Table Of ContentPrinciples of Environmental Chemistry
Principles of Environmental
Chemistry
Roy M Harrison
School of Geography, Earth and Environmental Sciences,
University of Birmingham, Birmingham, UK
ISBN-13:978-0-85404-371-2
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
rTheRoyalSocietyofChemistry2007
Allrightsreserved
Apart from fair dealing for the purposes of research for non-commercial purposes or for
privatestudy,criticismorreview,aspermittedundertheCopyright,DesignsandPatents
Act1988andtheCopyrightandRelatedRightsRegulations2003,thispublicationmaynot
be reproduced, stored or transmitted, in any form or by any means, without the prior
permissioninwritingofTheRoyalSocietyofChemistry,orinthecaseofreproductionin
accordancewiththetermsoflicencesissuedbytheCopyrightLicensingAgencyintheUK,
or in accordance with the terms of the licences issued by the appropriate Reproduction
RightsOrganizationoutsidetheUK.Enquiriesconcerningreproductionoutsidetheterms
statedhereshouldbesenttoTheRoyalSocietyofChemistryattheaddressprintedonthis
page.
PublishedbyTheRoyalSocietyofChemistry,
ThomasGrahamHouse,SciencePark,MiltonRoad,
CambridgeCB40WF,UK
RegisteredCharityNumber207890
Forfurtherinformationseeourwebsiteatwww.rsc.org
TypesetbyMacmillanIndiaLtd,Bangalore,India
PrintedbyHenryLingLtd,Dorchester,Dorset,UK
Preface
While this book is in its first edition, it nonetheless has a lengthy
pedigree, which derives from a book entitled Understanding Our Envi-
ronment: An Introduction to Environmental Chemistry and Pollution,
which ran to three editions, the last of which was published in 1999.
Understanding Our Environment has proved very popular as a student
textbook, but changes in the way that the subject is taught had neces-
sitated its splitting into two separate books.
When Understanding Our Environment was first published, neither
environmental chemistry nor pollution was taught in many universities,
and most of those courses which existed were relativelyrudimentary. In
many cases, no clear distinction was drawn between environmental
chemistry and pollution and the two were taught largely hand in hand.
Nowadays, the subjects are taught in far more institutions and in a far
more sophisticated way. There is consequently a need to reflect these
changes in what would have been the fourth edition of Understanding
Our Environment, and after discussion with contributors to the third
editionandwiththeRoyalSocietyofChemistry,itwasdecidedtodivide
the former book into two and create new books under the titles respec-
tively of An Introduction to Pollution Science and Principles of Environ-
mental Chemistry. Because of the authoritative status of the authors of
Understanding Our Environment and highly positive feedback which we
had received on the book, it was decided to retain the existing chapters
where possible while updating the new structure to enhance them
through the inclusion of further chapters.
This division of the earlier book into two new titles is designed to
accommodate the needs of what are now two rather separate markets.
An Introduction to Pollution Science is designed for courses within
degrees in environmental sciences, environmental studies and related
areasincludingtaughtpostgraduatecourses,whicharenotembeddedin
a specific physical science or life science discipline such as chemistry,
v
vi Preface
physics or biology. The level of basic scientific knowledge assumed of
thereaderisthereforeonlythatofthegeneralistandthebookshouldbe
accessible to a very wide readership including those outside of the
academic world wishing to acquire a broadly based knowledge of
pollution phenomena. The second title, Principles of Environmental
Chemistry assumes a significant knowledge of chemistry and is aimed
far more at courses on environmental chemistry which are embedded
within chemistry degree courses. The book will therefore be suitable for
students taking second or third year option courses in environmental
chemistry or those taking specialised Masters’ courses, having studied
the chemical sciences at first-degree level.
InthisvolumeIhavebeenfortunatetoretaintheservicesofanumber
of authors from Understanding Our Environment. The approach has
been to update chapters from that book where possible, although some
of the new authors have decided to take a completely different ap-
proach. The book initially deals with the atmosphere, freshwaters, the
oceans and the solid earth as separate compartments. There are certain
commoncrosscuttingfeaturessuchasnon-idealsolutionchemistry,and
where possible these are dealt with in detail where they first occur, with
suitablecross-referencingwhentheyre-appearatlaterpoints.Chemicals
in the environment do not respect compartmental boundaries, and
indeed many important phenomena occur as a result of transfers
between compartments. The book therefore contains subsequent chap-
tersonenvironmentalorganicchemistry,whichemphasisesthecomplex
behaviour of persistent organic pollutants, and on biogeochemical cy-
clingofpollutants,includingmajorprocessesaffectingbothorganicand
inorganic chemical species.
Iamgratefultotheauthorsformakingavailabletheirgreatdepthand
breadth of experience to the production of this book and for tolerating
my many editorial quibbles. I believe that their contributions have
createdabookofwidespreadappeal,whichwillfindmanyeagerreaders
both on taught courses and in professional practice.
Roy M. Harrison
Birmingham, UK
Contents
Chapter 1 Introduction 1
R.M. Harrison
1.1 The Environmental Sciences 1
1.2 Environmental Chemical Processes 3
1.3 Environmental Chemicals 3
1.4 Units of Concentration 5
1.4.1 Atmospheric Chemistry 5
1.4.2 Soils and Waters 6
1.5 The Environment as a Whole 7
References 7
Chapter 2 Chemistry of the Atmosphere 8
P.S. Monks
2.1 Introduction 8
2.2 Sources of Trace Gases in the Atmosphere 10
2.3 Initiation of Photochemistry by Light 11
2.4 Tropospheric Chemistry 17
2.5 Tropospheric Oxidation Chemistry 20
2.5.1 NitrogenOxidesandthePhotostationaryState 26
2.5.2 Production and Destruction of Ozone 28
2.5.3 Role of Hydrocarbons 35
2.5.4 Urban Chemistry 37
2.6 Night-Time Oxidation Chemistry 40
2.7 Ozone-Alkene Chemistry 46
2.8 Sulfur Chemistry 46
2.9 Halogen Chemistry 51
2.9.1 Tropospheric Halogens and Catalytic
Destruction of Ozone 56
vii
viii Contents
2.10 Stratospheric Chemistry 58
2.10.1 The Antarctic Ozone Hole 63
2.11 Summary 72
Questions 72
References 76
Chapter 3 Chemistry of Freshwaters 80
M.C. Graham and J.G. Farmer
3.1 Introduction 80
3.2 Fundamentals of Aquatic Chemistry 82
3.2.1 Introduction 82
3.2.2 Dissolution/Precipitation Reactions 91
3.2.3 Complexation Reactions in Freshwaters 94
3.2.4 Species Distribution in Freshwaters 97
3.2.5 Modelling Aquatic Systems 121
3.3 Case Studies 122
3.3.1 Acidification 122
3.3.2 Metals and Metalloids in Water 130
3.3.3 HistoricalPollutionRecordsandPerturbatory
Processes in Lakes 139
3.3.4 Nutrients in Water and Sediments 145
3.3.5 Organic Matter and Organic Chemicals
in Water 150
Questions and Problems 157
Further Reading 159
References 159
Chapter 4 Chemistry of the Oceans 170
S.J. de Mora
4.1 Introduction 170
4.1.1 The Ocean as a Biogeochemical Environment 170
4.1.2 Properties of Water and Seawater 173
4.1.3 Salinity Concepts 177
4.1.4 Oceanic Circulation 179
4.2 Seawater Composition and Chemistry 182
4.2.1 Major Constituents 182
4.2.2 Dissolved Gases 184
4.2.3 Nutrients 199
4.2.4 Trace Elements 201
4.2.5 Physico-Chemical Speciation 204
4.3 Suspended Particles and Marine Sediments 210
Contents ix
4.3.1 Description of Sediments and Sedimentary
Components 210
4.3.2 Surface Chemistry of Particles 213
4.3.3 Diagenesis 218
4.4 Physical and Chemical Processes in Estuaries 219
4.5 Marine Contamination and Pollution 223
4.5.1 Oil Slicks 223
4.5.2 Plastic Debris 226
4.5.3 Tributyltin 228
Questions 230
References 231
Chapter 5 The Chemistry of the Solid Earth 234
I.D. Pulford
5.1 Introduction 234
5.2 Mineral Components of Soil 238
5.2.1 Inputs 238
5.2.2 Primary Minerals 238
5.2.3 Secondary Minerals 240
5.2.4 Weathering Processes (See also Chapter 3) 246
5.3 Organic Components of Soil 248
5.4 Soil pH And Redox Potential 254
5.4.1 pH and Buffering 254
5.4.2 Soil Acidity 255
5.4.3 Soil Alkalinity 257
5.4.4 Influence of pH on Soils 258
5.4.5 Redox Potential 260
5.4.6 Reduction Processes in Soil 261
5.5 Chemical Reactions in Soil 263
5.5.1 Reactions in Soil Solution 263
5.5.2 Ion Exchange (Physisorption) 267
5.5.3 Ligand Exchange (Chemisorption) 271
5.5.4 Complexation/Chelation 273
5.5.5 Precipitation/Dissolution 273
5.5.6 Soil Processes 275
Questions 275
References 278
Chapter 6 Environmental Organic Chemistry 279
C.J. Halsall
6.1 Introduction 279
