Interfacial Chemistry of Rocks and Soils (Surfactant Science)

273 Pages·2021·87.578 MB·English

by  Noémi M. Nagy, József Kónya

Interfacial Chemistry of
Rocks and Soils
Surfactant Science Series
Founding Editor: Martin J. Schick (1918–1998)
Series Editor: Arthur T. Hubbard
Books in the Surfactant Science series emphasize surfaces and interfaces, including basic prin-
ciples, major developments, and important applications. A substantial proportion of all physical
phenomena involve interfaces in one way or another, and the practical and commercial applica-
tions of interface science are numerous. The series covers experimental phenomena, behavior and
properties, major advances, experimental approaches, essential instrumental methods, theoretical
strategies, and important applications. The level of presentation is intended for readers having a
basic scientific training, such as advanced science students encountering the book topic for the
first time, as well as scientific professionals refreshing their knowledge of engineering aspects of
the topic and interface science.
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Electrokinetic Particle Transport in Micro/Nano-fluidics: Direct Numerical Simulation
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Shizhi Qian and Ye Ai
Nuclear Magnetic Resonance Studies of Interfacial Phenomena
Vladimir M. Gun’ko and Vladimir V. Turov
The Science of Defoaming: Theory, Experiment and Applications
Peter R. Garrett
Soil Colloids: Properties and Ion Binding
Fernando V. Molina
Surface Tension and Related Thermodynamic Quantities of Aqueous Electrolyte Solutions
Norihiro Matubayasi
Electromagnetic, Mechanical, and Transport Properties of Composite Materials
Rajinder Pal
Silicone Dispersions
Edited by Yihan Liu
Wetting and Spreading Dynamics, Second Edition
Edited by Victor Starov, Manuel G. Velarde
Interfacial Chemistry of Rocks and Soils, Second Edition
Noémi Nagy, József Kónya
Surfactants from Renewable Raw Materials
Edited by Divya Bajpai Tripathy, Anjali Gupta, Arvind Kumar Jain, Anuradha Mishra
For more information about this series, please visit: https://www.crcpress.com/
Surfactant-Science/book-series/CRCSURFACSCI
Interfacial Chemistry of
Rocks and Soils
Second Edition
No mi M. Nagy
é
J zsef K nya
ó ó
The cover photo shows cation exchanged montmorillonites.
Second edition published 2022
by CRC Press
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© 2022 Taylor & Francis Group, LLC
First edition published by CRC Press 2009
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ISBN: 978-0-367-85682-3 (hbk)
ISBN: 978-1-032-11725-6 (pbk)
ISBN: 978-1-003-02008-0 (ebk)
DOI: 10.4324/9780429318726
Typeset in Times
by Deanta Global Publishing Services, Chennai, India
Contents
Preface to the First Edition .......................................................................................ix
Preface to the Second Edition ...................................................................................xi
Authors ...................................................................................................................xiii
Chapter 1 Components of Soil- and Rock-Solution Systems ................................1
1.1 Solid: Soil and Rock ..................................................................1
1.1.1 Mineral and Chemical Composition of Rocks
and Soils .......................................................................2
1.1.1.1 Silicates .........................................................3
1.1.1.2 Oxides ...........................................................9
1.1.1.3 Other Minerals ..............................................9
1.1.2 Organic Matter in Soil ..................................................9
1.1.3 Particle and Pore Sizes, External and Internal
Surfaces ......................................................................12
1.2 Liquid: Soil and Groundwater Solutions .................................14
1.2.1 Compositions of Natural Water ..................................14
1.2.2 Parameters Affecting Chemical Speciation ...............15
1.2.3 Dissolution and Precipitation of Solids ......................22
1.2.4 Properties of Very Dilute Solutions ...........................27
1.3 Interface of Rock/Soil–Aqueous Solutions .............................29
1.3.1 The Structure of the Interface ....................................30
1.3.2 Characterization of the Interface of Geological
System/Groundwater ..................................................33
1.3.2.1 Characterization of External Surfaces ........33
1.3.2.2 Characterization of Internal Surfaces .........40
1.3.3 Interfacial Processes Related to External and
Internal Surfaces ........................................................41
1.3.3.1 Adsorption ..................................................41
1.3.3.2 Ion Exchange ..............................................42
1.3.3.3 Precipitation ................................................45
1.3.3.4 Evaluation and Separation of
Interfacial Processes ...................................45
1.3.4 Quantitative Treatment of Interfacial Processes ........46
1.3.4.1 Adsorption Isotherms .................................46
1.3.4.2 Treatment of Ion Exchange Processes ........51
1.3.4.3 Treatment of Simultaneous Ion
Exchange and Adsorption Processes ..........65
1.3.4.4 Treatment of Heterogeneous Isotope
Exchange .....................................................66
1.3.5 Catalytic Effects of Clays ...........................................67
v
vi Contents
1.3.6 Kinetics of Interfacial Processes in Rocks
and Soils .....................................................................69
1.3.6.1 Steps of Interfacial Reactions .....................70
1.3.6.2 Kinetics of Heterogeneous Isotope
Exchange .....................................................75
1.3.6.3 Migration of Water-Soluble Substances
in Rocks and Soils ......................................75
1.3.6.4 Disposal of Nuclear Waste in
Geological Formations................................77
References ..........................................................................................79
Chapter 2 Interfacial Processes in Geological Systems: Studies on
Montmorillonite Model Substance .....................................................91
2.1 Use of Montmorillonite as a Model Substance: The
Important Interfacial Processes on Montmorillonite ..............92
2.1.1 Crystal Structure and Layer Charge of
Montmorillonite .........................................................92
2.1.2 Clay–Water Interactions .............................................95
2.1.3 Edge Charges of Montmorillonite ..............................96
2.1.4 Montmorillonite as a Model Substance ......................97
2.2 Cation Exchange: Outer-Sphere Complexation .......................98
2.3 Synthesis and Characterization of Cation-Exchanged
Montmorillonites ...................................................................103
2.4 Surface Acid–Base Properties of Montmorillonite ...............107
2.4.1 Formation of Edge Sites on Montmorillonite...........107
2.4.2 Effect of Permanent Charge on the Study of
Edge Charges............................................................108
2.4.3 Acid–Base Properties of Cation-Exchanged
Montmorillonites ......................................................109
2.5 Ion Adsorption on the External Surfaces ..............................113
2.5.1 Some Examples of Ion Sorption Processes on
Montmorillonite .......................................................114
2.5.1.1 Sorption of Zinc Ion on Montmorillonite .....114
2.5.1.2 Sorption of Manganese Ion on
Montmorillonite ........................................116
2.5.1.3 Sorption of Palladium Ion on
Montmorillonite ........................................116
2.5.1.4 Sorption of Lead Ion on Montmorillonite .....118
2.6 Separation of Interfacial Processes of Montmorillonite .......118
2.7 Role of Hydrogen Ions in the Interfacial and Dissolution
Processes of Montmorillonite ................................................120
2.7.1 Effect of Hydrogen Ion on the Cation Exchange
Processes ..................................................................122
2.7.2 Acidic Destruction of Montmorillonite ....................127
Contents vii
2.8 Effect of Complexation Agents .............................................128
2.8.1 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite System .....................................132
2.8.2 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite/Manganese(II) Ion System ......136
2.8.3 Effect of Stability Constants on the Cation
Composition of the Interlayer Space ........................138
2.8.4 Effect of Complex Formation in the EDTA/
Ca-Montmorillonite/Lead(II) Ion System ................140
2.9 Sorption of Organic Matter on Minerals ...............................142
2.9.1 Sorption of EDTA on Montmorillonite ....................143
2.9.2 Sorption of Valine on Montmorillonite ....................144
On the Layer Charges ...............................................145
On the Edge Sites .....................................................145
2.10 Transformations Initiated by Interfacial Processes of
Montmorillonite .....................................................................149
2.10.1 Oxidation of Mn(II) Ion and Formation
of a Nanolayer in the Interlayer Space of
Montmorillonite .......................................................150
2.10.2 Formation of an Iron(III) Oxidhydroxide
Nanolayer in the Interlayer Space of
Montmorillonite .......................................................153
2.10.3 Reduction of Ions .....................................................158
2.10.3.1 Reduction of Silver and Palladium Ion .....158
2.10.3.2 Reduction of Fe(III) Ions ..........................160
2.10.4 Heterogeneous Nucleation on Edge Site:
Formation of Lead Oxide Fine Particles on the
Edges of Montmorillonite ........................................160
2.10.5 Lanthanide Ion Exchange: Structural
Modification Due to the Exchange with Light
Lanthanide and Ittrium Ions .....................................169
2.10.6 Structural Change upon Heating Lanthanide-
Bentonites .................................................................171
2.11 Effect of Chemical Modification of Bentonite on
Sorption Properties: Sorption of Anions ...............................172
References ........................................................................................177
Chapter 3 Interfacial Reactions at Rock and Soil Interfaces ............................187
3.1 Relationship between the Interfacial Properties and the
Geological Origin of Bentonite Clay .....................................187
3.1.1 Geological and Mineral Characteristics of
Sajóbábony Bentonites .............................................188
3.1.2 Interfacial Properties of Bentonite Samples from
Sajóbábony (HU) ......................................................193
viii Contents
3.1.3 Relations of Geological Origin and Interfacial
Properties .................................................................196
3.1.4 Applications of Bentonites of Different
Interfacial Properties ................................................197
3.2 Migration of Water-Soluble Substances in Rocks .................198
3.2.1 Sorption and Migration of Carrier-Free
Radioactive Isotopes in Rocks .................................198
3.2.1.1 A Model Predicting Migration Rate on
the Basis of Mineral Composition ............198
3.2.1.2 The Application of the Linear Model
for the Sorption of Cs-137 and Sr-85
Ions............................................................201
3.2.2 Effect of Sorption on the Migration of Ions in
Bentonite ..................................................................208
3.2.3 Effect of Precipitation in Migration .........................210
3.3 Interfacial Acid–Base Properties of Soils .............................212
3.4 Sorption of Cyanide Anion on Soil and Sediment ................218
3.5 Sorption of Phosphate Anion on Soils ...................................225
References ........................................................................................229
Chapter 4 Experimental Methods in Studying Interfacial Processes of
Rocks and Soils ................................................................................233
4.1 Analysis of the Solid Phase ...................................................233
4.1.1 Methods of Chemical Analyses ...............................233
4.1.2 Study of Mineral Composition .................................235
4.1.3 Study of Morphology ...............................................236
4.1.4 Study of Soil Organic Matter ...................................240
4.2 Analysis of the Liquid Phase .................................................240
4.3 Study of Interfaces .................................................................241
References ........................................................................................247
Index ......................................................................................................................249
Preface to the First Edition
Geological formations, soils, and rocks are essential components of the environ-
ment. Their chemistry and chemical transformations play an important role in the
quality of life for all living beings. Both natural and anthropogenic processes can
result in effects that last for a long time. We have to comprehend the basic interac-
tions that take place between geological materials and different substances in order
to be able to drive the processes toward advantageous results. One important group
of these interactions occurs on the interface of rocks and soil. In these so-called
interfacial reactions, the structure of the soil and rocks does not change significantly;
however, they are the first step toward any chemical and other transformations of the
soils and rocks. Thus, it is very important to understand the interfacial processes of
rocks and soils.
Soils and rocks can adsorb or absorb a wide variety of substances from the envi-
ronment. The mechanism and strength of sorption, and the chemical transformations
due to sorption, are influenced by mineral structure, interfacial forces, the geologi-
cal environment, and the chemical species produced as a result of such factors. The
interactions are complicated because of the large variety of chemical entities pres-
ent. For example, the chemical structure of soils and rocks can vary, and there may
be many different substances present, depending on the actual geochemical envi-
ronment. Furthermore, the presence of groundwater, dissolved minerals, and other
components as well as the pH, redox conditions, gaseous components (e.g., carbon
dioxide), complex forming agents, organic matter, living organisms, etc., do have an
important influence on the interactions.
In this book, the processes at solid/liquid interfaces of soil and rock, in most cases
under environmental conditions, will be discussed. A scientifically correct descrip-
tion of interfacial processes requires the study of the properties of solid and liquid
phases and the interface, as well as the interactions of these phases. Previous books
typically focus on selected aspects of the subject, such as, for example, the properties
of the solid phase or the interactions of selected substances such as heavy metal ions
with solid/rock. We intend to present a comprehensive treatment of the solid–liquid-
interface system, emphasizing the importance of the chemical species produced in
a geological material/solution/interface interaction. We recommend the book to all
chemists, geologists, and soil scientists working in interfacial, environmental, and
soil sciences.
The book consists of four chapters. The first one deals with the individual compo-
nents of the studied systems: the solid, the solution, and the interface. “Solid” means
rocks and soils, namely, the main mineral and other solid components. In order that
the solid/liquid interactions become possible, these must be located in the Earth’s
crust where the groundwater is present. The liquid phase refers to soil solution and
groundwater, and also any solutions that are part of laboratory experiments studying
interfacial properties with the objective of understanding the principles behind the
reactions.
ix