, Tenth Edition
Environmental
Chemistry
Stanley Manahan
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
,Contents
Preface............................................................................................................................................ xxv
Acknowledgments..........................................................................................................................xxix
Author............................................................................................................................................ xxxi
Chapter 1 Environmental Chemistry and the Five Spheres of the Environment........................... 1
1.1 Earth and the Earth System................................................................................1
1.2 Biogeochemical Cycles in the Earth System......................................................1
1.2.1 Oxygen Cycle........................................................................................ 3
1.2.2 Nitrogen Cycle...................................................................................... 3
1.2.3 Sulfur Cycle.......................................................................................... 3
1.2.4 Phosphorus Cycle.................................................................................. 3
1.3 Natural Capital of the Earth System.................................................................. 4
1.4 What Is Environmental Chemistry?................................................................... 5
1.4.1 Environmental Chemistry and the Spheres of the Earth System..........6
1.5 Environmental Chemistry of Water and the Hydrosphere................................. 6
1.5.1 Water Pollution......................................................................................7
1.5.2 Water Treatment.................................................................................... 8
1.6 Environmental Chemistry of Air and the Atmosphere...................................... 8
1.6.1 Atmospheric Chemistry.......................................................................10
1.6.2 Air Pollution........................................................................................11
1.7 Environmental Chemistry of the Geosphere....................................................11
1.7.1 The Geosphere and Natural Capital.................................................... 13
1.7.2 Soil...................................................................................................... 13
1.7.3 Chemical Composition of Soil............................................................ 14
1.8 Environmental Chemistry of the Anthrosphere............................................... 14
1.8.1 Chemistry and the Anthrosphere.........................................................15
1.8.2 Industrial Ecology and Green Chemistry in the Anthrosphere...........16
1.9 Environmental Chemistry of the Biosphere.....................................................17
1.9.1 Biomaterials from the Biosphere........................................................ 19
1.9.2 Toxicological Chemistry and Biochemistry........................................ 20
1.9.3 Exposure to Toxic Substances.............................................................21
1.10 As We Enter the Anthropocene........................................................................ 21
1.10.1 Environmental Priorities for the Sustainocene....................................22
References................................................................................................................... 22
Further Reading...........................................................................................................23
Questions and Problems.............................................................................................. 23
Chapter 2 The Hydrosphere and Water Chemistry...................................................................... 25
2.1 Water: An Essential Part of Earth’s Natural Capital........................................ 25
2.2 Sources and Uses of Water............................................................................... 27
2.2.1 The Groundwater Crisis...................................................................... 28
2.3 H2O: Simple Formula, Remarkable Molecule.................................................. 29
2.4 Life in Water.................................................................................................... 31
2.5 Chemistry of Water.......................................................................................... 32
v
, 2.6 Gases in Water................................................................................................. 33
2.6.1 Oxygen in Water................................................................................. 33
2.7 Water Acidity and Carbon Dioxide in Water....................................................34
2.7.1 Carbon Dioxide in Water.................................................................... 35
2.8 Alkalinity..........................................................................................................38
2.8.1 Contributors to Alkalinity at Different pH Values............................. 39
2.8.2 Dissolved Inorganic Carbon and Alkalinity........................................ 40
2.8.3 Influence of Alkalinity on CO2 Solubility...........................................40
2.9 Calcium and Other Metals in Water.................................................................41
2.9.1 Hydrated Metal Ions as Acids............................................................. 41
2.9.2 Calcium in Water................................................................................ 42
2.9.3 Dissolved Carbon Dioxide and Calcium Carbonate Minerals............ 43
2.10 Complexation and Chelation............................................................................ 44
2.10.1 Occurrence and Importance of Chelating Agents in Water................ 46
2.11 Bonding and Structure of Metal Complexes.................................................... 47
2.11.1 Selectivity and Specificity in Chelation.............................................. 47
2.12 Calculations of Species Concentrations............................................................48
2.13 Complexation by Deprotonated Ligands.......................................................... 49
2.14 Complexation by Protonated Ligands...............................................................50
2.15 Solubilization of Lead Ion from Solids by NTA.............................................. 51
2.15.1 Reaction of NTA with Metal Carbonate............................................. 53
2.15.2 Effect of Calcium Ion on the Reaction of Chelating Agents
with Slightly Soluble Salts...................................................................54
2.16 Polyphosphates and Phosphonates in Water.....................................................55
2.16.1 Polyphosphates.................................................................................... 56
2.16.2 Hydrolysis of Polyphosphates..............................................................56
2.16.3 Complexation by Polyphosphates........................................................57
2.16.4 Phosphonates.......................................................................................57
2.17 Complexation by Humic Substances................................................................ 57
2.18 Complexation and Redox Processes................................................................. 59
References................................................................................................................... 59
Further Reading...........................................................................................................59
Questions and Problems.............................................................................................. 60
Chapter 3 Oxidation/Reduction in Aquatic Chemistry................................................................63
3.1 The Significance of Oxidation/Reduction in Aquatic Chemistry.....................63
3.2 The Electron and Redox Reactions.................................................................. 65
3.3 Electron Activity and pE.................................................................................. 67
3.4 The Nernst Equation.........................................................................................68
3.5 Reaction Tendency: Whole Reaction from Half-Reactions..............................69
3.6 The Nernst Equation and Chemical Equilibrium............................................. 70
3.7 The Relationship of pE to Free Energy............................................................ 71
3.8 Reactions in Terms of One Electron-Mole.......................................................71
3.9 The Limits of pE in Water................................................................................73
3.10 pE Values in Natural Water Systems................................................................74
3.11 pE–pH Diagrams.............................................................................................. 75
3.12 Humic Substances as Natural Reductants........................................................ 78
3.13 Photochemical Processes in Oxidation–Reduction...........................................79
3.14 Corrosion.......................................................................................................... 79
References................................................................................................................... 80
Further Reading.......................................................................................................... 81
Environmental
Chemistry
Stanley Manahan
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
,Contents
Preface............................................................................................................................................ xxv
Acknowledgments..........................................................................................................................xxix
Author............................................................................................................................................ xxxi
Chapter 1 Environmental Chemistry and the Five Spheres of the Environment........................... 1
1.1 Earth and the Earth System................................................................................1
1.2 Biogeochemical Cycles in the Earth System......................................................1
1.2.1 Oxygen Cycle........................................................................................ 3
1.2.2 Nitrogen Cycle...................................................................................... 3
1.2.3 Sulfur Cycle.......................................................................................... 3
1.2.4 Phosphorus Cycle.................................................................................. 3
1.3 Natural Capital of the Earth System.................................................................. 4
1.4 What Is Environmental Chemistry?................................................................... 5
1.4.1 Environmental Chemistry and the Spheres of the Earth System..........6
1.5 Environmental Chemistry of Water and the Hydrosphere................................. 6
1.5.1 Water Pollution......................................................................................7
1.5.2 Water Treatment.................................................................................... 8
1.6 Environmental Chemistry of Air and the Atmosphere...................................... 8
1.6.1 Atmospheric Chemistry.......................................................................10
1.6.2 Air Pollution........................................................................................11
1.7 Environmental Chemistry of the Geosphere....................................................11
1.7.1 The Geosphere and Natural Capital.................................................... 13
1.7.2 Soil...................................................................................................... 13
1.7.3 Chemical Composition of Soil............................................................ 14
1.8 Environmental Chemistry of the Anthrosphere............................................... 14
1.8.1 Chemistry and the Anthrosphere.........................................................15
1.8.2 Industrial Ecology and Green Chemistry in the Anthrosphere...........16
1.9 Environmental Chemistry of the Biosphere.....................................................17
1.9.1 Biomaterials from the Biosphere........................................................ 19
1.9.2 Toxicological Chemistry and Biochemistry........................................ 20
1.9.3 Exposure to Toxic Substances.............................................................21
1.10 As We Enter the Anthropocene........................................................................ 21
1.10.1 Environmental Priorities for the Sustainocene....................................22
References................................................................................................................... 22
Further Reading...........................................................................................................23
Questions and Problems.............................................................................................. 23
Chapter 2 The Hydrosphere and Water Chemistry...................................................................... 25
2.1 Water: An Essential Part of Earth’s Natural Capital........................................ 25
2.2 Sources and Uses of Water............................................................................... 27
2.2.1 The Groundwater Crisis...................................................................... 28
2.3 H2O: Simple Formula, Remarkable Molecule.................................................. 29
2.4 Life in Water.................................................................................................... 31
2.5 Chemistry of Water.......................................................................................... 32
v
, 2.6 Gases in Water................................................................................................. 33
2.6.1 Oxygen in Water................................................................................. 33
2.7 Water Acidity and Carbon Dioxide in Water....................................................34
2.7.1 Carbon Dioxide in Water.................................................................... 35
2.8 Alkalinity..........................................................................................................38
2.8.1 Contributors to Alkalinity at Different pH Values............................. 39
2.8.2 Dissolved Inorganic Carbon and Alkalinity........................................ 40
2.8.3 Influence of Alkalinity on CO2 Solubility...........................................40
2.9 Calcium and Other Metals in Water.................................................................41
2.9.1 Hydrated Metal Ions as Acids............................................................. 41
2.9.2 Calcium in Water................................................................................ 42
2.9.3 Dissolved Carbon Dioxide and Calcium Carbonate Minerals............ 43
2.10 Complexation and Chelation............................................................................ 44
2.10.1 Occurrence and Importance of Chelating Agents in Water................ 46
2.11 Bonding and Structure of Metal Complexes.................................................... 47
2.11.1 Selectivity and Specificity in Chelation.............................................. 47
2.12 Calculations of Species Concentrations............................................................48
2.13 Complexation by Deprotonated Ligands.......................................................... 49
2.14 Complexation by Protonated Ligands...............................................................50
2.15 Solubilization of Lead Ion from Solids by NTA.............................................. 51
2.15.1 Reaction of NTA with Metal Carbonate............................................. 53
2.15.2 Effect of Calcium Ion on the Reaction of Chelating Agents
with Slightly Soluble Salts...................................................................54
2.16 Polyphosphates and Phosphonates in Water.....................................................55
2.16.1 Polyphosphates.................................................................................... 56
2.16.2 Hydrolysis of Polyphosphates..............................................................56
2.16.3 Complexation by Polyphosphates........................................................57
2.16.4 Phosphonates.......................................................................................57
2.17 Complexation by Humic Substances................................................................ 57
2.18 Complexation and Redox Processes................................................................. 59
References................................................................................................................... 59
Further Reading...........................................................................................................59
Questions and Problems.............................................................................................. 60
Chapter 3 Oxidation/Reduction in Aquatic Chemistry................................................................63
3.1 The Significance of Oxidation/Reduction in Aquatic Chemistry.....................63
3.2 The Electron and Redox Reactions.................................................................. 65
3.3 Electron Activity and pE.................................................................................. 67
3.4 The Nernst Equation.........................................................................................68
3.5 Reaction Tendency: Whole Reaction from Half-Reactions..............................69
3.6 The Nernst Equation and Chemical Equilibrium............................................. 70
3.7 The Relationship of pE to Free Energy............................................................ 71
3.8 Reactions in Terms of One Electron-Mole.......................................................71
3.9 The Limits of pE in Water................................................................................73
3.10 pE Values in Natural Water Systems................................................................74
3.11 pE–pH Diagrams.............................................................................................. 75
3.12 Humic Substances as Natural Reductants........................................................ 78
3.13 Photochemical Processes in Oxidation–Reduction...........................................79
3.14 Corrosion.......................................................................................................... 79
References................................................................................................................... 80
Further Reading.......................................................................................................... 81
