Understanding Our Environment An Introduction to Environmental Chemistry and Pollution Third Edition Edited by Roy M Harrison The University of Birmingham, UK R S « C ROYAL SOCE ITY OF CHEMS ITRY ISBN 0-85404-584-8 A catalogue record for this book is available from the British Library © The Royal Society of Chemistry 1999 All rights reserved Apart from any fair dealing for the purposes of research or private study, or criticism or review as permitted under the terms of the UK Copyright, Designs and Patents Act, 1988, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 OWF, UK For further information see our web site at www.rsc.org Typeset by Paston PrePress Ltd, Beccles, Suffolk Printed by Redwood Books Ltd, Trowbridge, Wiltshire Preface The field of environmental chemistry goes from strength to strength Twenty-five years ago it existed in the UK in the form of a few isolated research groups in Universities, Polytechnics, and Research Institutes, but was very definitely a minority interest It was not taught appreciably in academic institutions and few books dealt with any aspect of the subject The awakening of environmental awareness, first in a few specialists and subsequently in the general public has led to massive changes Environmental chemistry is now a component (optional or otherwise) of many chemistry degree courses, it is taught in environmental science courses as an element of increasing substance, and there are even a few degree courses in the subject Research opportunities in environmental chemistry are a growth area as new programmes open up to tackle local, national, regional, or global problems of environmental chemistry at both fundamental and applied levels Industry is facing ever tougher regulations regarding the safety and environmental acceptability of its products When invited to edit the second edition of 'Understanding Our Environment', I was delighted to take on the task The first edition had sold well, but had never really met its original very difficult objective of providing an introduction to environmental science for the layman It has, however, found widespread use as a textbook for both undergraduate and postgraduate-level courses and deserved further development with this in mind I therefore endeavoured to produce a book giving a rounded introduction to environmental chemistry and pollution, accessible to any reader with some background in the chemical sciences Most of the book was at a level comprehensible by others such as biologists and physicians who have a modest acquaintance with basic chemistry and physics The book was intended for those requiring a grounding in the basic concepts of environmental chemistry and pollution The third edition follows very much the same ethos as the second, but I have tried to encourage chapter authors to develop a more international approach through the use of case studies, and to make the book more easily useable for teaching in a wide range of contexts by the incorporation of worked examples where appropriate and of student questions The book is a companion volume to 'Pollution: Causes, Effects and Control' (also published by the Royal Society of Chemistry) which is both more diverse in the subjects covered, and in some aspects appreciably more advanced Mindful of the quality and success of the second edition, it is fortunate that many of the original authors have contributed revised chapters to this book (A G Clarke, R M Harrison, B J Alloway, S J de Mora, C N Hewitt, R Allott, and S Smith) I am pleased also to welcome new authors who have produced a new view on topics covered in the earlier book (A S Tomlin, J G Farmer, M C Graham, and A Skinner) The coverage is broadly the same, with some changes in emphasis and much updating The authors have been chosen for their deep knowledge of the subject and ability to write at the level of a teaching text, and I must express my gratitude to all of them for their hard work and willingness to tolerate my editorial quibbles The outcome of their work, I believe, is a book of great value as an introductory text which will prove of widespread appeal Roy M Harrison Birmingham Contributors R Allott, AEA Technology, Risley, Warrington, WA3 6AT, UK B J Alloway, Department of Soil Science, University of Reading, Whiteknights, Reading, RG6 6DW, UK A G Clarke, Department of Fuel and Energy, Leeds University, Leeds, LS2 9JT, UK S J de Mora, Departement d'Oceanographie, Universite du Quebec a Rimouski, 300, allee des Ursulines, Rimouski, Quebec, G5L 3Al, Canada J G Farmer, Environmental Chemistry Unit, Department of Chemistry, The University of Edinburgh, King's Buildings, West Main Road, Edinburgh, EH9 3JJ, UK M C Graham, Environmental Chemistry Unit, Department of Chemistry, The University of Edinburgh, King's Buildings, West Main Road, Edinburgh, EH9 3JJ, UK R M Harrison, Institute of Public and Environmental Health, The University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK C N Hewitt, Institute of Environmental and Natural Sciences, Lancaster University, Lancaster, LAl 4YQ, UK A Skinner, Environment Agency, Olton Court, 10 Warwick Road, Solihull, B92 7HX, UK S Smith, Division of Biosphere Sciences, King's College, University of London, Campden Hill Road, London, W8 7AH, UK A S Tomlin, Department of Fuel and Energy, Leeds University, Leeds, LS2 9JT, UK Contents Preface v Contributors xvi Introduction 1 The Environmental Sciences The Chemicals of Interest 3 Units of Concentration The Environment as a Whole Bibliography The Atmosphere The Global Atmosphere 1.1 The Structure of the Atmosphere 1.1.1 Troposphere and Stratosphere 1.1.2 Atmospheric Circulation 1.1.3 The Boundary Layer 9 10 11 1.2 Greenhouse Gases and the Global Climate 1.2.1 The Global Energy Balance 1.2.2 The Carbon Dioxide Cycle 1.2.3 Global Warming 1.2.4 Climate Change 1.2.5 International Response 12 12 14 14 17 18 1.3 Depletion of Stratospheric Ozone 1.3.1 The Ozone Layer 1.3.2 Ozone Depletion 1.3.3 The Antarctic Ozone ‘Hole’ 1.3.4 Effects of International Control Measures 19 19 20 21 This page has been reformatted by Knovel to provide easier navigation 24 vii viii Contents Atmospheric Transport and Dispersion of Pollutants 25 2.1 Wind Speed and Direction 25 2.2 Atmospheric Stability 2.2.1 The Lapse Rate 2.2.2 Temperature Inversions 28 28 30 2.3 Dispersion from Chimneys 2.3.1 Ground-level Concentrations 2.3.2 Plume Rise 2.3.3 Time Dependence of Average Concentrations 31 31 32 Mathematical Modeling of Dispersion 33 Emissions to Atmosphere and Air Quality 35 3.1 Natural Emissions 3.1.1 Introduction 3.1.2 Sulfur Species 3.1.3 Nitrogen Species 3.1.4 Hydrocarbons 35 35 36 37 38 3.2 Emissions of Primary Pollutants 3.2.1 Carbon Monoxide and Hydrocarbons 3.2.2 Nitrogen Oxides 3.2.3 Sulfur Dioxide 3.2.4 Particulate Matter 3.2.5 Emissions Limits 3.2.6 Emissions Inventories 38 38 40 41 41 43 43 3.3 Air Quality 3.3.1 Air Quality Standards 3.3.2 Air Quality Monitoring 3.3.3 Air Quality Trends 3.3.4 Vehicular Emissions – CO and Hydrocarbons 3.3.5 Nitrogen Oxides 3.3.6 Sulfur Oxides 3.3.7 Vehicular Particulates 44 44 44 47 2.4 This page has been reformatted by Knovel to provide easier navigation 33 47 48 50 51 Contents 3.3.8 3.3.9 ix Heavy Metals Toxic Organic Micropollutants (TOMPS) 52 Gas Phase Reactions and Photochemical Ozone 53 4.1 Gas Phase Chemistry in the Troposphere 4.1.1 Atmospheric Photochemistry and Oxidation 4.1.2 Ozone 53 Trends in Ozone Levels 58 Particles and Acid Deposition 59 5.1 Particle Formation and Properties 5.1.1 Particle Formation 5.1.2 Particle Composition 5.1.3 Deliquescent Behaviour 5.1.4 Optical Properties 59 59 60 60 61 5.2 Droplets and Aqueous Phase Chemistry 62 5.3 Deposition Mechanisms 5.3.1 Dry Deposition of Gases 5.3.2 Wet Deposition 5.3.3 Deposition of Particles 63 63 64 65 5.4 Acid Rain 5.4.1 Rainwater Composition 5.4.2 The Effects 5.4.3 Patterns of Deposition and Critical Loads Assessment 66 66 67 Questions 69 4.2 52 53 56 68 Color Plates 70a Freshwaters 71 Introduction 71 Fundamentals of Aquatic Chemistry 74 2.1 74 74 Introduction 2.1.1 Concentration and Activity This page has been reformatted by Knovel to provide easier navigation x Contents 2.1.2 2.1.3 Ionic Strength Equilibria and Equilibrium Constants 75 77 Dissolution/Precipitation Reactions 2.2.1 Physical and Chemical Weathering Processes 2.2.2 Solubility 2.2.3 Influence of Organic Matter 79 2.3 Complexation Reactions in Freshwaters 2.3.1 Outer and Inner Sphere Complexes 2.3.2 Hydrolysis 2.3.3 Inorganic Complexes 2.3.4 Surface Complex Formation 2.3.5 Organic Complexes 82 82 82 83 84 84 2.4 Species Distribution in Freshwaters 85 2.4.1 pH as a Master Variable 85 2.4.2 pε as a Master Variable 97 2.4.3 pε – pH Relationships 100 2.5 Modeling Aquatic Systems 106 2.2 79 80 81 Case Studies 106 3.1 3.2 Acidification 3.1.1 Diatom Records 3.1.2 Aluminium 3.1.3 Acid Mine Drainage and Ochreous Deposits 3.1.4 Acid Mine Drainage and the Release of Heavy Metals 106 106 107 Metals in Water 3.2.1 Arsenic in Groundwater 3.2.2 Lead in Drinking Water 3.2.3 Cadmium in Irrigation Water 3.2.4 Selenium in Irrigation Water 3.2.5 Aquatic Contamination by Gold Ore Extractants 112 112 113 114 115 This page has been reformatted by Knovel to provide easier navigation 108 109 117 Contents 3.3 Historical Pollution Records and Perturbatory Processes in Lakes 3.3.1 Records – Lead in Lake Sediments 3.3.2 Perturbatory Processes in Lake Sediments 3.3.3 Onondaga Lake xi 119 119 119 123 3.4 Nutrients in Water and Sediments 125 3.4.1 Phosphorus and Eutrophication 125 3.4.2 Nitrate in Groundwater 129 3.5 Organic Matter and Organic Chemicals in Water 130 3.5.1 BOD and COD 130 3.5.2 Synthetic Organic Chemicals 131 Treatment 134 4.1 Purification of Water Supplies 134 4.2 Waste Treatment 135 Questions 136 Further Reading 138 The Oceanic Environment 139 Introduction 139 1.1 The Ocean as a Biogeochemical Environment 139 1.2 Properties of Water and Seawater 142 1.3 Salinity Concepts 146 1.4 Oceanic Circulation 148 Seawater Composition and Chemistry 150 2.1 Major Constituents 150 2.2 Dissolved Gases 2.2.1 Gas Solubility and Air-sea Exchange Processes 2.2.2 Oxygen 2.2.3 Carbon Dioxide and Alkalinity This page has been reformatted by Knovel to provide easier navigation 153 153 155 158 449 Index terms Links Intellectual deficits 393 Internal loading 126 Internet 435 Ion pairs 82 Ionic strength 75 IPPC 105 419 Directive 404 Iridium 177 Irish Sea 247 Iron 121 178 186 Irrigation water 114 Isokinetic sampling 292 152 181 188 Isoprene 38 Itai-Itai 113 233 80 204 172 182 189 K Kaolinite Kesterson Reservoir 115 Krypton 154 Kyoto 18 L Lagrangian trajectory modeling Lakes 34 257 sediments 369 119 Land contaminants 214 Land Use Planning 418 Landfilling 232 235 This page has been reformatted by Knovel to provide easier navigation 176 184 190 177 185 450 Index terms Landfill sites tax Links 273 429 Lanthanum 152 Lapse rate 28 Lead 52 171 197 260 391 lead-210 113 173 234 341 152 185 250 346 169 186 257 354 164 181 184 119 Leaded paintwork 262 Leaded petrol 261 Leblane Process 123 Lichens 355 Life Cycle Analysis 430 Lifetimes 240 264 Ligands 96 Liming 129 Limits 400 Line sources 269 Lithium 140 152 30 358 London smog 140 176 241 342 Long-path absorption measurements 324 Los Angeles 359 Lysocline 164 M Magnesium 151 188 deficiency 374 152 This page has been reformatted by Knovel to provide easier navigation 451 Index terms Manganese Marine aerosol Links 121 140 152 153 171 172 181 188 173 182 189 176 184 177 185 178 186 155 340 174 388 186 242 247 birds 384 environment 383 mammals 378 Mathematical modeling 33 Mean ion activity coefficient 76 Measurement of gaseous air pollutants 267 314 Mediterranean Sea 145 157 158 Mercury 117 175 142 176 152 188 Mesophyll tissues 344 Metal cations 210 344 354 38 155 complexation 93 ion mobility 96 pollution 388 toxicity 96 Metalliferous mining 233 Metals 339 in dusts 288 Meteorological data 318 Methaemoglobinaemia 130 Methane 13 Methanesulfonate 167 Methylation 113 Methyl bromide Methyl tert-butyl ether Methylchloroform 23 133 25 243 This page has been reformatted by Knovel to provide easier navigation 452 Index terms Links Methyl iodide 155 Methylmercury 118 390 Methyl radicals 54 Minamata 118 MINTEQA2 106 Mirabilite 144 Mixed acidity constant 341 346 15 23 25 388 390 78 Modeling of environmental dispersion 303 Molybdenum 185 Monitoring 267 protocol 317 Monomethylarsonic acid 113 Monsoons 148 Montreal Protocol 339 Multi-functionability approach 412 Mussel Watch 352 N National Air Quality Strategy 44 National Radiological Protection Board 278 National Survey of Air Pollution 276 Neon 154 Neutralization 129 Nickel 152 169 171 173 185 Nitrate 59 168 60 186 129 259 157 408 167 186 259 radical 167 Nitrate Vulnerable Zones 422 Nitrite 157 This page has been reformatted by Knovel to provide easier navigation 453 Index terms Nitrogen deposition Links 154 259 373 dioxide 41 242 340 344 oxides 37 40 48 155 259 13 37 246 145 164 169 188 190 249 250 264 334 338 340 156 365 N-Nitroso compounds Nitrous oxide Non-conservative 130 198 Non-conservative behaviour 142 Non-sea salt sulfate 151 Nonylphenol 132 North Sea 196 Number of sampling sites 316 Nutrients 98 O Objectives Occult deposition 400 64 Ocean basins 257 Octanol-water partition coefficient 211 Oil 383 spills 385 Organic contaminants Organic material 210 215 81 139 147 149 158 164 176 186 345 378 Organochlorine pesticides 352 Organochlorines 212 216 Organophosphate 216 350 Organophosphorus 131 Orthophosphate 126 This page has been reformatted by Knovel to provide easier navigation 381 454 Index terms Outer sphere complexes Links 82 Over-abstraction 398 Oxides of nitrogen 260 Oxygen 140 142 153 154 155 156 157 169 171 186 13 344 19 354 56 360 245 363 325 373 depletion 20 142 layer 19 150 157 168 212 384 218 386 231 339 Ozone P Pacific Ocean 149 Pacific oyster 379 PAHs 53 352 Palladium 177 Paraquat 209 Parathion 217 217 Particle formation 59 Particles 59 249 Paniculate matter 59 360 Partition coefficients Parts per billion Pasquill stability class PCBs 264 307 53 132 217 219 235 345 379 347 381 375 376 377 Pedogenic processes 202 Peritachlorophenol 410 Permeability 206 Peroxyacetyl nitrate 58 This page has been reformatted by Knovel to provide easier navigation 455 Index terms Links Peroxybenzoyl nitrate 58 Pesticides 72 131 211 352 pH 85 153 161 181 189 139 157 162 182 140 158 163 183 142 159 164 186 Phenol 338 Phosphate 125 167 168 170 Phosphorus 122 152 169 Photic zone 142 156 158 164 344 Photochemical ozone 53 Photochemical ozone creation potential (POCP) 57 Photochemical smog Photosynthesis PHREEQC Pinene 152 160 177 188 168 359 98 106 38 Pit lakes Pitzer equation 110 77 Placer gold 117 Planned emissions 270 Plants 362 Platinum 177 Plume rise 32 Plutonium 248 282 42 51 PM10 Podzolization 107 Point of zero charge 181 Point sources 269 Polar stratospheric clouds 340 182 22 This page has been reformatted by Knovel to provide easier navigation 360 361 456 Index terms Pollution control permit Polonium Links 190 191 197 200 152 172 184 188 156 157 177 427 185 Polychlorinated biphenyls see PCBs Polychlorinated dibenzodioxins 53 Polycyclic aromatic hydrocarbons, see PAHs Pore waters 121 Potassium 151 Potential density 146 Potential temperature 142 Precaution 413 Precision 321 Prerequisites for monitoring 316 Presentation of data 326 Primary minerals 79 Primary pollutants 36 Primary producers 367 Productivity 129 Protection zone 422 Proton transfer 101 Purification 134 Pycnocline 146 Pyrite 104 pε 97 145 322 135 140 186 pε–pH diagrams 100 Q QSAR 335 Quality assessment 398 Quality control procedures 317 This page has been reformatted by Knovel to provide easier navigation 457 Index terms Quartz Links 80 R Radon 277 Rain 255 Rainout 64 Rainwater composition 66 Reclamation 226 Recycling 430 Red Sea 145 Redox conditions 207 Redox equilibria 100 Redox intensity 97 Redox processes 99 Redox-sensitive elements 99 Reedbed 135 Remediating contaminated land 411 Remote sensing of pollutant 324 Reproduction 374 Residence time 142 Resistances to transfer 252 Respirable particles 341 Respiration 253 151 181 99 Respiratory disease 358 Respiratory tract 340 Restoration 128 Revelle factor 164 Risk Assessment 347 Risk-based Corrective Action 413 River water 255 Riverine suspended particulate matter 254 360 This page has been reformatted by Knovel to provide easier navigation 197 458 Index terms Links Rubidium 140 Ruthenium 177 S Saanich Inlet 157 Salinity 142 143 145 146 147 148 187 150 188 151 197 153 162 Salinization 115 Scandium 152 Scavenging coefficient Scavenging ratio 64 252 Sea breezes 31 Sea-salt 37 Seal populations 185 60 378 Secondary minerals 80 Secondary pollutants 36 135 Sediment 110 258 cores 123 soil and biological monitoring 285 Sedimentation 294 velocities 65 Selenium 115 142 Sellafield 247 283 Semen quality 381 Sewage effluent 382 Sewage sludge 114 Sigma-tee 146 Silicate 167 Silicic acid Silicon 176 218 168 170 169 181 81 152 This page has been reformatted by Knovel to provide easier navigation 459 Index terms Links Silver 177 Site investigation 220 Smectites 204 Smelting 110 233 42 50 Smoke particles 186 358 Sodium 151 172 152 173 184 Soil 201 262 370 and sediment sampling methods 302 cleaning 226 constituents 203 formation 202 organic matter 205 profile 202 properties 206 Solubility 81 Solubility product 81 Solvay process 123 Solvents 235 Soot 188 153 175 176 115 41 Source inventory 319 Source monitoring 271 Southern Ocean 148 Speciation 171 339 Specific conductance 75 Specific Ion Interaction Theory 77 Stability field 104 Stability limits of water 100 Standards 400 172 174 402 This page has been reformatted by Knovel to provide easier navigation 460 Index terms Stomata Stratosphere Stratospheric ozone depletion Strontium Subsidence inversion Subsidiarity Links 337 341 239 19 325 142 151 152 30 416 Sulfate 59 Sulfite 62 Sulfur 151 176 Sulfur dioxide 41 344 50 355 Sulfurous acid 62 Superfund 411 Supersaturation 153 Supply chain pressures 433 Surface charge 181 Surface complex 84 Surface resistance 246 Surface tension 143 Surfactants 143 Suspended particulates 299 Synthetic pyrethroids 131 106 358 T 2,4,5-T 216 Tailing ponds 110 TBT 195 196 197 TCDD 216 217 377 TCDF 216 217 Temperature inversions 217 30 This page has been reformatted by Knovel to provide easier navigation 151 362 340 461 Index terms Tertiary treatment 2,3,7,8-Tetrachlorodibenzodioxin Links 135 Tetraethyl lead 260 Tetramethyl lead 260 Thallium 176 Thermocline 145 Thorium 152 185 76 180 Titanium 152 153 Toluene 134 Tin Total suspended particulate matter 42 Toxic Organic Micropollutants (TOMPS) 52 Toxicity tests 185 299 333 334 Tradeable permits Trajectories 430 28 Transfer velocity 252 Tributyltin 194 Trichloroethene 133 Trigger concentrations 224 Tropopause 198 379 225 Tube wells 112 Turbidity 117 U Underground fuel tanks 413 Uniform emission standards 402 Units of concentration 403 405 Upwelling 149 Uranium 152 Uranium dioxide 153 168 This page has been reformatted by Knovel to provide easier navigation 462 Index terms Links US ambient air quality standards 323 US National Air Sampling Network 298 UV radiation 142 V Vanadium 152 Vegetation 337 Vehicular emissions Vermiculite 47 205 Vienna Convention 24 Visibility 61 Vitellogenin 133 Vivianite 126 Volatile organic compounds (VOCs) Volatilization 39 382 57 141 W Washout 64 coefficient 253 Waste disposal 232 Waste Framework Directive 429 Waste management hierarchy 430 Waste treatment 135 Waste waters 135 WATEQ4F 106 253 Water meadows 125 Quality Objectives 401 resources 431 sampling methods 300 table 112 This page has been reformatted by Knovel to provide easier navigation 463 Index terms Links Water Framework Directive 417 Weathering 179 of rock 255 Weddell Sea 149 Wet deposition 193 195 198 152 186 169 188 170 189 171 250 64 Wetlands 128 Wheal Jane tin mine 109 Wind shear 192 11 X Xylene 134 Z Zinc 122 185 Zooplankton 368 This page has been reformatted by Knovel to provide easier navigation