Understanding our environment – an introduction to environmental chemistry and pollution roy m harrison

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
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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

1. Introduction ..................................................................

1

1.

The Environmental Sciences ...........................................

1

2.

The Chemicals of Interest ................................................

3

3.

Units of Concentration .....................................................

5

4.

The Environment as a Whole ..........................................

7

5.

Bibliography .....................................................................

7

2. The Atmosphere ...........................................................

9

1.

The Global Atmosphere ...................................................

9

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
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

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24

vii


viii

Contents
2.

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
3.

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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.

4.2
5.

52

53
56

68

Color Plates ............................................................................ 70a

3. Freshwaters ..................................................................

71

1.

Introduction ......................................................................

71

2.

Fundamentals of Aquatic Chemistry ................................

74

2.1

74
74

Introduction ...........................................................
2.1.1 Concentration and Activity .........................

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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

3.

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

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108
109

117


Contents
3.3

4.

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

4. The Oceanic Environment ........................................... 139
1.

2.

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 ....................

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153
153
155
158


xii

Contents
2.2.4

3.

Dimethyl Sulfide and Climatic
Implications ................................................ 165

2.3

Nutrients ................................................................ 167

2.4

Trace Elements ..................................................... 169

2.5

Physico-chemical Speciation ................................. 171

Suspended Particles and Marine Sediments ................... 177
3.1

Description of Sediments and Sedimentary
Components .......................................................... 177

3.2

Surface Chemistry of Particles ..............................
3.2.1 Surface Charge .........................................
3.2.2 Adsorption Processes ................................
3.2.3 Ion Exchange Reactions ............................
3.2.4 Role of Surface Chemistry in
Biogeochemical Cycling ............................

3.3

181
181
182
183
184

Diagenesis ............................................................ 185

4.

Physical and Chemical Processes in Estuaries ............... 186

5.

Marine Contamination and Pollution ................................ 190
5.1

Oil Slicks ............................................................... 191

5.2

Plastic Debris ........................................................ 193

5.3

Tributyltin ............................................................... 194

Questions ................................................................................ 197

5. Land Contamination and Reclamation ....................... 199
1.

Introduction ...................................................................... 199

2.

Soil: Its Formation, Constituents, and Properties ............ 201
2.1

Soil Formation ....................................................... 202

2.2

Soil Constituents ................................................... 203
2.2.1 The Mineral Fraction .................................. 204
2.2.2 Soil Organic Matter .................................... 205

2.3

Soil Properties ....................................................... 206
2.3.1 Soil Permeability ........................................ 206
2.3.2 Soil Chemical Properties ........................... 207

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Contents

2.3.3

xiii

Adsorption and Decomposition of
Organic Contaminants ............................... 210

3.

Sources of Land Contaminants ....................................... 212

4.

Characteristics of Some Major Groups of Land
Contaminants .................................................................. 214
4.1

Heavy Metals ........................................................ 214

4.2

Organic Contaminants ........................................... 215

4.3

Sewage Sludge ..................................................... 218

5.

Possible Hazards from Contaminated Land .................... 219

6.

Methods of Site Investigation .......................................... 220

7.

Interpretation of Site Investigation Data .......................... 223

8.

Reclamation of Contaminated Land ................................ 226

9.

8.1

Ex Situ Methods .................................................... 226
8.1.1 ‘Dig and Dump’ .......................................... 226
8.1.2 Soil Cleaning ............................................. 226

8.2

In Situ Methods ..................................................... 227
8.2.1 Physico-chemical Methods ........................ 227
8.2.2 Biological Methods .................................... 229

8.3

Specific Techniques for Gasworks Sites ............... 230

Case Studies ................................................................... 230
9.1

Gasworks Sites ..................................................... 230

9.2

Soil Contamination by Landfilling and Waste
Disposal ................................................................ 232

9.3

Heavy Metal Contamination from Metalliferous
Mining and Smelting .............................................. 233

9.4

Heavy Metal Contamination of Domestic Garden
Soils in Urban Areas .............................................. 234

9.5

Land Contamination by Solvents, PCBs, and
Dioxins Following a Fire at an Industrial Plant ...... 235

10. Conclusions ..................................................................... 235
Questions ................................................................................ 236

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xiv

Contents

6. Environmental Cycling of Pollutants .......................... 237
1.

2.

Introduction: Biogeochemical Cycling .............................. 237
1.1

Environmental Reservoirs ..................................... 239

1.2

Lifetimes ................................................................ 240
1.2.1 Influence of Lifetime on Environmental
Behaviour .................................................. 243

Rates of Transfer between Environmental
Compartments ................................................................. 244
244

2.1

Air-land Exchange ................................................

2.2

Air-sea Exchange ................................................. 247

3.

Transfers in Aquatic Systems .......................................... 254

4.

Biogeochemical Cycles ................................................... 257

5.

4.1

Case Study 1: the Biogeochemical Cycle of
Nitrogen ................................................................. 259

4.2

Case Study 2: Aspects of the Biogeochemical
Cycle of Lead ........................................................ 260

Environmental Partitioning of Long-lived Species ........... 264

Questions ................................................................................ 265

7. Environmental Monitoring Strategies ........................ 267
1.

Objectives of Monitoring .................................................. 267

2.

Types of Monitoring ......................................................... 269
2.1

2.2

Source Monitoring .................................................
2.1.1 General Objectives ....................................
2.1.2 Stationary Source Sampling for Gaseous
Emissions ..................................................
2.1.3 Mobile Source Sampling for Gaseous
Effluents .....................................................
2.1.4 Source Monitoring for Liquid Effluents .......
2.1.5 Source Monitoring for Solid Effluents ........

271
271
271
271
272
272

Ambient Environment Monitoring .......................... 274
2.2.1 General Objectives .................................... 274
2.2.2 Ambient Air Monitoring .............................. 274

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Contents
2.2.3
2.2.4
3.

5.

6.

Environmental Water Monitoring ............... 279
Sediment, Soil, and Biological
Monitoring .................................................. 285

Sampling Methods ........................................................... 291
3.1

4.

xv

Air Sampling Methods ...........................................
3.1.1 Intake Design .............................................
3.1.2 Sample Collection ......................................
3.1.3 Flow Measurement and Air Moving
Devices ......................................................

291

291
293
300

3.2

Water Sampling Methods ...................................... 300

3.3

Soil and Sediment Sampling Methods .................. 302

Modeling of Environmental Dispersion ............................ 303
4.1

Atmospheric Dispersal .......................................... 305

4.2

Aquatic Mixing ....................................................... 309

4.3

Variability in Soil and Sediment Pollutant
Levels .................................................................... 311

Duration and Extent of Survey ......................................... 311
5.1

Duration of Survey and Frequency of

Sampling ............................................................... 311

5.2

Methods of Reducing Sampling Frequency .......... 315

5.3

Number of Sampling Sites ..................................... 316

Prerequisites for Monitoring ............................................. 316
6.1

Monitoring Protocol ............................................... 317

6.2

Meteorological Data .............................................. 318

6.3

Source Inventory ................................................... 319

6.4

Suitability of Analytical Techniques ....................... 320

6.5

Environmental Quality Standards .......................... 322

7.

Remote Sensing of Pollutant ........................................... 324

8.

Presentation of Data ........................................................ 326

Questions ................................................................................ 328

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xvi

Contents

8. Ecological and Health Effects of Chemical
Pollution ........................................................................ 331
1.

Introduction ...................................................................... 331

2.

Toxicity: Exposure-response Relationships ...................

3.

Exposure ......................................................................... 336

4.

Absorption ....................................................................... 339

5.

Internal Pathways ............................................................ 342

6.

Ecological Risk Assessment ............................................ 347

7.

Individuals, Populations, and Communities and the
Role of Biomarkers .......................................................... 349

8.

Health Effects of the Major Air Pollutants ........................ 358

9.

Effect of Air Pollution on Plants ....................................... 362

333

10. Ecological Effects of Acid Deposition .............................. 366

11. Forest Decline ................................................................. 373
12. Effects of Pollutants on Reproduction and Development:
Evidence of Endocrine Disruption ................................... 374
12.1 Eggshell Thinning .................................................. 375
12.2 GLEMEDS ............................................................. 377
12.3 Marine Mammals ................................................... 378
12.4 Imposex in Gastropods ......................................... 379
12.5 Endocrine Disruptors ............................................. 380
13. Hydrocarbons in the Marine Environment ....................... 383
14. Health Effects of Metal Pollution ...................................... 388
14.1 Mercury ................................................................. 388
14.2 Lead ...................................................................... 391
15. Conclusion ....................................................................... 394
Questions ................................................................................ 395

9. Managing Environmental Quality ............................... 397
1.

Introduction ...................................................................... 397

2.

Objectives, Standards, and Limits ................................... 400
2.1

Environmental Objectives ...................................... 400

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Contents

3.

4.

5.

6.

xvii

2.2

Environmental Standards ...................................... 401

2.3

Emission Limits ..................................................... 402

2.4

Integrating Limit Values and Quality Standards ....
2.4.1 Use-related Approach ................................
2.4.2 Uniform Emission Standards .....................
2.4.3 Sectoral Approach .....................................

2.5

Specifying Standards ............................................ 405

2.6

Remediation Targets ............................................. 411

2.7

The Principles of No Deterioration and
Precaution ............................................................. 413

404
404
405
405

Legislation to Control and Prevent Pollution .................... 413
3.1

Origins of Pollution Control Legislation ................. 414

3.2

Trends in European Environmental Legislation ..... 415

3.3

Reporting Environmental Performance ................. 417

3.4

Pollution Control and Land Use Planning .............. 418

Pollution Control Agencies .............................................. 420
4.1

Structure and Organization of Pollution Control
Agencies ............................................................... 420

4.2

Forestalling Pollution ............................................. 422

4.3

Other Regulatory Action ........................................ 426

Economic Instruments for Managing Pollution ................ 427
5.1

Alternatives to Pollution Regulation by Permit ...... 427

5.2

Tradeable Permits ................................................. 430

Public and Commercial Pressures to Improve the
Environment .................................................................... 432
6.1

Environmental Management Systems ................... 432

6.2

Public Opinion and the Environment ..................... 434

Questions ................................................................................ 435

Index ................................................................................... 437

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CHAPTER 1

Introduction
ROY M. HARRISON

1 THE ENVIRONMENTAL SCIENCES
It may surprise the student of today to learn that 'the environment' has
not always been topical and indeed that environmental issues have
become a matter of widespread public concern only over the past
twenty years or so. Nonetheless, basic environmental science has existed
as a facet of human scientific endeavour since the earliest days of
scientific investigation. In the physical sciences, disciplines such as
geology, geophysics, meteorology, oceanography, and hydrology, and
in the life sciences, ecology, have a long and proud scientific tradition.
These fundamental environmental sciences underpin our understanding
of the natural world, and its current-day counterpart perturbed by
human activity, in which we all live.
The environmental physical sciences have traditionally been concerned with individual environmental compartments. Thus, geology is

centred primarily on the solid earth, meteorology on the atmosphere,
oceanography upon the salt water basins, and hydrology upon the
behaviour of fresh waters. In general (but not exclusively) it has been the
physical behaviour of these media which has been traditionally perceived
as important. Accordingly, dynamic meteorology is concerned primarily
with the physical processes responsible for atmospheric motion, and
climatology with temporal and spatial patterns in physical properties of
the atmosphere (temperature, rainfall, etc.). It is only more recently that
chemical behaviour has been perceived as being important in many of
these areas. Thus, while atmospheric chemical processes are at least as
important as physical processes in many environmental problems such as
stratospheric ozone depletion, the lack of chemical knowledge has been
extremely acute as atmospheric chemistry (beyond major component
ratios) only became a matter of serious scientific study in the 1950s.


There are two major reasons why environmental chemistry has
flourished as a discipline only rather recently. Firstly, it was not
previously perceived as important. If environmental chemical composition is relatively invariant in time, as it was believed to be, there is little
obvious relevance to continuing research. Once, however, it is perceived
that composition is changing (e.g. CO2 in the atmosphere; 137Cs in the
Irish Sea) and that such changes may have consequences for humankind,
the relevance becomes obvious. The idea that using an aerosol spray in
your home might damage the stratosphere, although obvious to us
today, would stretch the credulity of someone unaccustomed to the
concept. Secondly, the rate of advance has in many instances been
limited by the available technology. Thus, for example, it was only in
the 1960s that sensitive reliable instrumentation became widely available
for measurement of trace concentrations of metals in the environment.
This led to a massive expansion in research in this field and a substantial

downward revision of agreed typical concentration levels due to
improved methodology in analysis. It was only as a result of James
Lovelock's invention of the electron capture detector that CFCs were
recognized as minor atmospheric constituents and it became possible to
monitor increases in their concentrations (see Table 1). The table
exemplifies the sensitivity of analysis required since concentrations are
at the ppt level (1 ppt is one part in 1012 by volume in the atmosphere) as
well as the substantial increasing trends in atmospheric halocarbon
concentrations, as measured up to 1990. The implementation of the
Montreal Protocol, which requires controls on production of CFCs and
Table 1 Atmospheric halocarbon concentrations and trends*
Concentration
(PPt)

Annual Change
(PPt)

Halocarbon

Pre-industrial

1992

To 1990

Since 1992

CCl 3 F (CFC-Il)
CCl 2 F 2 (CFC-12)
CClF 3 (CFC-13)

C 2 Cl 3 F 3 (CFC-113)
C 2 Cl 2 F 4 (CFC-IM)
C 2 ClF 5 (CFC-115)
CCl 4
CH 3 CCl 3

0
0
0
0
0
0
0
0

268
503
<10
82
20
<10
132
135

+ 9.5
+ 16.5

0
+7

+ 4-5

0

+ 2.0
+ 6.0

-0.5
-10

Lifetime
(years)
50
102
400
85
300
1700
42
4.9

*Data from: Intergovernmental Panel on Climate Change, 'Climate Change—The IPCC Scientific
Assessment', ed. J. T. Houghton, G. J. Jenkins, and J. J. Ephraums, Cambridge University Press,
Cambridge, 1990; and 'Climate Change 1995, The Science of Climate Change', ed. J. T. Houghton,
L. G. Meira Filho, B. A. Callendar, N. Harris, A. Kattenberg, and K. Maskell, Cambridge
University Press, Cambridge, 1996.


some other halocarbons, has led to a slowing and even a reversal of
annual concentration trends since 1992 (see Table 1).

2

THE CHEMICALS OF INTEREST

A very wide range of chemical substances are considered in this book.
They fall into three main categories:
(a) Chemicals of concern because of their human toxicity. Some metals
such as lead, cadmium and mercury are well known for their
adverse effects on human health at high levels of exposure. These
metals have no known essential role in the human body and
therefore exposures can be divided into two categories (see Figure
1). For these non-essential elements, at very low exposures the
metals are tolerated with little, if any, adverse effect, but at higher
exposures their toxicity is exerted and health consequences are
seen. In the case of the so-called essential trace elements (see also
Figure 1) the human body requires a certain level of the element,
and if intakes are too low then deficiency syndrome diseases will
result. These can have consequences as severe as the ones which
result from excessive intakes. In between, there is an acceptable
range of exposures within which the body is able to regulate an
optimum level of the element.
Environmental exposure to chemical carcinogens is very topical
despite the minuscule risks associated with many such exposures
at typical environmental concentrations. Examples are benzene
(largely from vehicle emissions) and polynuclear aromatic hydrocarbons (generated by combustion of fossil fuels). Figure 2 shows
the structures of benzene, benzo(a)pyrene (the best known of the
carcinogenic polycyclic aromatic hydrocarbons), and 2,3,7,8tetrachlorodibenzodioxin (the most toxic of the chlorinated
dioxin group of compounds). Despite great public concern over
emissions of the last compound, the evidence for carcinogenicity
in humans is quite limited.

(b) Chemicals which cause damage to non-human biota but are not
believed to harm humans at current levels of exposure. Many
elements and compounds come into this category. For example,
copper and zinc are essential trace elements for humans and
environmental exposures very rarely present a risk to health.
These elements are, however, toxic to growing plants and there
are regulations limiting their addition to soil in materials such as
sewage sludge which is disposed of to the land. Another category
of substance for which there is ample evidence of harm to biota,


ESSENTIAL
TRACE
ELEMENT

Beneficial

Uptake
Deleterious

INESSENTIAL
TRACE
ELEMENT

Beneficial

Figure 1 Comparison of the consequences of exposure to essential and inessential trace
elements. For the essential trace elements, Region A represents the deficiency
syndrome when intakes are insufficient, Area B is the optimum exposure window
and in Area C, excessive intake leads to toxic consequences. In the case of the

inessential trace element at low exposures (Zone E) the element is tolerated and
little if any adverse effect occurs. In Zone F toxic symptoms are developed

(a)
Figure 2

(b)

(C)

Some molecules believed to have human carcinogenic potential: (a) benzene;
(b) benzofa.Jpyrene; (c) 2,3,7,8-tetrachlorodibenzodioxin


but as yet little, if any, hard evidence of impacts on human
populations, are the endocrine-disrupting chemicals (also termed
oestrogenics). These synthetic chemicals mimic natural hormones
and can disrupt the reproduction and growth of wildlife species.
Thus, for example, bis-tributyl tin oxide (TBTO) interferes with
the sexual development of oysters and its use as an anti-fouling
paint for inshore vessels is now banned in most parts of the world.
A wide range of other chemicals including polychlorinated biphenyls (PCBs), dioxins, and many chlorinated pesticides are also
believed to have oestrogenic potential, although the level of
evidence for adverse effects is variable.
(c) Chemicals not directly toxic to humans or other biota at current
environmental concentrations, but capable of causing environmenta
damage. The prime example is the CFCs which found widespread
use precisely because of their stability and low toxicity to humans,
but which at parts per trillion levels of concentration are capable
of causing major disruption to the chemistry of the stratosphere.

3 UNITS OF CONCENTRATION
The concentration units used in environmental chemistry are often
confusing to the newcomer. Concentrations of pollutants in soils are
most usually expressed in mass per unit mass, for example, milligrams of
lead per kilogram of soil. Similarly, concentrations in vegetation are also
expressed in mg kg~ l or fig kg~ l . In the case of vegetation and soils, it is
important to distinguish between wet weight and dry weight concentrations, in other words, whether the kilogram of vegetation or soil is
determined before or after drying. Since the moisture content of vegetation can easily exceed 50%, the data can be very sensitive to this
correction.
In aquatic systems, concentrations can also be expressed as mass per
unit mass and in the oceans some trace constituents are present at
concentrations of ng kg" 1 or fig kg""1. More often, however, sample
sizes are measured by volume and concentrations expressed as ng 1~1 or
/ng 1"l. In the case of freshwaters, especially, concentrations expressed as
mass per litre will be almost identical to those expressed as mass per
kilogram. As a kind of shorthand, however, water chemists sometimes
refer to concentrations as if they were ratios by weight, thus, mg I" 1 are
expressed as parts per million (ppm), jag 1~l as parts per billion (ppb) and
ng I""1 as parts per trillion (ppt). This is unfortunate as it leads to
confusion with the same units used in atmospheric chemistry with a quite
different meaning.
Concentrations of trace gases and particles in the atmosphere can be


expressed also as mass per unit volume, typically /ig m 3. The difficulty
with this unit is that it is not independent of temperature and pressure.
Thus, as an airmass becomes warmer or colder or changes in pressure so
its volume will change, but the mass of the trace gas will not. Therefore,
air containing 1 fig m~ 3 of sulfur dioxide in air at 0 0C will contain less
than 1 fig m~ 3 of sulfur dioxide in air if heated to 25 0C. For gases (but

not particles) this difficulty is overcome by expressing the concentration
of a trace gas as a volume mixing ratio. Thus, 1 cm3 of pure sulfur
dioxide dispersed in 1 m3 of polluted air would be described as a
concentration of 1 part per million (ppm). Reference to the gas laws
tells us that not only is this one part per 106 by volume, it is also one
molecule in 106 molecules and one mole in 106 moles, as well as a partial
pressure of 10~6 atmospheres. Additionally, if the temperature and
pressure of the airmass change, this affects the trace gas in the same way
as the air in which it is contained and the volume mixing ratio does not
change. Thus, ozone in the stratosphere is present in the air at
considerably higher mixing ratios than in the lower atmosphere (troposphere), but if the concentrations are expressed in fig m~ 3 they are little
different because of the much lower density of air at stratospheric
attitudes. Chemical kineticists often express atmospheric concentrations
in molecules per cubic centimetre (molec cm" 3 ), which has the same
problem as the mass per unit volume units.
Worked Example

The concentration of nitrogen dioxide in polluted air is 85 ppb. Express
this concentration in units of fig m~~3 and molec cm""3 if the air
temperature is 200C and the pressure 1005 mb (1.005 x 105 Pa).
Relative molecular mass of NO2 is 46; Avogadro number is 6.022 x
1023.
The concentration OfNO2 is 85 fA m~3. At 20 0C and 1005 mb,
8 5 x

1 0

6

2 7 3

n
'UAz
~
85 ,1i M
NO
2 weigh46 x - ^ ^ x —
Q<

1 0 0 5

x ~

= 161 x 10~ 6 g
NO2 concentration = 1 6 1 ^ m " 3
This is equivalent to 161 pg cm" 3 , and
161 x 10~12
23
161 pg NO2 contain 6.022 x 10 x
46
12
= 2.1 x 10 molecules
and NO2 concentration = 2.1 x 1012 molec cm" 3 .


4 THE ENVIRONMENT AS A WHOLE
A facet of the chemically centred study of the environment is a greater
integration of the treatment of environmental media. Traditional
boundaries between atmosphere and waters, for example, are not a
deterrent to the transfer of chemicals (in either direction), and indeed

many important and interesting processes occur at these phase boundaries.
In this book, the treatment first follows traditional compartments
(Chapters 2, 3, 4, and 5) although some exchanges with other compartments are considered. Fundamental aspects of the science of the atmosphere, waters, and soils are described, together with current
environmental questions, exemplified by case studies. Subsequently,
quantitative aspects of transfer across phase boundaries are described
and examples given of biogeochemical cycles (Chapter 6). Monitoring
considerations are covered in Chapter 7, with the effects of chemical
pollution in Chapter 8, and finally the regulatory aspects in Chapter 9.
5 BIBLIOGRAPHY
For readers requiring knowledge of basic chemical principles:
R.M. Harrison and SJ. de Mora, 'Introductory Chemistry for the Environmental
Sciences', Cambridge University Press, Cambridge, 2nd Edn., 1996.
For more detailed information upon pollution phenomena:
'Pollution: Causes, Effects and Control', ed. R.M. Harrison, Royal Society of Chemistry,
Cambridge, 3rd Edn., 1996.


CHAPTER 2

The Atmosphere
A. G. CLARKE AND A. S. TOMLIN

1
1.1

THE GLOBAL ATMOSPHERE
The Structure of the Atmosphere

1.1.1 Troposphere and Stratosphere. The vertical structure of the
atmosphere, showing the features that are most relevant to the problems

covered in this chapter, is illustrated in Figure 1. The figure shows the
stratosphere, troposphere and boundary layer (that closest to the earth's
surface). The difference between the layers is characterized by changes in
temperature with height, and with changes in structure of the layers such
as cloud cover and turbulence. The depth of the troposphere is 8-15 km,
the lowest values occurring at the poles and the highest at the equator
with some seasonal variations. Within this layer occurs most of the
variability of conditions which leads to 'the weather' as the layman
experiences it. The stratosphere is relatively cloud-free and considerably
less turbulent—hence long distance passenger jets fly at stratospheric
altitudes. Within the troposphere temperature decreases with height
owing to the decreasing influence of radiation from the earth's surface,
but as we enter the stratosphere the temperature starts to increase again.
The turning point is called the tropopause. This situation of a layer of
warmer, less dense air over a layer of cooler, denser air is quite stable.
Consequently air is mixed across the tropopause very slowly unless
special events such as tropospheric folding occur.
We normally think of 'air pollution' in terms of the troposphere,
within which most pollutants have a fairly limited lifetime before they are
washed out by rain, removed by reaction, or deposited to the ground.
However, if pollutants are injected directly into the stratosphere they can
remain there for long periods because of slow downward mixing,
resulting in noticeable effects over the whole globe. Thus major volcanic


Stratopause
STRATOSPHERE
Pressure
mb
Intercontinental

airliner

Altitude

High level cloud
(Cirrus)

Tropopause

Storm
clouds
(Cumulonimbus)

TROPOSPHERE

Low level cloud
(Stratus)
Boundary layer
Temperature K
Figure 1

The vertical structure of the atmosphere. The temperature profile would be
typical for latitude 60° N in summer. Note the change of scale used for the upper
half of the figure

eruptions injecting fine dust into the stratosphere can lead to a reduction
in the amount of solar energy reaching the ground for more than a year
after the event. Other global problems relating to events in the stratosphere such as the possibility of damage to the ozone layer are discussed
later.
7.7.2 Atmospheric Circulation. To understand both global and local

environmental problems we must first understand how pollutants
circulate throughout the atmosphere. The main driving forces for the
circulation of the atmosphere are the incident solar radiation and the
earth's rotation. Because of the sun's angle, the amount of solar energy
falling on a given area varies with latitude so that the poles are cold and
the equatorial regions warm. Warm air rises at the equator and cold air
flows inwards from both North and South. A similar situation occurs at
the poles where warm air flows towards them and falls in the cold regions
there. The rotation of the earth affects the circulation patterns in a