, Ten t h E d i t i o n
Environmental
Chemistry
,
, Ten t h E d i t i o n
Environmental
Chemistry
Stanley Manahan
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
,CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2017 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
Version Date: 20161107
International Standard Book Number-13: 978-1-4987-7693-6 (Hardback)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to
publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials
or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material repro
duced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any
form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming,
and recording, or in any information storage or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copy
right.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400.
CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been
granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identifica
tion and explanation without intent to infringe.
Library of Congress Cataloging‑in‑Publication Data
Names: Manahan, Stanley E., author.
Title: Environmental chemistry / Stanley Manahan.
Description: Tenth edition. | New York : CRC Press, [2017] | Includes bibliographical references and index.
Identifiers: LCCN 2016033397| ISBN 9781498776936 (hardcover : alk. paper) | ISBN 9781498776967 (e-book)
Subjects: LCSH: Environmental chemistry.
Classification: LCC QD31.2 .M35 2017 | DDC 628--dc23
LC record available at https://lccn.loc.gov/2016033397
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
,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
,vi Contents
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
,Contents vii
Further Reading.......................................................................................................... 81
Questions and Problems ............................................................................................. 81
Chapter 4 Phase Interactions in Aquatic Chemistry ................................................................... 85
4.1 Chemical Interactions Involving Solids, Gases, and Water ............................ 85
4.2 Importance and Formation of Sediments ........................................................ 85
4.2.1 Formation of Sediments ..................................................................... 86
4.2.2 Organic and Carbonaceous Sedimentary Materials .......................... 87
4.3 Solubilities ....................................................................................................... 87
4.3.1 Solubilities of Solids........................................................................... 88
4.3.2 Solubilities of Gases ........................................................................... 89
4.4 Colloidal Particles in Water .............................................................................90
4.4.1 Colloids in Water and Contaminant Transport by Colloids ............... 91
4.4.2 Kinds of Colloidal Particles ............................................................... 91
4.4.3 Colloid Stability .................................................................................92
4.5 The Colloidal Properties of Clays ................................................................... 93
4.6 Aggregation of Colloidal Particles ..................................................................94
4.6.1 Flocculation of Colloids by Polyelectrolytes ......................................94
4.6.2 Flocculation of Bacteria by Polymeric Materials............................... 95
4.7 Surface Sorption by Solids .............................................................................. 95
4.8 Solute Exchange with Bottom Sediments .......................................................96
4.8.1 Trace-Level Metals in Suspended Matter and Sediments ..................97
4.8.2 Phosphorus Exchange with Bottom Sediments.................................. 98
4.8.3 Organic Compounds on Sediments and Suspended Matter ............... 98
4.8.4 Bioavailability of Sediment Contaminants ...................................... 100
4.9 Interstitial Water ............................................................................................ 101
4.10 Phase Interactions in Chemical Fate and Transport ...................................... 101
4.10.1 Rivers................................................................................................ 101
4.10.2 Lakes and Reservoirs ....................................................................... 101
4.10.3 Exchange with the Atmosphere ........................................................ 102
4.10.4 Exchange with Sediments ................................................................ 102
References ................................................................................................................ 103
Further Reading........................................................................................................ 103
Questions and Problems ........................................................................................... 104
Chapter 5 Aquatic Microbial Biochemistry .............................................................................. 107
5.1 Aquatic Biochemical Processes..................................................................... 107
5.1.1 Microorganisms at Interfaces ........................................................... 107
5.2 Algae.............................................................................................................. 108
5.3 Fungi.............................................................................................................. 110
5.4 Protozoa......................................................................................................... 110
5.5 Bacteria.......................................................................................................... 110
5.5.1 Autotrophic and Heterotrophic Bacteria .......................................... 111
5.5.2 Oxic and Anoxic Bacteria ................................................................ 112
5.6 The Prokaryotic Bacterial Cell ...................................................................... 112
5.7 Kinetics of Bacterial Growth ........................................................................ 113
5.8 Bacterial Metabolism .................................................................................... 113
5.8.1 Factors Affecting Bacterial Metabolism .......................................... 114
5.8.2 Microbial Oxidation and Reduction ................................................. 116
,viii Contents
5.9 Microbial Transformations of Carbon ........................................................... 116
5.9.1 Methane-Forming Bacteria .............................................................. 116
5.9.2 Bacterial Utilization of Hydrocarbons ............................................. 118
5.9.3 Microbial Utilization of Carbon Monoxide ..................................... 118
5.10 Biodegradation of Organic Matter ................................................................ 119
5.10.1 Oxidation.......................................................................................... 119
5.10.2 Microbial Oxidation of Hydrocarbons ............................................. 119
5.10.3 Other Biochemical Processes in Biodegradation of Organics ......... 120
5.11 Microbial Transformations of Nitrogen......................................................... 121
5.11.1 Nitrogen Fixation.............................................................................. 122
5.11.2 Nitrification ...................................................................................... 123
5.11.3 Nitrate Reduction ............................................................................. 123
5.11.4 Denitrification .................................................................................. 124
5.12 Microbial Transformations of Phosphorus and Sulfur .................................. 124
5.12.1 Phosphorus Compounds................................................................... 124
5.12.2 Sulfur Compounds ........................................................................... 125
5.12.3 Oxidation of H2S and Reduction of Sulfate by Bacteria .................. 125
5.12.4 Microorganism-Mediated Degradation of Organic Sulfur
Compounds....................................................................................... 125
5.13 Microbial Transformations of Halogens and Organohalides ........................ 126
5.14 Microbial Transformations of Metals and Metalloids ................................... 127
5.14.1 Acid Mine Waters............................................................................. 128
5.14.2 Microbial Transitions of Selenium ................................................... 129
5.14.3 Microbial Corrosion ......................................................................... 130
References ................................................................................................................ 130
Further Reading........................................................................................................ 131
Questions and Problems ........................................................................................... 131
Chapter 6 Water Pollutants and Water Pollution....................................................................... 135
6.1 Nature and Types of Water Pollutants ........................................................... 135
6.1.1 Markers of Water Pollution .............................................................. 135
6.2 Elemental Pollutants...................................................................................... 135
6.3 Heavy Metals ................................................................................................. 137
6.3.1 Cadmium .......................................................................................... 137
6.3.2 Lead.................................................................................................. 138
6.3.3 Mercury ............................................................................................ 138
6.4 Metalloids ...................................................................................................... 139
6.5 Organically Bound Metals and Metalloids ................................................... 140
6.5.1 Organotin Compounds ..................................................................... 141
6.6 Inorganic Species .......................................................................................... 142
6.6.1 Cyanide............................................................................................. 142
6.6.2 Ammonia and Other Inorganic Pollutants ....................................... 142
6.6.3 Asbestos in Water ............................................................................. 143
6.7 Algal Nutrients and Eutrophication............................................................... 143
6.8 Acidity, Alkalinity, and Salinity.................................................................... 144
6.9 Oxygen, Oxidants, and Reductants ............................................................... 145
6.10 Organic Pollutants ......................................................................................... 146
6.10.1 Bioaccumulation of Organic Pollutants ........................................... 146
6.10.2 Sewage.............................................................................................. 146
, Contents ix
6.10.3 Soaps, Detergents, and Detergent Builders ...................................... 147
6.10.3.1 Soaps................................................................................. 147
6.10.3.2 Detergents ......................................................................... 148
6.10.3.3 Microbial Toxins............................................................... 149
6.11 Pesticides in Water......................................................................................... 150
6.11.1 Natural Product Insecticides, Pyrethrins, and Pyrethroids .............. 152
6.11.2 The Emergence of Neonicotinoid Insecticides................................. 153
6.11.3 DDT and Organochlorine Insecticides............................................. 154
6.11.4 Organophosphate Insecticides.......................................................... 154
6.11.5 Carbamates....................................................................................... 155
6.11.6 Fungicides ........................................................................................ 156
6.11.7 Herbicides......................................................................................... 156
6.11.8 Bipyridylium Compounds ................................................................ 157
6.11.9 Herbicidal Heterocyclic Nitrogen Compounds ................................ 157
6.11.10 Chlorophenoxy Herbicides ............................................................... 158
6.11.11 Miscellaneous Herbicides ................................................................ 158
6.12 Organochlorine Compounds in Water........................................................... 159
6.12.1 By-Products of Pesticide Manufacture............................................. 159
6.12.2 Polychlorinated Biphenyls ................................................................ 160
6.12.3 1,2,3-Trichloropropane in Groundwater........................................... 161
6.12.4 Naturally Occurring Chlorinated and Brominated Compounds...... 162
6.13 Emerging Water Pollutants, Pharmaceuticals, and Household Wastes ......... 162
6.13.1 Bactericides and Antibiotics............................................................. 163
6.13.2 Estrogenic Substances in Wastewater Effluents ............................... 164
6.13.3 Biorefractory Organic Pollutants ..................................................... 164
6.14 Radionuclides in the Aquatic Environment................................................... 166
References ................................................................................................................ 170
Further Reading........................................................................................................ 170
Questions and Problems ........................................................................................... 171
Chapter 7 World Water Crisis and Climate Change: Water Renovation and Recycling........... 175
7.1 The Most Important Body of Water—You .................................................... 175
7.2 Water Treatment and Water Use .................................................................... 176
7.3 Municipal Water Treatment ........................................................................... 176
7.3.1 Failures in Water Treatment ............................................................. 176
7.4 Treatment of Water for Industrial and Commercial Use ............................... 177
7.5 Wastewater Treatment ................................................................................... 178
7.5.1 Industrial Wastewater Treatment...................................................... 178
7.6 Advanced Water Treatment ........................................................................... 178
7.7 Aeration of Water .......................................................................................... 179
7.8 Removal of Solids.......................................................................................... 179
7.8.1 Dissolved Air Flotation .................................................................... 180
7.8.2 Membrane Filtration Processes ........................................................ 181
7.9 Removal of Calcium and Other Metals ......................................................... 182
7.9.1 Removal of Iron and Manganese ..................................................... 185
7.9.2 Removal of Heavy Metals from Water............................................. 185
7.10 Removal of Biodegradable Organics from Water and Sewage Treatment .... 186
7.10.1 Biodegradable Organics Removal from Wastewater........................ 186
7.10.2 Membrane Bioreactor....................................................................... 189
Environmental
Chemistry
,
, Ten t h E d i t i o n
Environmental
Chemistry
Stanley Manahan
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
,CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2017 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed on acid-free paper
Version Date: 20161107
International Standard Book Number-13: 978-1-4987-7693-6 (Hardback)
This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to
publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials
or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material repro
duced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint.
Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any
form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming,
and recording, or in any information storage or retrieval system, without written permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copy
right.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400.
CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been
granted a photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identifica
tion and explanation without intent to infringe.
Library of Congress Cataloging‑in‑Publication Data
Names: Manahan, Stanley E., author.
Title: Environmental chemistry / Stanley Manahan.
Description: Tenth edition. | New York : CRC Press, [2017] | Includes bibliographical references and index.
Identifiers: LCCN 2016033397| ISBN 9781498776936 (hardcover : alk. paper) | ISBN 9781498776967 (e-book)
Subjects: LCSH: Environmental chemistry.
Classification: LCC QD31.2 .M35 2017 | DDC 628--dc23
LC record available at https://lccn.loc.gov/2016033397
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
,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
,vi Contents
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
,Contents vii
Further Reading.......................................................................................................... 81
Questions and Problems ............................................................................................. 81
Chapter 4 Phase Interactions in Aquatic Chemistry ................................................................... 85
4.1 Chemical Interactions Involving Solids, Gases, and Water ............................ 85
4.2 Importance and Formation of Sediments ........................................................ 85
4.2.1 Formation of Sediments ..................................................................... 86
4.2.2 Organic and Carbonaceous Sedimentary Materials .......................... 87
4.3 Solubilities ....................................................................................................... 87
4.3.1 Solubilities of Solids........................................................................... 88
4.3.2 Solubilities of Gases ........................................................................... 89
4.4 Colloidal Particles in Water .............................................................................90
4.4.1 Colloids in Water and Contaminant Transport by Colloids ............... 91
4.4.2 Kinds of Colloidal Particles ............................................................... 91
4.4.3 Colloid Stability .................................................................................92
4.5 The Colloidal Properties of Clays ................................................................... 93
4.6 Aggregation of Colloidal Particles ..................................................................94
4.6.1 Flocculation of Colloids by Polyelectrolytes ......................................94
4.6.2 Flocculation of Bacteria by Polymeric Materials............................... 95
4.7 Surface Sorption by Solids .............................................................................. 95
4.8 Solute Exchange with Bottom Sediments .......................................................96
4.8.1 Trace-Level Metals in Suspended Matter and Sediments ..................97
4.8.2 Phosphorus Exchange with Bottom Sediments.................................. 98
4.8.3 Organic Compounds on Sediments and Suspended Matter ............... 98
4.8.4 Bioavailability of Sediment Contaminants ...................................... 100
4.9 Interstitial Water ............................................................................................ 101
4.10 Phase Interactions in Chemical Fate and Transport ...................................... 101
4.10.1 Rivers................................................................................................ 101
4.10.2 Lakes and Reservoirs ....................................................................... 101
4.10.3 Exchange with the Atmosphere ........................................................ 102
4.10.4 Exchange with Sediments ................................................................ 102
References ................................................................................................................ 103
Further Reading........................................................................................................ 103
Questions and Problems ........................................................................................... 104
Chapter 5 Aquatic Microbial Biochemistry .............................................................................. 107
5.1 Aquatic Biochemical Processes..................................................................... 107
5.1.1 Microorganisms at Interfaces ........................................................... 107
5.2 Algae.............................................................................................................. 108
5.3 Fungi.............................................................................................................. 110
5.4 Protozoa......................................................................................................... 110
5.5 Bacteria.......................................................................................................... 110
5.5.1 Autotrophic and Heterotrophic Bacteria .......................................... 111
5.5.2 Oxic and Anoxic Bacteria ................................................................ 112
5.6 The Prokaryotic Bacterial Cell ...................................................................... 112
5.7 Kinetics of Bacterial Growth ........................................................................ 113
5.8 Bacterial Metabolism .................................................................................... 113
5.8.1 Factors Affecting Bacterial Metabolism .......................................... 114
5.8.2 Microbial Oxidation and Reduction ................................................. 116
,viii Contents
5.9 Microbial Transformations of Carbon ........................................................... 116
5.9.1 Methane-Forming Bacteria .............................................................. 116
5.9.2 Bacterial Utilization of Hydrocarbons ............................................. 118
5.9.3 Microbial Utilization of Carbon Monoxide ..................................... 118
5.10 Biodegradation of Organic Matter ................................................................ 119
5.10.1 Oxidation.......................................................................................... 119
5.10.2 Microbial Oxidation of Hydrocarbons ............................................. 119
5.10.3 Other Biochemical Processes in Biodegradation of Organics ......... 120
5.11 Microbial Transformations of Nitrogen......................................................... 121
5.11.1 Nitrogen Fixation.............................................................................. 122
5.11.2 Nitrification ...................................................................................... 123
5.11.3 Nitrate Reduction ............................................................................. 123
5.11.4 Denitrification .................................................................................. 124
5.12 Microbial Transformations of Phosphorus and Sulfur .................................. 124
5.12.1 Phosphorus Compounds................................................................... 124
5.12.2 Sulfur Compounds ........................................................................... 125
5.12.3 Oxidation of H2S and Reduction of Sulfate by Bacteria .................. 125
5.12.4 Microorganism-Mediated Degradation of Organic Sulfur
Compounds....................................................................................... 125
5.13 Microbial Transformations of Halogens and Organohalides ........................ 126
5.14 Microbial Transformations of Metals and Metalloids ................................... 127
5.14.1 Acid Mine Waters............................................................................. 128
5.14.2 Microbial Transitions of Selenium ................................................... 129
5.14.3 Microbial Corrosion ......................................................................... 130
References ................................................................................................................ 130
Further Reading........................................................................................................ 131
Questions and Problems ........................................................................................... 131
Chapter 6 Water Pollutants and Water Pollution....................................................................... 135
6.1 Nature and Types of Water Pollutants ........................................................... 135
6.1.1 Markers of Water Pollution .............................................................. 135
6.2 Elemental Pollutants...................................................................................... 135
6.3 Heavy Metals ................................................................................................. 137
6.3.1 Cadmium .......................................................................................... 137
6.3.2 Lead.................................................................................................. 138
6.3.3 Mercury ............................................................................................ 138
6.4 Metalloids ...................................................................................................... 139
6.5 Organically Bound Metals and Metalloids ................................................... 140
6.5.1 Organotin Compounds ..................................................................... 141
6.6 Inorganic Species .......................................................................................... 142
6.6.1 Cyanide............................................................................................. 142
6.6.2 Ammonia and Other Inorganic Pollutants ....................................... 142
6.6.3 Asbestos in Water ............................................................................. 143
6.7 Algal Nutrients and Eutrophication............................................................... 143
6.8 Acidity, Alkalinity, and Salinity.................................................................... 144
6.9 Oxygen, Oxidants, and Reductants ............................................................... 145
6.10 Organic Pollutants ......................................................................................... 146
6.10.1 Bioaccumulation of Organic Pollutants ........................................... 146
6.10.2 Sewage.............................................................................................. 146
, Contents ix
6.10.3 Soaps, Detergents, and Detergent Builders ...................................... 147
6.10.3.1 Soaps................................................................................. 147
6.10.3.2 Detergents ......................................................................... 148
6.10.3.3 Microbial Toxins............................................................... 149
6.11 Pesticides in Water......................................................................................... 150
6.11.1 Natural Product Insecticides, Pyrethrins, and Pyrethroids .............. 152
6.11.2 The Emergence of Neonicotinoid Insecticides................................. 153
6.11.3 DDT and Organochlorine Insecticides............................................. 154
6.11.4 Organophosphate Insecticides.......................................................... 154
6.11.5 Carbamates....................................................................................... 155
6.11.6 Fungicides ........................................................................................ 156
6.11.7 Herbicides......................................................................................... 156
6.11.8 Bipyridylium Compounds ................................................................ 157
6.11.9 Herbicidal Heterocyclic Nitrogen Compounds ................................ 157
6.11.10 Chlorophenoxy Herbicides ............................................................... 158
6.11.11 Miscellaneous Herbicides ................................................................ 158
6.12 Organochlorine Compounds in Water........................................................... 159
6.12.1 By-Products of Pesticide Manufacture............................................. 159
6.12.2 Polychlorinated Biphenyls ................................................................ 160
6.12.3 1,2,3-Trichloropropane in Groundwater........................................... 161
6.12.4 Naturally Occurring Chlorinated and Brominated Compounds...... 162
6.13 Emerging Water Pollutants, Pharmaceuticals, and Household Wastes ......... 162
6.13.1 Bactericides and Antibiotics............................................................. 163
6.13.2 Estrogenic Substances in Wastewater Effluents ............................... 164
6.13.3 Biorefractory Organic Pollutants ..................................................... 164
6.14 Radionuclides in the Aquatic Environment................................................... 166
References ................................................................................................................ 170
Further Reading........................................................................................................ 170
Questions and Problems ........................................................................................... 171
Chapter 7 World Water Crisis and Climate Change: Water Renovation and Recycling........... 175
7.1 The Most Important Body of Water—You .................................................... 175
7.2 Water Treatment and Water Use .................................................................... 176
7.3 Municipal Water Treatment ........................................................................... 176
7.3.1 Failures in Water Treatment ............................................................. 176
7.4 Treatment of Water for Industrial and Commercial Use ............................... 177
7.5 Wastewater Treatment ................................................................................... 178
7.5.1 Industrial Wastewater Treatment...................................................... 178
7.6 Advanced Water Treatment ........................................................................... 178
7.7 Aeration of Water .......................................................................................... 179
7.8 Removal of Solids.......................................................................................... 179
7.8.1 Dissolved Air Flotation .................................................................... 180
7.8.2 Membrane Filtration Processes ........................................................ 181
7.9 Removal of Calcium and Other Metals ......................................................... 182
7.9.1 Removal of Iron and Manganese ..................................................... 185
7.9.2 Removal of Heavy Metals from Water............................................. 185
7.10 Removal of Biodegradable Organics from Water and Sewage Treatment .... 186
7.10.1 Biodegradable Organics Removal from Wastewater........................ 186
7.10.2 Membrane Bioreactor....................................................................... 189
