From the origin of the Earth to climate change, this textbook presents the chemistry of the environment using the full strength of physical, inorganic, and organic chemistry, in addition to the necessary mathematics and physics, using modern notation and terminology. It provides a broad yet thorough description of the environment and the environmental impact of human activity using scientific principles.
Chemistry and the Environment describes the chemistry of Earth's atmosphere, hydrosphere, and lithosphere (including soils) and the biogeochemical cycles. The book presents a variety of industrial processes, from paper and steel to energy and pesticide production, focusing discussion on the environmental impact of these processes and showing how increasing environmental awareness has led to improved methods. The text provides an accessible account of environmental chemistry while paying attention to the fundamental basis of the science, showing derivations of formulas and giving primary references and historical insight. The authors make consistent use of professionally accepted nomenclature (IUPAC and SI), allowing transparent access to the material by students and scientists from other fields.
The authors created this textbook primarily for their own courses, and it has been developed through many years of feedback from students and colleagues. The book will be invaluable for advanced undergraduate and graduate students in environmental chemistry courses, and for professionals in chemistry and allied fields.
“This outstanding text brings together fundamental information about the natural chemistry of the Earth and its atmosphere and the environmental impacts of anthropogenic chemicals. It is well suited for upper-level undergraduate and graduate students and researchers in chemistry, Earth sciences, and atmospheric science.”
“Both authors have excellent scientific standing and complementary backgrounds. They have combined well on this excellent textbook, based on their long experience of teaching environmental chemistry to undergraduate students at the University of Copenhagen. There are many textbooks on environmental chemistry aimed at undergraduate and graduate courses, but this is one of the best that I have come across. It will be adopted for courses in every university for the next decade and beyond due to its logical and comprehensive content. I strongly recommend this excellent textbook for environmental chemistry and related courses at the graduate and undergraduate levels.”
“Harnung and Johnson have produced a textbook on environmental chemistry that is firmly rooted in physical and chemical principles and follows a strict quantitative and analytical approach. Nevertheless, the accessible style and informative footnotes make it a joy to read and explore for graduate students and professionals alike. It perfectly fills the gap left by more phenomenological introductions to the field.”
Sven E. Harnung is a Senior Lecturer in the Department of Chemistry at the University of Copenhagen and was Head of Department for 12 years. He teaches courses on environmental, inorganic, physical, and analytical chemistry, including pharmaceutical applications. His current research concentrates on magnetic studies of single-molecule magnets. He is the author of three chemistry textbooks in Danish. Dr. Harnung has organized several congresses, including an International Union of Pure and Applied Chemistry (IUPAC) General Assembly. He has been a member of the Danish National Committee for Chemistry for more than 30 years, and he is a Fellow of IUPAC. He has served as a board member of the journals Acta Chemica Scandinavica and Physical Chemistry Chemical Physics.
Matthew S. Johnson is a Senior Lecturer at the Department of Chemistry at the University of Copenhagen. He teaches courses on environmental chemistry, physical and quantum chemistry, and scientific writing. His main research interest is atmospheric chemistry, including kinetics, spectroscopy, and stable isotopes in atmospheric trace gases. He is a coauthor of more than 70 articles in peer-reviewed journals. He has invented and patented a method for efficient emissions control and improving building energy efficiency. He was awarded a Fulbright Fellowship to study stratospheric chemistry at the Max-lab electron storage ring in Lund, Sweden. He has worked as a researcher for Honeywell and Medtronic and has research collaborations with many groups around the world, including Ford Motor Company and the Tokyo Institute of Technology.
CAMBRIDGE UNIVERSITY PRESS
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Cambridge University Press
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Information on this title: www.cambridge.org/9781107682573
© Sven E. Harnung and Matthew S. Johnson 2012
This publication is in copyright. Subject to statutory exception and to the provisions of relevant collective licensing agreements, no reproduction of any part may take place without the written permission of Cambridge University Press.
First published 2012
Printed in the United States of America
A catalog record for this publication is available from the British Library.
Library of Congress Cataloging in Publication Data
ISBN 978-1-107-02155-6 Hardback
ISBN 978-1-107-68257-3 Paperback
Additional resources for this publication at www.cambridge.org/harnung.
Cambridge University Press has no responsibility for the persistence or accuracy of URLs for external or third-party Internet Web sites referred to in this publication and does not guarantee that any content on such Web sites is, or will remain, accurate or appropriate.
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Preface
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xi |
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Acknowledgments
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xiii |
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Introduction
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1 |
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1 The Earth
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4 |
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1.1 Origin of the Earth
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4 |
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a. Big Bang
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4 |
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b. The solar system
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7 |
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c. The Earth
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10 |
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1.2 Structure of the Earth
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14 |
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a. Classical measurements
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14 |
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b. Internal structure of the Earth
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17 |
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1.3 Geological periods and dating
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21 |
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a. Geological periods
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21 |
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b. Radioactive dating
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23 |
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c. Isotopic fractionation
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26 |
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1.4 Features of the Earth's development
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31 |
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a. Plate tectonics
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31 |
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b. Chemistry mediated by water and biota
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34 |
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c. Global chemistry of life
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35 |
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2 Environmental dynamics
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37 |
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2.1 Introduction
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37 |
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a. Basic concepts
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37 |
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b. Time dependence of concentration
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40 |
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c. Field
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43 |
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d. Transport
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44 |
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2.2 Fluid dynamics
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45 |
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a. Basic properties of the flux density
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45 |
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b. Open physicochemical systems
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49 |
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c. Continuity equations
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51 |
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d. Equations of motion
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54 |
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e. Applications of the equations of motion
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56 |
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f. Applications of the continuity equation
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65 |
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2.3 Chemical thermodynamics
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69 |
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a. Basic concepts
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70 |
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b. Phase equilibria
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81 |
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2.4 Chemical kinetics
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91 |
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a. Basic concepts
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92 |
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b. Description of elementary reactions
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92 |
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c. Temperature dependence of reaction rates
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94 |
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3 The Spheres
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98 |
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3.1 The lithosphere
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99 |
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a. Abundance of the elements
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100 |
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b. The rock-forming minerals
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102 |
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c. Igneous rocks
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109 |
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d. Sedimentary rocks
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112 |
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e. Metamorphic rocks
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114 |
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3.2 The hydrosphere
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115 |
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a. Chemical composition of natural waters
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116 |
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b. Analytical characteristics of environmental waters
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117 |
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c. Physicochemical properties of water
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121 |
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3.3 The atmosphere
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124 |
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a. Chemical composition
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124 |
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b. Hydrosphere-atmosphere equilibria
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126 |
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c. The physics of the atmosphere
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128 |
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3.4 Biota
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131 |
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a. Chemical composition of biota
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131 |
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b. The cell
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135 |
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4 Chemistry of the atmosphere
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140 |
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4.1 Tropospheric chemistry
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142 |
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a. The hydroxyl radical
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142 |
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b. Nonmethane hydrocarbons
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151 |
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c. Tropospheric aerosols
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154 |
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d. Henry's law and deposition
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155 |
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4.2 Stratospheric chemistry
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156 |
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a. The Chapman mechanism: Ox
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157 |
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b. The radicals HOx
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159 |
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c. The radicals NOx
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160 |
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d. The radicals ClOx and coupling of the cycles
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161 |
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e. The ozone hole
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163 |
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f. Midlatitude ozone depletion
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166 |
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5 Chemistry of the hydrosphere
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169 |
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5.1 Acid-base chemistry
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170 |
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a. Acid-base properties of water
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171 |
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b. An acid and its conjugate base
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172 |
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c. Oligovalent acids
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178 |
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d. Polyvalent acids
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187 |
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5.2 Coordination chemistry
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189 |
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a. Complex formation
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190 |
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b. Lewis acids and bases
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194 |
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c. Coordination chemistry of natural waters
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196 |
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5.3 Electrolytic properties
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200 |
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a. Redox chemistry of natural waters
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201 |
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b. Aqueous solutions of electrolytes
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206 |
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6 Chemistry of the pedosphere
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217 |
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6.1 Structure of soil
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218 |
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a. Soil profile
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218 |
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b. Regolith and groundwater
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220 |
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6.2 Physics of soil water
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222 |
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a. The saturated zone
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222 |
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b. The vadose zone
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224 |
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c. Flowing groundwater
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226 |
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6.3 Chemistry of soils
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228 |
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a. Structure of soil minerals
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230 |
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b. The soil solution
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236 |
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c. Soil adsorption phenomena
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238 |
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d. Soil colloid phenomena
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246 |
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e. Soil organic matter
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248 |
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7 Global cycles of the elements
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250 |
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7.1 Biogeochemical cycles
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250 |
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7.2 Carbon
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251 |
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a. Reservoirs of carbon
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251 |
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b. Fluxes of carbon dioxide
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253 |
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c. Fluxes of methane
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255 |
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d. Anthropogenic sources of atmospheric carbon dioxide
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255 |
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7.3 Nitrogen
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256 |
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a. Natural nitrogen fixation
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256 |
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b. Industrial nitrogen fixation
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261 |
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7.4 Phosphorus
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263 |
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7.5 Sulfur
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265 |
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a. Natural sulfur cycles
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266 |
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b. Anthropogenic sulfur cycles
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267 |
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7.6 Chlorine
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270 |
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7.7 Aluminium and silicon
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272 |
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8 The chemicals industry
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273 |
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8.1 Introduction
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273 |
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a. Energy
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274 |
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b. A survey of the chemicals industry
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275 |
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c. The agriculture and food industries
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277 |
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d. Chemical production
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279 |
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8.2 Heavy industry
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282 |
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a. Cement
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282 |
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b. Coal and steel
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285 |
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c. Metals
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289 |
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d. Pulp and paper
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292 |
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8.3 The inorganic chemicals industry
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294 |
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a. The electrolytic cell
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296 |
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b. Sodium hydroxide
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299 |
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c. Sodium carbonate
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299 |
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d. Chlorine
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302 |
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8.4 The biotechnology industry
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304 |
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8.5 Sustainable synthetic chemistry: Green chemistry
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304 |
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9 Environmental impact of selected chemicals
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310 |
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9.1 Pesticides
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310 |
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a. Insecticides
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312 |
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b. Herbicides
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315 |
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c. Fungicides
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318 |
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d. Enantiomeric xenobiotics
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320 |
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9.2 Organochlorine compounds
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323 |
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a. Dioxins and (polychloro)biphenyls
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323 |
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b. Hexachlorocyclohexane, HCH, and pentachlorocyclohexene, PCCH
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326 |
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c. Bromocyclenes
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328 |
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9.3 Metal compounds
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328 |
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9.4 Detergents
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330 |
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a. Soaps
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331 |
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b. Syndets
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332 |
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c. The Gibbs isotherm
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334 |
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9.5 Water treatment
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335 |
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a. Domestic water
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336 |
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b. Industrial water
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338 |
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c. General methods
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339 |
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10 The chemistry of climate change
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343 |
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10.1 The physics of thermal radiation
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344 |
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a. Quantitative expressions
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344 |
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b. Radiation theory
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345 |
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c. Application to the Sun-Earth system
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348 |
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10.2 Astronomical forcing
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352 |
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a. The insolation formula
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353 |
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b. Time dependence of insolation
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355 |
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c. Climate recorded in sediments and glacial ice
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358 |
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10.3 Modern climate
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360 |
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a. Causes of climate change
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361 |
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b. Energy flux densities in the atmosphere
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361 |
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c. Radiant forcing
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362 |
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d. Global warming potential
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365 |
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e. Climate sensitivity
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365 |
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f. Climate change
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367 |
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Appendix 1
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371 |
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A1.1 Symbols of the elements
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371 |
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A1.2 Atomic weights of the elements
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372 |
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A1.3 The international system of units, SI
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375 |
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A1.4 Nonstandard units and suffixes
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376 |
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A1.5 Transport properties
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377 |
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A1.6 Electricity
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377 |
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A1.7 General chemistry
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378 |
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A1.8 Fundamental constants
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379 |
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A1.9 α-Amino acids of proteins
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379 |
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A1.10 The Greek alphabet
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380 |
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Appendix 2
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381 |
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A2.1 Polyvalent acids
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381 |
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A2.2 Mononuclear complexes
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385 |
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a. Polynuclear complexes
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387 |
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Appendix 3
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389 |
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A3.1 The activity of electrolytes
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389 |
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a. The Debye-Hückel limiting law
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389 |
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Appendix 4
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393 |
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A4.1 Convection
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393 |
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Appendix 5
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396 |
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A5.1 Parameters of the insolation formula, Equation 10.29
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396 |
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a. The 24-h mean insolation at a geographical latitude ϕ
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396 |
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b. The ecliptic
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398 |
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References
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401 |
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Name index
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415 |
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Subject index
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417 |