Preface ........................................................ xi
1 TRANSPORT OF POLLUTANTS
1.1 Introduction ............................................ I
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
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
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
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
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
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
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
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
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 О 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
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
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.С Additional Notes ............................... 410
References .................................................... 412
Index ......................................................... 415
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