François M.M. Morel is the Albert G. Blanke, Jr. Professor of Geosciences Emeritus at Princeton University. Janet G. Hering is Director Emerita of the Swiss Federal Institute of Aquatic Science and Technology and Professor Emerita of Environmental Biogeochemistry at ETH Zurich and of Environmental Chemistry at the École Polytechnique Fédérale de Lausanne. Laura Sigg is an internationally renowned expert in the aquatic geochemistry and ecotoxicology of trace metals. She is a former researcher at EAWAG, the Swiss Federal Institute of Aquatic Science and Technology, and Adjunct Professor at the Department of Environmental Systems Science of ETH Zurich.

• Preface xiAbout the Companion Website xiv1 Introduction to the Chemistry of Natural Waters 11.1 Water: Its Properties and Global Cycle 11.2 Chemical Processes in Natural Waters 61.3 Conservation, Thermodynamics, and Kinetics 13References 162 Conservation Principles and Equilibrium Calculations 172.1 Mole Balance Equations 182.2 Properties of Components 212.3 Solving Chemical Equilibrium Problems 252.4 Some Practical Considerations 342.5 Notation, Symbols, and Units 352.6 Components: A Matter of Terminology and History 38Problems 40References 423 Thermodynamics and Kinetics in Natural Waters 433.1 The Free Energy of Chemical Systems 453.2 Energetics of Chemical Reactions 483.3 Reaction Rates and Mechanisms 503.4 Effects of Ionic Strength on Equilibrium 563.5 Effect of Ionic Strength on Kinetics 623.6 Effect of Pressure on Equilibrium 633.7 Effect of Pressure on Kinetics 653.8 Effect of Temperature on Equilibrium 663.9 Effect of Temperature on Kinetics 683.10 Concentration Gradients in Equilibrium Systems 69Problems 73References 774 Acids and Bases: Alkalinity and pH in Natural Waters 794.1 Natural Weak Acids and Bases 804.2 Alkalinity and Related Concepts 824.3 Acid–Base Calculations for Natural Waters 914.4 Equilibrium with the Gas Phase 974.5 Mixing of Two Waters 1104.6 Effects of Biological Processes on pH and Alkalinity 1134.7 Humic Acids in Natural Waters 1184.8 Exchange Between Natural Waters and the Atmosphere 123Problems 131References 1355 Solid Dissolution and Precipitation: Acquisition and Control of Alkalinity 1385.1 The Chemical Nature of Rocks 1405.2 The Solubility of the Major Elements in the Upper Continental Crust: Si, Al, and Fe (+O) 1475.3 Alkalinity in Freshwaters: The Solubility of Ca, Mg, Na, and K 1505.4 The Control of Alkalinity in the Oceans 1615.5 Solubility of Trace Metals 1665.6 The Phase Rule 1765.7 Kinetics of Precipitation and Dissolution 178Problems 189References 1926 Complexation 1956.1 Aqueous Complexes 1966.2 Interactions Among Major Ions in Natural Waters 2046.3 Inorganic Complexation of Trace Metals 2076.4 Organic Complexation 2176.5 Complexation Kinetics 2366.6 Trace Metal Bioavailability to Microorganisms: The Case of Zn 247Problems 253References 2557 Oxidation–Reduction 2627.1 Definitions, Notations, and Conventions 2647.2 Comparison Among Redox Couples 2747.3 Energetics of Microbial Processes 2807.4 Redox Equilibrium Calculations 2937.5 pe–pH Diagrams 3007.6 Reactive Redox Species in Natural Waters 3097.7 Redox Kinetics 3197.8 The Bioavailability of Iron in Natural Waters 326Problems 330References 3318 Reactions on Solid Surfaces 3368.1 Aquatic Particles 3378.2 Coordinative Properties of Surfaces 3408.3 Chemical Reactions at (Conceptually) Isolated Surface Sites 3458.4 Electrostatic Interactions on Surfaces 3518.5 Acid–Base Reactions on Hydrous Ferric Oxide (HFO) 3578.6 Adsorption of Metals and Ligands on Hydrous Ferric Oxide (HFO) 3648.7 Other Reactions Involving Solid Phases 3678.8 Kinetic Considerations 369Problems 371References 372Index 377

François M.M. Morel is the Albert G. Blanke, Jr. Professor of Geosciences Emeritus at Princeton University. Janet G. Hering is Director Emerita of the Swiss Federal Institute of Aquatic Science and Technology and Professor Emerita of Environmental Biogeochemistry at ETH Zurich and of Environmental Chemistry at the École Polytechnique Fédérale de Lausanne. Laura Sigg is an internationally renowned expert in the aquatic geochemistry and ecotoxicology of trace metals. She is a former researcher at EAWAG, the Swiss Federal Institute of Aquatic Science and Technology, and Adjunct Professor at the Department of Environmental Systems Science of ETH Zurich.

• Preface xiAbout the Companion Website xiv1 Introduction to the Chemistry of Natural Waters 11.1 Water: Its Properties and Global Cycle 11.2 Chemical Processes in Natural Waters 61.3 Conservation, Thermodynamics, and Kinetics 13References 162 Conservation Principles and Equilibrium Calculations 172.1 Mole Balance Equations 182.2 Properties of Components 212.3 Solving Chemical Equilibrium Problems 252.4 Some Practical Considerations 342.5 Notation, Symbols, and Units 352.6 Components: A Matter of Terminology and History 38Problems 40References 423 Thermodynamics and Kinetics in Natural Waters 433.1 The Free Energy of Chemical Systems 453.2 Energetics of Chemical Reactions 483.3 Reaction Rates and Mechanisms 503.4 Effects of Ionic Strength on Equilibrium 563.5 Effect of Ionic Strength on Kinetics 623.6 Effect of Pressure on Equilibrium 633.7 Effect of Pressure on Kinetics 653.8 Effect of Temperature on Equilibrium 663.9 Effect of Temperature on Kinetics 683.10 Concentration Gradients in Equilibrium Systems 69Problems 73References 774 Acids and Bases: Alkalinity and pH in Natural Waters 794.1 Natural Weak Acids and Bases 804.2 Alkalinity and Related Concepts 824.3 Acid–Base Calculations for Natural Waters 914.4 Equilibrium with the Gas Phase 974.5 Mixing of Two Waters 1104.6 Effects of Biological Processes on pH and Alkalinity 1134.7 Humic Acids in Natural Waters 1184.8 Exchange Between Natural Waters and the Atmosphere 123Problems 131References 1355 Solid Dissolution and Precipitation: Acquisition and Control of Alkalinity 1385.1 The Chemical Nature of Rocks 1405.2 The Solubility of the Major Elements in the Upper Continental Crust: Si, Al, and Fe (+O) 1475.3 Alkalinity in Freshwaters: The Solubility of Ca, Mg, Na, and K 1505.4 The Control of Alkalinity in the Oceans 1615.5 Solubility of Trace Metals 1665.6 The Phase Rule 1765.7 Kinetics of Precipitation and Dissolution 178Problems 189References 1926 Complexation 1956.1 Aqueous Complexes 1966.2 Interactions Among Major Ions in Natural Waters 2046.3 Inorganic Complexation of Trace Metals 2076.4 Organic Complexation 2176.5 Complexation Kinetics 2366.6 Trace Metal Bioavailability to Microorganisms: The Case of Zn 247Problems 253References 2557 Oxidation–Reduction 2627.1 Definitions, Notations, and Conventions 2647.2 Comparison Among Redox Couples 2747.3 Energetics of Microbial Processes 2807.4 Redox Equilibrium Calculations 2937.5 pe–pH Diagrams 3007.6 Reactive Redox Species in Natural Waters 3097.7 Redox Kinetics 3197.8 The Bioavailability of Iron in Natural Waters 326Problems 330References 3318 Reactions on Solid Surfaces 3368.1 Aquatic Particles 3378.2 Coordinative Properties of Surfaces 3408.3 Chemical Reactions at (Conceptually) Isolated Surface Sites 3458.4 Electrostatic Interactions on Surfaces 3518.5 Acid–Base Reactions on Hydrous Ferric Oxide (HFO) 3578.6 Adsorption of Metals and Ligands on Hydrous Ferric Oxide (HFO) 3648.7 Other Reactions Involving Solid Phases 3678.8 Kinetic Considerations 369Problems 371References 372Index 377

François M.M. Morel is the Albert G. Blanke, Jr. Professor of Geosciences Emeritus at Princeton University. Janet G. Hering is Director Emerita of the Swiss Federal Institute of Aquatic Science and Technology and Professor Emerita of Environmental Biogeochemistry at ETH Zurich and of Environmental Chemistry at the École Polytechnique Fédérale de Lausanne. Laura Sigg is an internationally renowned expert in the aquatic geochemistry and ecotoxicology of trace metals. She is a former researcher at EAWAG, the Swiss Federal Institute of Aquatic Science and Technology, and Adjunct Professor at the Department of Environmental Systems Science of ETH Zurich.

• Preface xiAbout the Companion Website xiv1 Introduction to the Chemistry of Natural Waters 11.1 Water: Its Properties and Global Cycle 11.2 Chemical Processes in Natural Waters 61.3 Conservation, Thermodynamics, and Kinetics 13References 162 Conservation Principles and Equilibrium Calculations 172.1 Mole Balance Equations 182.2 Properties of Components 212.3 Solving Chemical Equilibrium Problems 252.4 Some Practical Considerations 342.5 Notation, Symbols, and Units 352.6 Components: A Matter of Terminology and History 38Problems 40References 423 Thermodynamics and Kinetics in Natural Waters 433.1 The Free Energy of Chemical Systems 453.2 Energetics of Chemical Reactions 483.3 Reaction Rates and Mechanisms 503.4 Effects of Ionic Strength on Equilibrium 563.5 Effect of Ionic Strength on Kinetics 623.6 Effect of Pressure on Equilibrium 633.7 Effect of Pressure on Kinetics 653.8 Effect of Temperature on Equilibrium 663.9 Effect of Temperature on Kinetics 683.10 Concentration Gradients in Equilibrium Systems 69Problems 73References 774 Acids and Bases: Alkalinity and pH in Natural Waters 794.1 Natural Weak Acids and Bases 804.2 Alkalinity and Related Concepts 824.3 Acid–Base Calculations for Natural Waters 914.4 Equilibrium with the Gas Phase 974.5 Mixing of Two Waters 1104.6 Effects of Biological Processes on pH and Alkalinity 1134.7 Humic Acids in Natural Waters 1184.8 Exchange Between Natural Waters and the Atmosphere 123Problems 131References 1355 Solid Dissolution and Precipitation: Acquisition and Control of Alkalinity 1385.1 The Chemical Nature of Rocks 1405.2 The Solubility of the Major Elements in the Upper Continental Crust: Si, Al, and Fe (+O) 1475.3 Alkalinity in Freshwaters: The Solubility of Ca, Mg, Na, and K 1505.4 The Control of Alkalinity in the Oceans 1615.5 Solubility of Trace Metals 1665.6 The Phase Rule 1765.7 Kinetics of Precipitation and Dissolution 178Problems 189References 1926 Complexation 1956.1 Aqueous Complexes 1966.2 Interactions Among Major Ions in Natural Waters 2046.3 Inorganic Complexation of Trace Metals 2076.4 Organic Complexation 2176.5 Complexation Kinetics 2366.6 Trace Metal Bioavailability to Microorganisms: The Case of Zn 247Problems 253References 2557 Oxidation–Reduction 2627.1 Definitions, Notations, and Conventions 2647.2 Comparison Among Redox Couples 2747.3 Energetics of Microbial Processes 2807.4 Redox Equilibrium Calculations 2937.5 pe–pH Diagrams 3007.6 Reactive Redox Species in Natural Waters 3097.7 Redox Kinetics 3197.8 The Bioavailability of Iron in Natural Waters 326Problems 330References 3318 Reactions on Solid Surfaces 3368.1 Aquatic Particles 3378.2 Coordinative Properties of Surfaces 3408.3 Chemical Reactions at (Conceptually) Isolated Surface Sites 3458.4 Electrostatic Interactions on Surfaces 3518.5 Acid–Base Reactions on Hydrous Ferric Oxide (HFO) 3578.6 Adsorption of Metals and Ligands on Hydrous Ferric Oxide (HFO) 3648.7 Other Reactions Involving Solid Phases 3678.8 Kinetic Considerations 369Problems 371References 372Index 377