Preface xi

About the Companion Website xiv

1 Introduction to the Chemistry of Natural Waters 1

1.1 Water: Its Properties and Global Cycle 1

1.2 Chemical Processes in Natural Waters 6

1.3 Conservation, Thermodynamics, and Kinetics 13

References 16

2 Conservation Principles and Equilibrium Calculations 17

2.1 Mole Balance Equations 18

2.2 Properties of Components 21

2.3 Solving Chemical Equilibrium Problems 25

2.4 Some Practical Considerations 34

2.5 Notation, Symbols, and Units 35

2.6 Components: A Matter of Terminology and History 38

Problems 40

References 42

3 Thermodynamics and Kinetics in Natural Waters 43

3.1 The Free Energy of Chemical Systems 45

3.2 Energetics of Chemical Reactions 48

3.3 Reaction Rates and Mechanisms 50

3.4 Effects of Ionic Strength on Equilibrium 56

3.5 Effect of Ionic Strength on Kinetics 62

3.6 Effect of Pressure on Equilibrium 63

3.7 Effect of Pressure on Kinetics 65

3.8 Effect of Temperature on Equilibrium 66

3.9 Effect of Temperature on Kinetics 68

3.10 Concentration Gradients in Equilibrium Systems 69

Problems 73

References 77

4 Acids and Bases: Alkalinity and pH in Natural Waters 79

4.1 Natural Weak Acids and Bases 80

4.2 Alkalinity and Related Concepts 82

4.3 Acid–Base Calculations for Natural Waters 91

4.4 Equilibrium with the Gas Phase 97

4.5 Mixing of Two Waters 110

4.6 Effects of Biological Processes on pH and Alkalinity 113

4.7 Humic Acids in Natural Waters 118

4.8 Exchange Between Natural Waters and the Atmosphere 123

Problems 131

References 135

5 Solid Dissolution and Precipitation: Acquisition and Control of Alkalinity 138

5.1 The Chemical Nature of Rocks 140

5.2 The Solubility of the Major Elements in the Upper Continental Crust: Si, Al, and Fe (+O) 147

5.3 Alkalinity in Freshwaters: The Solubility of Ca, Mg, Na, and K 150

5.4 The Control of Alkalinity in the Oceans 161

5.5 Solubility of Trace Metals 166

5.6 The Phase Rule 176

5.7 Kinetics of Precipitation and Dissolution 178

Problems 189

References 192

6 Complexation 195

6.1 Aqueous Complexes 196

6.2 Interactions Among Major Ions in Natural Waters 204

6.3 Inorganic Complexation of Trace Metals 207

6.4 Organic Complexation 217

6.5 Complexation Kinetics 236

6.6 Trace Metal Bioavailability to Microorganisms: The Case of Zn 247

Problems 253

References 255

7 Oxidation–Reduction 262

7.1 Definitions, Notations, and Conventions 264

7.2 Comparison Among Redox Couples 274

7.3 Energetics of Microbial Processes 280

7.4 Redox Equilibrium Calculations 293

7.5 pe–pH Diagrams 300

7.6 Reactive Redox Species in Natural Waters 309

7.7 Redox Kinetics 319

7.8 The Bioavailability of Iron in Natural Waters 326

Problems 330

References 331

8 Reactions on Solid Surfaces 336

8.1 Aquatic Particles 337

8.2 Coordinative Properties of Surfaces 340

8.3 Chemical Reactions at (Conceptually) Isolated Surface Sites 345

8.4 Electrostatic Interactions on Surfaces 351

8.5 Acid–Base Reactions on Hydrous Ferric Oxide (HFO) 357

8.6 Adsorption of Metals and Ligands on Hydrous Ferric Oxide (HFO) 364

8.7 Other Reactions Involving Solid Phases 367

8.8 Kinetic Considerations 369

Problems 371

References 372

Index 377

The definitive text for water chemistry professionals and students worldwide.

Principles and Applications of Aquatic Chemistry provides a solid foundation for understanding the chemistry of lakes, oceans, rivers, estuaries, and other natural waters. Acclaimed for its user-friendly pedagogy, this classic textbook explains aquatic chemistry through the powerful application of the “tableau system,” which provides a systematic way to organize complex chemical equilibrium problems.

Now in its second edition, this title contains an entirely new introductory chapter and new coverage of ocean acidification, advances in dissolution kinetics, bioavailability of trace metals, redox kinetics, and updated thermodynamic data. The use of computer programs to calculate chemical equilibrium in natural waters is illustrated. Throughout this edition, revised and streamlined material is supported by new real-world examples and full-color illustrations.

Accessible to those with diverse backgrounds in the sciences and engineering, this essential textbook

• Covers the fundamentals of aquatic science, including chemical thermodynamics, acid-base, precipitation-dissolution, coordination, reduction-oxidation and adsorption reactions
• Explains the use of equilibrium calculations, essential tools for understanding the chemical composition of aquatic systems and the fate of inorganic pollutants
• Provides quantitative treatments of the kinetics of chemical reactions in natural waters
• Features new and updated content that reflects advances in understanding the chemistry of natural waters
• Includes new end-of-chapter questions of various levels of difficulty and a solutions manual

This comprehensive guide remains the perfect textbook for advanced students in chemistry, environmental science and engineering, marine science, geochemistry, oceanography, geology, fisheries, forestry, and environmental policy and management. It is also a valuable reference text for industry professionals, academic researchers, policymakers, and college and university instructors in relevant fields.