AIR POLLUTION AND ACID RAIN: The Biological Impact

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1 A DIRECTOR OF BIOCHEMISTRY, DEPARTMENT OF BIOLOGICAL SCIENCES, UNIVERSITY OF LANCASTER, UK AIR POLLUTION AND ACID RAIN: The Biological Impact Longman Scientific & Technical Copublished in the United States with John Wiley & Sons, Inc., New York

2 Contents 'I do not mean to say that all rain is acid; it is found with so much ammonia in it as to overcome the acidity; but in general, I think, the acid prevails in the town' From Air and Rain The Beginning of a Chemical Climatology written in 1872 by Robert Angus Smith. Acknowledgements xiv Chapter 1. Introduction Definitions and terms Units and concentrations Levels and limits Detection and indicators Thresholds and injury Composition and climate Particles and suspended matter 19 Selected bibliography 22 Chapter 2. Sulphur dioxide Sources and cycling of sulphur 23 (a) Man-made atmospheric changes 23 (b) Natural changes 27 (c) Microbial changes 29 (d) Reactions of sulphur dioxide in water and tissue fluids 36 ix

3 Air pollution and acid rain (e) Reactions of sulphite with y biomolecules / 2.2 Plants (a) Stomatal access (b) Internal resistance and buffering (c) Sulphur metabolism (d) Chloroplastidic damage (e) Long-term effects 2.3 Health effects (a) Irritant properties (b) Industrial and urban hazards (c) Toxicity of SO2 and SO^ within tissues Selected bibliography Chapter 3. Nitrogen-based air pollutants 3.1 Formation and sources (a) The Nitrogen cycle (b) Nitrous oxide (c) Combustion (d) Atmospheric oxidations (e) Dry-deposition / (f) Ammonia volatilisation / 3.2 Plants (a) Access (b) Root uptake (c) Damage or benefit? (d) Crops under glass (e) Prospectives 3.3 Health effects (a) Industrial accidents (b) The domestic scene (c) Lung damage (d) Metabolic changes Selected bibliography Chapter 4. Acid rain 4.1 Formation and deposition of acidity (a) Definitions and distinctions (b) Cloudwater acidity (c) Generation of sulphuric acid (d) Nitric acid formation (e) Other sources of acidity and alkalinity (f) Dispersion and transport (g) Removal and deposition

4 Contents 4.2 Consequences to physical systems 110 (a) Plant nutrients and soil acidity 110 (b) Evaporation and sublimation 115 (c) Acidity in rivers and lakes Plants 119 (a) Leaf injury and cuticular weathering 119 (b) Physiological and biochemical changes 120 (c) Foliar leaching and reproduction Animals 122 (a) Effects on water bodies and fisheries 122 (b) Mechanisms of toxicity in fish 124 (c) Effects on invertebrates and birds 127 (d) Direct or indirect effects upon humans 127 Selected bibliography 129 Chapter 5. Ozone, PAN and photochemical smog Formation and sources 130 (a) Monatomic oxygen, ozone and hydroxyl radicals 130 (b) Sprays, refrigerants and solvents 133 (c) Unburnt hydrocarbons and photochemical smog Damage mechanisms 137 (a) Deterioration of materials 137 (b) Ozonolysis or peroxidation? 138 (c) Protein sensitivity 140 (d) Peroxyacyl nitrates 141 /' (e) Natural free-radical scavenging 142 /' 5.3 Plants 146 (a) Access 146 (b) Cellular changes and damage 148 (c) Visible injury 149 (d) Peroxyacyl nitrate damage Animals 151 (a) Hazards at work 151 (b) Short- and long-term exposures 152 (c) Biochemical and physiological changes 154 (d) Cellular models 155 (e) Mutagenesis 157 Selected bibliography 157 Chapter 6. Other pollutants - global and local Oxygen? 159 (a) Evolution of the atmosphere 159 xi

5 Air pollution and acid rain Chapter 7. (b) Anaerobes versus aerobes (c) Photorespiration in plants (d) Hyperoxia 6.2 Carbon dioxide (a) The 'Greenhouse effect' (b) CO2 enrichment and deprivation in crops (c) C4 photosynthesis and CAM metabolism (d) Asphyxiation 6.3 Carbon monoxide (a) Sources and sinks (b) Plant uptake (c) The oldest industrial poison (d) Blood biochemistry and pollution 6.4 Hydrogen sulphide (a) Malodorous emissions (b) Emission by plants and microbes (c) Accidents 6.5 Hydrogen fluoride and fluoride ions (a) Ubiquitous by-product (b) Accumulation by plants (c) Fluorosis in animals (d) Human fluorosis, fluoridation and dental health Selected bibliography Interactions, 'recent forest decline' and odier considerations 7.1 Interactions (a) Uncertain contributions of stress (b) Synergistic or more-than-additive? (c) Effects of mixed pollutants on plants (d) Mechanisms of pollutant interaction (e) Do 'cocktails' affect humans? 7.2 'Recent forest decline' neuartige Waldschdden (a) Occurrence and classification (b) Possible causes (c) The 'bad-practice' hypothesis (d) The 'acid rain' or 'soil leaching' hypothesis (e) The 'ozone' or 'photochemical' hypothesis Xll

6 Contents (f) The 'modifier' or 'pollution-enhanced stress/infection' hypothesis 215 (g) The 'ammonium' or 'excess nitrogen deposition' hypothesis 217 (h) The 'chloroethene' or 'photoactivation' hypothesis 219 (i) Alternative hypotheses 220 (j) The 'multi-interaction' hypothesis Genetic adaptation in response to air pollution 222 (a) Industrial melanism 222 (b) Sensitivity and tolerance Overview 229 (a) Models 229 (b) Vegetational impact 230 (c) Plants versus animals 233 (d) Humans, fishes and other unfortunates 234 (e) Where next? 237 Selected bibliography 237 Appendix Air pollutant conversions Free radicals and singlets Photosynthesis Oxidative phosphorylation and respiration Acidity, ph, pa^ and microequivalents Historical and etymological postscript 257 General bibliography 260 Index 262 Xlll

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