PREFACE
1 THE HYDROLOGIC CYCLE
Composition of Rainwater
Hydrology
Groundwater
Groundwater as a Resource and Groundwater Contamination
Nonmeteoric Types of Water
Chemical Terms in Hydrology
Suggested Reading
2 CHEMICAL BACKGROUND
Units and Terminology
Equilibrium Thermodynamics
Equilibrium Constant
Measurements of Disequilibrium
Activity-Concentration Relationships
Activities of Ionic Species
Complex Formation
Apparent Equilibrium Constants
Computer Codes
Review Questions
Suggested Reading
3 THE CARBONATE SYSTEM AND PH CONTROL
Carbonic Acid System
Alkalinity and Titration Curves
Alkalinity Titration
Gran Plots
Calcium Carbonate Solubility
Dolomite
High-Magnesium Calcite
Ground and Surface Waters in Carbonate Terrains
Review Questions
Suggested Reading
4 CLAY MINERALS AND CATION EXCHANGE
Mineralogy and Composition
Brucite [Mg(OH)2] and Gibbsite [Al(OH)3]
Kaolinite and Related Minerals
2:1 Clay Minerals
Chlorite
Mixed-Layer Clays
Sepiolite and Palygorskite
Colloid Properties
The Double Layer
Membrane Filtration
lon Exchange
Review Questions
Suggested Reading
5 ADSORPTION
Empirical Equations
Linear Distribution Coefficient
Freundlich Isotherm
Langmuir Isotherm
Surface Complexation
Acid-Base Equilibria
Adsorption of Metal Cations
Adsorption of Anions
The Electric Double Layer
Modeling Adsorption with MINTEQA2
Review Questions
Suggested Reading
6 ORGANIC COMPOUNDS IN NATURAL WATERS
Natural Organic Matter
Structure of Natural Organic Solutes
Functional Groups
Humic Substances
Dissolved Organic Carbon (DOC) in Natural Environments
Organic Pollutants
Solubility and Related Properties
Adsorption
Biodegradation and Bioremediation
Review Questions
Suggested Reading
7 REDOX EQUILIBRIA
The Standard Hydrogen Electrode and Thermodynamic Conventions
Use of Eh as a Variable
Use of pe as a Variable
Definition of pe and Eh by Redox Pairs
Measurement of Eh
Redox Calculations Using WATEQ4F
pe-pH and Eh-pH Diagrams
System Fe-O-H2O
System Fe-O-H2O-CO2
System Fe-O-H2O-S
Eh-pH Diagrams
Partial Pressure or Fugacity-Fugacity Diagrams
Review Questions
Suggested Reading
8 REDOX CONDITIONS IN NATURAL WATERS
Photosynthesis
Respiration and Decay
Redox Buffering
Lakes
The Ocean
Groundwater
Summary
Review Questions
Suggested Reading
9 HEAVY METALS AND METALLOIDS
Sources of Heavy Metals
Speciation
Organic Matter and Complex Formation
Equilibrium Solubility Control
Solubility in Redox Reactions
pe-pH and Eh-pH Diagrams
Roll-Front Uranium Deposits
Adsorption and Coprecipitation Controls
Adsorption by Hydrous Iron and Manganese Oxides
Adsorption by Silicates and Carbonates
Adsorption by Solid Organic Matter
Uptake by Living Organisms
Behavior of Specific Elements
Copper, Zinc, Cadmium, and Lead
Arsenic and Selenium
Chromium
Mercury
Summary
Review Questions
Suggested Reading
10 STABILITY RELATIONSHIPS AND SILICATE EQUILIBRIA
Solubility Equilibria (Congruent Solution)
Solubility of Magnesium Silicates
Solubility of Gibbsite
Solubility of Aluminosilicates
Incongruent Solution and Stability Diagrams
Uncertainty in Mineral Stability Diagrams
Review Questions
Suggested Reading
11 KINETICS
Nucleation
Dissolution and Growth
Surface Reaction Mechanisms
Diffusion Control
Dissolution of Calcite in Seawater
Growth of Calcite and Aragonite in Seawater
Dissolution of Silicates
Effect of Solution Composition on Dissolution Rates
Relative Dissolution Rates of Different Minerals
Comparisons Between Laboratory and Field Dissolution Rates
Review Questions
Suggested Reading
12 WEATHERING AND WATER CHEMISTRY
Soil Formation
The Mass-Balance Approach to Catchment Processes and Mineral Weathering Reactions
Catchment Processes
Mineral Weathering Reactions
Mass-Balance Calculations in Groundwater Systems
The Thermodynamic Approach to Mineral Weathering Reactions
The Statistical Approach
Case Studies
Mackenzie River System, Canada
Amazon and Orinoco River Systems
Absaroka Mountains, Wyoming
Mattole River, California
Cascade Mountains, Washington; Loch Vale, Colorado
Adirondack Mountains, New York
Waters from Ultramafic Rocks
Rhine River
Summary
Thermodynamic Controls on Clay Mineral Formation
Environmental Factors and Water Chemistry
Review Questions
Suggested Reading
13 ACID WATER
Acidity and Alkalinity
Solubility of Aluminum Hydroxide
Acid Deposition
Cation Exchange
Anion Mobility and Anion Exchange
Processes Affecting Sulfate Mobility
Biological Processes
Chemical Weathering
Integrated Models
Environmental Effects
Acid Mine Drainage
Prediction of Acid Generation
Prevention of Acid Generation
Review Questions
Suggested Reading
14 ISOTOPES
Stable Isotopes
Fractionation Processes
18O/16O and D/H
13C/12C
34S/32S
15N/14N
Radioactive Isotopes
Tritium
14C
Chlorine-36
Radon 222
Radiogenic Isotopes: Strontium-87
Review Questions
Suggested Reading
15 EVAPORATION AND SALINE WATERS
Evaporation of Sierra Nevada Spring Water
Chemical Divides and the Hardie-Eugster Model
Modifications of the Hardie-Eugster Model
Magnesium Carbonate Formation
Sulfate Reduction and Sulfide Oxidation
Ion Exchange and Adsorption
Cyclic Wetting and Drying
Examples
Lake Magadi Basin, Kenya
Teels Marsh, Nevada
Evaporation of Seawater
Persian Gulf Sabkhas
Saline Formation Waters
Summary
Review Questions
Suggested Reading
16 TRANSPORT AND REACTION MODELING
The Advection-Diffusion Equation
Advection
Diffusion and Dispersion
Chemical Reaction and Retardation
Reaction Path Modeling
Application to Contaminant Transport in Groundwater
Chemical Evolution of Groundwater
Review Questions
Suggested Reading
REFERENCES
GLOSSARY OF GEOLOGICAL TERMS
APPENDIX I PIPER AND STIFF DIAGRAMS
APPENDIX II STANDARD-STATE THERMODYNAMIC DATA FOR SOME COMMON SPECIES
APPENDIX III EQUILIBRIUM CONSTANTS AT 25°C AND ENTHALPIES OF REACTION FOR SELECTED REACTIONS
ANSWERS TO PROBLEMS
AUTHOR INDEX
SUBJECT INDEX
