
Sr
Y
Zr
Nb Mo
Tc
Ru
85.47
87.62 88.91
91.22 92.91 95.94 99.91 101.1
55
56 57 71
72
7
74
75
76
n=6 6s4f5d6p
Cs Ba
t
f
Ta
W
Re
as
133.0 137.3
178.5 180.9
183.9 186.2 190.2
87
88 89 103
n=7
7s5f6d7p
Fr
Ra
j
223 226.0
57
58 59
60
61
62
t Lanthanide
series
La
Ce
Pr
Nd
Pm
Sm
138.9 140.1
140.9
144.2 145 150.4
89
90
91
9
93
94
j Actinide series
Ac
Th Pa
U
Np
Pu
227
232
231 238 237.0
242
§ Variable valence shells.
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PERIODIC T BLE
xxvii
PERIODIC T BLE
O
THE ELEMENTS
Noble gas
Transition
elements d
Representative elements
elements
VIII
IB
liB lIlA IVA
VA
VIA
VIlA
0
(d
7
s
§ (d
B
s
§
s d o
s
s2p
s p
s
p
3 s
p
4 s
p
S s
p
6
2
He
4 003
5
6
7
8
9 10
B
C
N
0
F Ne
10.81 12.01 14.01 16 00
19 00
20 18
13
14 15 16 17 18
Al
Si
P
S
CI Ar
26.98 28.09
30 97 32 06
35 45
39 95
27 28 29 30 31 32 33 34 35 36
Co Ni
Cu
Zn Ga
Ge As
Se
Br
Kr
58 93
58.71
63 54
65 37 69 72
72.59
74 92
78.96
79.91
83 80
45
46
47
48
49
50
51
52 53 54
h
Pd
Ag
Cd
In
Sn Sb
Te I
Xe
102 9
106 4
107.9
112 4
114.9 118 7 12l 8 127 6 126 9 13l 3
78
79
80
81
82 83
84 85
86
r Pt Au
Hg
Tl
Pb Bi Po At
Rn
192 2
195.1
197 0
200 6
204 4
207 2 209 0
210 210
222
63 64 65 66 67
68
69 70
71
Eu
Gd
Tb
Dy
Ho Er Tm Yb Lu
152 157.2
159 162.5
164.9 167.3 168 9 173
175
95
96 97 98
99
100
101
102
103
Am Cm
Bk
Cf
Es
Fm
Md
No Lr
243 247 247 249
254
253
256
254 257