Physical and Chemical Processes in the Aquatic Environment

Erik R. Christensen is a UWM Distinguished Professor Emeritus in the College of Engineering and Applied Science of the University of Wisconsin-Milwaukee. In 2008 he was nominated by UWM for Wisconsin Distinguished Professorship. He has published >80 journal articles, one book chapter, and edited a book: Contaminated Aquatic Sediments (1993), based on an international conference. He is an associate editor and frequent reviewer for many journals.

Preface xi

1 TRANSPORT OF POLLUTANTS 1

1.1 Introduction, 1

1.2 Advection–Diffusion Equation with Reaction, 2

1.3 Steady-State Mixing in Estuaries, 4

1.3.1 Determination of Diffusivity D from Salinity Measurements, 5

1.3.2 Pollutant Prediction for an Estuary with Uniform Discharge, 5

1.3.3 Salinity in an Infinite Estuary with a Large Freshwater Discharge, 8

1.3.4 Conservative Pollutant Prediction for an Infinite Estuary with a Large Freshwater Discharge, 9

1.4 Time-Dependent Mixing in Rivers and Soil Systems, 10

1.5 Vertical Mixing, 14

1.5.1 The Radon Method, 16

1.5.2 The Tritium–helium-3 Method, 17

1.5.3 Evaluation of Mixing Based on Density Gradients, 19

1.6 Hydrodynamic Models, 20

1.7 Groundwater Plumes, 22

1.8 Sediment Mixing, 23

References, 25

2 SEDIMENTATION PROCESSES 28

2.1 Introduction, 28

2.2 210Pb Dating of Sediments, 29

2.2.1 Measurement of 210Pb Activity, 30

2.2.2 210Pb Activity Profiles, 33

2.3 137Cs and 239+240Pu Dating of Sediments, 38

2.4 Dated Records of Metals and Organic Pollutants, 42

2.5 Deconvolution of Sedimentary Records, 49

2.6 Chemical and Biological Degradation, 55

2.7 Sediments as a Source of Pollutants, 56

2.7.1 Phosphorus, 57

2.7.2 Metals, 57

2.7.3 Acid-volatile Sulfides, 58

2.7.4 Organics, 59

References, 60

3 ATMOSPHERIC INTERACTIONS 65

3.1 Introduction, 65

3.2 Atmospheric Deposition Processes, 66

3.2.1 Gaseous vs. Particulate Chemicals in the Atmosphere, 66

3.2.2 Dry Deposition with Aerosols, 68

3.2.3 Wet Deposition, 75

3.2.4 Gas Exchange, 78

3.3 Deposition and Gas Exchange of Organic Contaminants, 84

3.4 Marine and Freshwater Microlayers, 87

3.5 Case Study: Emission of VOCs from Wastewater Treatment Plants, 89

3.6 The Fugacity Model, 93

3.6.1 Fugacity Definitions and Basic Equations, 94

3.6.2 Levels of Complexity, 101

3.6.3 Example Calculations – Chlorobenzene, 103

References, 108

4 WATER CHEMISTRY 113

4.1 Introduction, 113

4.2 Carbonate and Alkalinity, 115

4.2.1 Dissolved CO2 and Carbonate Speciation in Water, 115

4.2.2 Solving Equilibrium pH, 117

4.2.3 Alkalinity, 120

4.2.4 Buffer Index, 124

4.3 Sulfur Chemistry, 127

4.3.1 Sulfur Redox Reactions in Water, 128

4.3.2 Sulfur in Sediment, 132

4.3.3 Acid Rain, 133

4.4 Impact of Global Warming on Natural Waters, 135

References, 136

5 NUTRIENTS 138

5.1 Introduction, 138

5.2 Input of Nutrients and Acidity, 140

5.3 Eutrophication, 143

5.3.1 Eutrophication Control, 148

5.3.2 Harmful Algal Blooms, 149

5.3.3 Cladophora, 155

5.4 Nitrogen, 156

5.4.1 The Nitrogen Cycle, 156

5.4.2 Nitrification and Denitrification, 159

5.4.3 N Removal, 166

5.5 Phosphorus, 169

5.5.1 The Phosphorus Cycle, 169

5.5.2 P Removal, 170

5.5.3 Case Study: Phosphorus from Wastewater Treatment, Stormwater, and Rivers in Milwaukee, Wisconsin, 172

5.6 Vitamins and Trace Metals, 173

References, 180

6 METALS 185

6.1 Introduction, 185

6.2 Trends, Measurement, and Toxicity, 186

6.3 Major Sources and Reactions of Metals in Water, 193

6.3.1 Atmospheric Deposition of Metals, 193

6.3.2 Hydration, Hydrolysis, and Complex Formation, 196

6.3.3 Dissolution of Metals from Minerals, 201

6.4 Behavior of Selected Metals in Water, 203

6.4.1 Mercury, 203

6.4.2 Zinc and Cadmium, 204

6.4.3 Arsenic, 207

6.5 Zero-Valent Iron in Remediation of Contaminated Water, 209

6.5.1 Dechlorination of Chlorinated Hydrocarbons, 209

6.5.2 Reduction of Uranium Carbonate, Chromate,

and Arsenate, 214

References, 215

7 ORGANIC POLLUTANTS 220

7.1 Introduction, 220

7.2 Important Organic Pollutant Groups, 221

7.2.1 Petrochemicals and Industrial Solvents, 221

7.2.2 Polycyclic Aromatic Hydrocarbons (PAHs), 223

7.2.3 Polychlorinated Biphenyls (PCBs), 223

7.2.4 Polyhalogenated Dibenzo-p-Dioxins and Dibenzofurans (PXDD/Fs), 226

7.2.5 Polybrominated Diphenyl Ethers (PBDEs) and other Flame Retardants, 226

7.2.6 Organochlorine Pesticides (OCPs), 232

7.2.7 Other Pesticides, 236

7.2.8 Perfluorinated Compounds (PFCs), 239

7.2.9 Pharmaceuticals and Personal Care Products (PPCPs) and other Endocrine Disrupting Compounds (EDCs), 240

7.3 Descriptors of Organic Molecules, 243

7.4 Basic Physicochemical Properties, 245

7.4.1 Vapor Pressure, 246

7.4.2 Aqueous Solubility, 247

7.4.3 Henry’s Law Constant, 248

7.4.4 Octanol–Water Partition Coefficient, 248

7.4.5 Air–Octanol Partition Coefficient, 249

7.5 Distribution of Organic Chemicals in Aquatic Environment, 249

7.5.1 Air–Water, 250

7.5.2 Water–Sediment, 250

7.5.3 Water–Biota and Sediment–Biota, 251

7.6 Transformations in Water, 252

7.6.1 Hydrolysis, 253

7.6.2 Photochemical Degradation, 255

7.6.3 Biological Degradation, 257

7.6.4 Case Study: Transformation of PBDEs in the Environment, 259

References, 261

8 PATHOGENS 268

8.1 Introduction, 268

8.2 Bacteria, 271

8.3 Protozoa, 272

8.3.1 Cryptosporidium, 273

8.4 Molecular Techniques for Detection of Pathogens, 276

8.4.1 Water, 276

8.4.2 Biosolids, 277

8.5 Pathogen Indicator Organisms and Surrogates, 277

8.5.1 Bacillus Subtilis, 280

8.5.2 E. Coli and Fecal Coliforms, 280

8.6 Bacterial Contamination of Recreational Waters, 281

8.6.1 Modeling, 283

8.6.2 Beaches, 286

8.6.3 Recreational Pools, 287

8.7 Pathogen Removal in Water and Wastewater Treatment, 288

8.7.1 Water, 288

8.7.2 Wastewater and Solid Waste, 289

8.7.3 Inactivation Kinetics, 290

References, 295

9 TRACERS 298

9.1 Introduction, 298

9.2 Natural vs. Artificial Tracers, 299

9.3 Radioisotopes, 300

9.4 Stable Isotopes, 301

9.5 Applications of Tracer Technology, 305

9.5.1 Stable Isotope Tracers, 305

9.5.2 N and O Stable Isotopic Compositions of Nitrate Sources, 309

9.5.3 Other Physical and Chemical Tracers, 310

9.5.4 Molecular-Based Biological Tracers, 314

9.6 Chemical Mass Balance Modeling, 315

9.6.1 CMB Model for PAHs in Kinnickinnic River, Wisconsin, 316

9.7 Factor Analysis, 320

9.7.1 Non-negative Constraints Matrix Factorization, 322

9.7.2 Positive Matrix Factorization, 331

9.7.3 Unmix, 335

References, 341

10 ECOTOXICOLOGY 347

10.1 Introduction, 347

10.2 Bioassays, 349

10.2.1 Fish, 350

10.2.2 Algae, 350

10.2.3 Daphnia, 351

10.3 Molecular Biology Tools, 353

10.3.1 Polymerase Chain Reaction (PCR), 353

10.3.2 Fluorescent in Situ Hybridization (FISH), 354

10.3.3 Gene Expression, 354

10.3.4 Biomarkers, 355

10.4 Human Health, 357

10.4.1 Fisheries Advisories, 357

10.4.2 Mercury, 358

10.4.3 Polychlorinated Biphenyls (PCBs), 358

10.5 Endocrine-Disrupting Chemicals, 359

10.6 Types of Toxicity, 360

10.6.1 Disinfection Byproducts, 361

10.6.2 Detoxification and Degradation, 361

10.6.3 Antibiotics, 362

10.6.4 Nanomaterials, 363

10.7 Models and Toxicity Tests, 364

10.7.1 Dose–Response Models for Single Toxicants, 364

10.7.2 Dose–Response Models for Multiple Toxicants, 369

10.7.3 Pulsed Toxicity Tests, 374

10.7.4 Chronic Toxicity Tests, 375

10.8 Quality Criteria, 376

10.8.1 Sediment Quality Criteria, 376

10.8.2 Water Quality Criteria, 381

10.8.3 Total Maximum Daily Loads, 381

References, 383

11 AMBIENT WATER QUALITY CRITERIA 389

11.1 Introduction, 389

11.2 A Primer on Ambient Water Quality Regulations, 390

11.3 Current US Water Quality Criteria, 391

11.3.1 Aquatic Life Criteria, 402

11.3.2 Human Health Criteria, 403

11.3.3 Organoleptic Effects, 404

11.4 Water Quality Databases, 404

APPENDIX 11.A Footnote for Table 11.1, 405

APPENDIX 11.B Footnote for Table 11.2, 408

APPENDIX 11.C Additional Notes, 410

References, 412

Index 415

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