Description
Book SynopsisBased on the author's 15 years of teaching water-rock interactions and tried and tested in the classroom, Environmental Surfaces and Interfaces covers everything from the theory of charged particle surfaces to how minerals grow and dissolve to new frontiers in W-R interactions, such as nanoparticles, geomicrobiology, and climate change.
Table of ContentsPreface xv
Constants and Units xvii
Periodic Table of the Elements
1 Some Fundamental Chemical Thermodynamic and Kinetic Concepts 1
Concentration Units 1
Thermodyamic Versus Kinetic Approaches 2
Introductory Thermodynamics 3
Gibbs Energy 4
Chemical Potential and Activity 4
Equilibrium Constants 5
Calculating the Equilibrium Constant from Gibbs Energy Changes 6
Temperature Effects on Keq 8
Calculating Activities 9
Saturation Indices (SIs) 12
Carbonate Equilibria in Open or Closed Systems 13
Calcite Equilibria in a System Open to Atmospheric Carbon Dioxide 14
Redox Reactions 17
Metal Speciation Diagrams 19
A Brief Introduction to Kinetics 20
Overall Versus Elementary Reactions 20
Molecularity and Reaction Order 21
Transition State Theory and the Arrhenius Equation 24
Michaelis-Menten Kinetics 25
The Elovich Equation for Chemisorption Kinetics 26
Simultaneous Versus Sequential Reaction Sequences 27
Transport Versus Surface Control of Mineral Growth and Dissolution Rates 28
Rate Laws for Surface-Controlled Mineral Growth and Dissolution 30
Equilibration Time in Porous Media 31
Questions for Further Thought 31
Further Reading 34
2 The Hydrologic Cycle as Context for Environmental Surfaces and Interfaces 35
The Structure and Fundamental Properties of Water 35
The Chemical Composition of the Earth 37
The Critical Zone 38
The Hydrologic Cycle 38
Oceans 39
Atmosphere 40
Underground water 43
Soils and Soil Water 44
Groundwater 45
Surface Waters: Focus on Rivers 52
Stream Load 52
Gibbs Plots 54
The Hyporheic Zone 56
The OTIS Model and Solute Transport in Streams 56
Particle Transport and Sedimentation 57
Water Budgets and Chemical Fluxes in Terrestrial Ecosystems 59
Questions for Further Thought 62
Further Reading 66
3 Some Minerals of Special Interest to Environmental Surface Chemistry 67
Gibbsite 67
Quartz 68
Kaolinite 69
Smectite: Example Montmorillonite 71
Fe(hydr)oxides 73
Hematite 73
Goethite 73
Lepidocrocite 76
Maghemite 77
Ferrihydrite 77
Magnetite 77
Manganese Oxides 77
Calcite 78
Feldspars 79
Zeolites 79
Questions for Further Thought 81
Further Reading 81
4 Some Key Techniques for Investigating Surfaces and Interfaces 82
A Brief Overview of Some Commonly Used Techniques 82
In-Depth Descriptions of Some Key Techniques 86
Scanning Electron Microscopy (SEM) 86
Transmission Electron Microscopy (TEM) 87
Scanning Tunneling Microscopy (STM) 90
Case Study: Imaging Parameters and High-Resolution Imaging of Hematite 91
AFM and Interfacial Forces 92
X-Ray Photoelectron Spectroscopy (XPS) 99
BET Surface Area Measurements 100
Some Synchrotron-Based Techniques 103
Microscopies for Biofilm Imaging 108
Questions for Further Thought 108
Further Reading 111
5 Surfaces and Interfaces 112
What is a Surface? What is an Interface? 112
The Challenges of Defining Surfaces and Interfaces 113
Surfaces are Complex 114
Relaxation and Reconstruction 114
Surface Sites 115
Surface Microtopography 116
Surface Free Energy 117
Water Near Surfaces 119
Dynamic Surfaces 120
Bacterial Substrates 120
Fractal Properties of Surfaces and Environmental Particles 120
Interdisciplinary Topic of Study 123
Surface Free Energy and Surface Excess 124
Surface Tension and Related Phenomena 126
Surfactants and Micelles 126
Contact Angle 127
The Young-Laplace Equation 128
Meniscus and Capillarity 128
The Gibbs Equation 130
Some Approaches to Surface and Interface Modeling 130
Case Study: Bacteria–Mineral–Gas Interactions in the Vadose Zone 132
Questions for Further Thought 133
Further Reading 135
6 The Charged Interface and Surface Complexation 136
Some Evidence for Surface Charge 136
Sources of Mineral Surface Charge 137
Points of Zero Charge 139
Case Study: The Surface Charge Properties of Kaolinitic Soils 140
Sorption Terminology 141
Cation Exchange Capacity 145
Sorption Isotherms 148
Adsorption Isotherm Equations 151
The Langmuir Isotherm Equation 151
The Freundlich Isotherm Equation 152
The Frumkin Isotherm Equation 153
The Double Layer, Gouy-Chapman Theory 153
Beyond Gouy-Chapman: Surface Complexation Models 155
Constant Capacitance Model (CCM) 161
The Diffuse Double Layer (DDL) Model 161
Triple Layer Model (TLM) 161
Charge Distribution CD/MUSIC Model 162
Model Verification and Validation 163
Case Study: Incorporating the Work Associated with Removal of Water During Adsorption into the TLM 164
DLVO Theory and Colloid Attachment in Porous Media 165
Questions for Further Thought 168
Further Reading 172
7 Sorption: Inorganic Cations and Anions 173
A Typical Sorption Experiment Design 174
Metal Cation Sorption 176
The Complexity of Cation Adsorption 179
Inorganic Anion Adsorption 183
Phosphate Adsorption 184
Nitrate Adsorption 186
Sulfate Adsorption 186
Carbonate Sorption 186
Importance of Redox State and Valence to Inorganic Ion Adsorption 187
Chromium 187
Neptunium 188
Uranium 188
Selenium 188
Case Study: Arsenic Speciation and Mobility 189
Questions for Further Thought 192
Further Reading 193
8 Sorption: Organic Compounds 194
A Brief Introduction to Organic Chemistry 195
Some Organic Compounds of Interest in Environmental Surface Chemistry 200
Polymers 200
Organic Surfactants, Including Fatty Acids 200
Humic Substances 201
Polycyclic Aromatic Hydrocarbons (PAHs) 202
Substituted Nitrobenzenes (SNBs) 204
Volatile Organic Compounds (VOCs) 205
Sorption of Simple Organic Ligands, Surfactants, and Natural Organic Matter 205
Adsorption of Simple Organic Ligands 205
Adsorption of Anionic Surfactants, Fatty Acids 207
Sorption of Cationic Surfactants 208
Sorption of Phospholipid Surfactants: Biomedical Implications 209
Adsorption of Humic And Fulvic Acids (NOM) 210
Metal–Ligand Coadsorption: Ternary Surface Complexes 214
Sorption of Some Organic Pollutants 215
Vapor Pressure, Solubility, and Density 215
The Octanol-Water Partition Constant, Kow 218
Organic Fuel and Solvent Leaks: Volatilization, Solubility, Density, and Kow 219
The Hammett Constant σ for Substituted Aromatic Acids Based on the Benzene Ring 220
Case Study: Sorption of SNBs 221
Molecular Dynamics (MD) Modeling of Atrazine Absorption 223
The K d Approach to Hydrophobic Organic Compound Transport in Porous Media 224
Activated Carbon and Sorption of VOCs 226
Questions for Further Thought 227
Further Reading 230
9 Mineral Nucleation and Growth 231
Saturation State and Mineral Nucleation: An Example of the Confluence of Thermodynamics and Kinetics 231
Hydroxypyromorphite Nucleation 233
Heterogeneous Nucleation and Epitaxial Growth 233
From Nucleation to Growth 236
Ostwald Ripening 236
Transport and Surface Controlled Growth 236
The Special Importance of Kink Sites 237
BCF Theory 238
Growth Mode and Driving Force 240
Case Study: Calcite Birth and Spread versus Spiral Growth: BCF Theory 241
Rates of Step Advancement 242
Impurities and Growth at Steps 245
Monte Carlo Simulations of Crystal Growth 246
Biomineralization 247
Carbonate Precipitation in the Marine Environment 249
Questions for Further Thought 251
Further Reading 252
10 Mineral Weathering and Dissolution 253
Chemical, Physical, and Biological Weathering 253
Thermodynamics of Mineral Weathering 256
Kinetics of Mineral Dissolution 260
Etch Pit Formation 261
Oxalate Promoted Dissolution of Hematite 263
Comparison of Laboratory- and Field-Based Dissolution Rates 264
Reactive Surface Area and Feldspar Dissolution 266
Rainfall and Weathering: An Example from the Hawaiian Islands 269
Case Study: Weathering in the Antarctic Dry Valleys 270
Reactors for Dissolution Experiments 273
The Use of Radiogenic Isotopes in Weathering Studies 276
Questions for Further Thought 276
Further Reading 279
11 Plants as Environmental Surfaces 280
Ecohydrology and Soil Moisture Balance 280
Some Notes on Angiosperm Physiology 282
The Nutrient Needs of Plants 282
Effects of Plants on Mineral Dissolution and Weathering 284
Modes of Plant Elemental Cycling 287
Plants and Biomineralization: Phytoliths 287
Plants and Formations in Limestone Caves 289
Phytoremediation as an Example of Plant-Mineral-Contaminant Interactions 291
Case Study: Phytoremediation of Atrazine 293
Questions for Further Thought 294
Further Reading 295
12 Microorganisms As Environmental Surfaces 296
How Microorganisms “make a Living” 298
Metabolic Pathways 298
Microbial Redox Reactions and Michaelis-Menten Kinetics 303
Microbial Temperature Ranges and Extremophiles 305
Microbial Growth Curves 306
Bacterial Groups 307
Bacterial Cell Walls 307
Bacterial Adhesion and Biofilms 309
Bacterial–Metal Interactions 312
Bacterial-Promoted Mineral Dissolution 313
Dissolution of Fe(III)(hydr)oxides by DIRB 313
Dissimilatory Metal-Reducing Bacteria 315
Microbial Effects on Carbonate Dissolution 315
The Importance of Field-Based Studies 317
Case Study: The In Situ Microcosm Approach 318
Coupling In Situ Microcosms with Community Analysis 318
Siderophores 320
Microbial Biomineralization 322
Carbonate Precipitation 322
Fe(III)(hydr)oxide Precipitaton: BIOS 323
Banded Iron Formations (BIF) 324
(Alumino)silicate Precipitation 326
Case Study: Bioremediation of U at the Oak Ridge National Laboratory Site 327
Microbial Fuel Cells 329
Questions for Further Thought 332
Further Reading 333
13 Environmental Nanoscience and Nanotechnology 335
What is a Nanoparticle? 335
Nanoparticle Occurrence and Distribution 337
What Makes a Nanoparticle Different? 339
Nanoparticle Surface Area, Stability, and Reactivity 340
Nanoparticles Have a Different Electronic Structure 340
How Electronic Structure Influences Nanoparticle Behavior 342
Nanoparticle Disorder and Defect Structures 343
Ferrihydrite Size, Structure, and Stability 343
Effects of pH and Adsorbed Ions on Nanoparticle Stabilities 344
Case Study: Fe(hydr)oxide Size and Stability 345
Secondary Growth of Nanoparticles 346
Self-Assembly and Templating 348
Nanoparticle Transport in Porous Media 348
The Emergence of Nanotechnology 350
Potential Environmental Effects of Engineered Nanoparticles 351
Questions for Further Thought 353
Further Reading 354
14 The Big Picture: Interface Processes and the Environment 356
Reactive Transport Models for Metals and Radionuclides in Porous Media 356
The K d Approach Encounters Difficulties for Metals and Radionuclides 356
Comparison of the K d versus Surface Complexation Modeling Approaches 357
Acid Rain Effects on Chemical Weathering 358
What Makes Rainfall Acidic? 359
Effects of Acid Rain 360
Acid Rain and Chemical Weathering 360
The Small Watershed Approach 362
NETPATH and PHREEQC 362
The Clean Air Act and Acid Rain Over Time 363
Acid Mine Drainage 364
The Environmental Problem 365
Nanoparticles and AMD 365
Hydrobiogeochemical and Photoreductive Processes 365
Biofilms and AMD 367
Potential Remediation Strategies 369
Environmental Particles and Climate Change 369
Climate Forcing and Feedbacks 370
Volcanoes and Climate 373
CO2 and Weathering 374
Modeling the C Cycle Over Geologic Time 376
Scaling Phenomena: Integrating Observations from the Atomic to the Watershed to the Global Scale 378
The Concept of the Macroscope 378
Embedded Sensor Network Systems 379
Sensors for Surface and Interface Phenomena 380
New Opportunities: New Challenges 380
Questions for Further Thought 381
Further Readings 383
Glossary of Terms 385
References 405
Index 437
