Enviromental Chemistry Peter O'Neill

Environmental Chemistry
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Environmental Chemistry
Third edition
PETER O ’NEILL
Department o f Environmental Sciences
University o f Plymouth
Plymouth, U K
E 5
BLACKIE ACADEMIC & PROFESSIONAL
An Imprint of Chapman & Hall
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First edition 1985

Reprinted 1990, 1991
Second edition 1993
Third edition 1998
© 1998 Thom son Science
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Library of Congress Catalog Card Number: 98-70685
Contents
Preface vii
PART ONE THE OXYGEN-RICH PLANET 1

1 History of the Earth 3
1.1 Development of life 6
1.2 D istribution o f the elements 10
1.3 Geochemical cycles 13
2 Oxygen 17
2.1 M olecular oxygen in the atm osphere 19
PART TWO M A JO R ELEM ENTS FO U N D IN LIVING

M ATTER 33
3 Hydrogen 38
3.1 Isotopes of hydrogen 41
3.2 W ater 43
3.3 Hydroxyl radical form ation 59
4 Carbon 61
4.1 The carbon cycle 61
4.2 Aqueous systems 61
4.3 Photosynthesis and the form ation of carbon compounds 65
4.4 Energy 74
4.5 Geochemical accumulation of solar energy 78
4.6 Greenhouse effect 79
5 Nitrogen 89
5.1 N atural transform ation processes in the nitrogen cycle 91
5.2 Nitrogen oxides in the atm osphere 95
5.3 Nitrogen fertilizers 100
5.4 N itrate in water supplies 102
5.5 Balanced diets and food production 103
6 Sulfur 106
6.1 The sulfur cycle 106
6.2 The sulfur dioxide problem 113
7 Phosphorus 123
VI E NVI RONMENTAL CHEMISTRY
PART THREE M A JO R ELEM ENTS IN THE EARTH’S CRUST 129

8 Silicon 134
8.1 Silicate minerals 134
8.2 W eathering 135
9 Iron 141
9.1 Iron in natural systems 141
9.2 Iron in industrial systems 152
9.3 Corrosion 155
10 Aluminium 158
10.1 Aluminium in industrial systems 158
10.2 Aluminium in solution 161
11 Calcium and magnesium 164

11.1 Form ation of calcareous rocks 166
11.2 W ater hardness 167
11.3 H eart disease 169
12 Sodium and potassium 172

12.1 Clay minerals 173
12.2 Potassium fertilizers 176
12.3 Fluids in organisms 177
12.4 Radioactive potassium 179
PART FO UR M INOR ELEM ENTS A N D ENVIRONM ENTAL

PRO BLEM S 181
13 Lead 190
14 Mercury 196
15 Zinc and cadmium 201
15.1 Sewage-sludge disposal 202
15.2 Toxicity of cadmium 206
15.3 Zinc 206
16 Uranium 208
16.1 Nuclear energy 209
16.2 Radioactive wastes 215
16.3 Fate of dispersed radioactive wastes 220
17 Radon 227
17.1 R adon in buildings 230
17.2 Biological effects 231
18 Hazardous organic compounds 233

18.1 Synthetic organic com pounds 233
18.2 Dioxins 234
18.3 D D T and related com pounds 238
18.4 Polychlorinated biphenyls, PCBs 239
18.5 Polynuclear aromatic hydrocarbons, PAHs 241
18.6 Endocrine-disrupting chemicals 243
Appendix Chemical compound formation 248

Glossary 254
Index 265
Preface
Since the first and second editions o f this b ook were w ritten know ledge of
the E a rth ’s chem ical environm ent has increased. Y et there is still great
uncertainty ab o u t the future changes th a t m ay result from hum an activities.
It has becom e increasingly clear th a t these activities have the capacity to
cause large-scale disruption o f the n atu ral environm ent, b u t w hether th at
capacity will becom e a reality is a m atter o f dispute. The increase in the
w o rld ’s p o p u latio n and the increased m obilization o f chemical species are
producing global as well as local changes to the environm ent. However,
whilst there is clear evidence th a t decline in stratospheric ozone concen
tratio n s is occurring and th a t governm ents have com bined together to take
preventative actions, the equally clear evidence th a t tropospheric ozone
concentrations are increasing has n o t b ro u g h t ab o u t such concerted action.
Similarly, there is a lack o f action to reduce the emissions o f greenhouse
gases. A lthough here the evidence th a t the m easurable increases in con
centration are actually causing the predicted climate changes is less clear. In
this edition m any chapters have been up-dated to include new inform ation.
A new chapter on uranium and the problem s associated with the develop
m ent o f the nuclear pow er industry and m ilitary w eaponary has ben added.
T here is also a new section on endocrine disrupting organic chemicals.
A lthough the m ajority o f this new m aterial is connected w ith pollution, it
m ust still be em phasized th a t environm ental chem istry is m uch m ore than
the study o f pollution. Only by understanding the natu ral m obility o f the
elements and their com pounds can the changes th a t hum an activities bring
a b o u t be appreciated.
The breakdow n o f rock to form soils, the uptake o f the mobilized
chemicals by plants and the return o f the dead plant m aterial to the soil ready
for further u ptake has long been know n as a ‘biogeochem ical’ cycle
(indicating the interaction o f biology, geology and chemistry). The biogeo
chemical cycle is only one p art o f the general geochemical cycle in which
m aterial is m oved from the land to the sea, possibly having entered the
atm osphere, and then being reincorporated in the land mass. The elements
m ove thro u g h their cycles in fits and starts, with m any variations in chemical
form occurring along the way. Environm ental chem istry attem pts to explain
why a specific change occurs and why a particular pathw ay has been
followed: o f necessity, there is overlap w ith biology, geology and physics.
viii ENVIRONMENTAL CHEMISTRY
One possible definition o f environm ental chem istry is the study o f the role o f
chemical elements in the synthesis and decom position o f natu ral m aterials o f
all kinds, including the changes specifically b ro ught ab out by hum an actions.
The selection o f topics for inclusion in this book proved difficult. The
guiding principle has been to provide a bro ad survey illustrating the
o peratio n o f n atu ral systems, w ith some diversions to show how hum an
activities can m odify these systems. A fo u r-p art form at has been chosen to
allow the grouping together o f related environm ental topics. M ost readers
will have at least a know ledge o f chem istry, but the text should be
understandable even to those w ithout this. A glossary giving brief explana
tions o f term s and concepts used in the text is included. Bold type is used to
indicate first appearances o f term s th a t are to be found in the glossary or
th a t are explained in the text. The b o o k will have achieved its objective if,
after reading it, you have gained some insight into the operation o f chemical
processes near the E a rth ’s surface, and discovered th a t environm ental
chem istry is an exciting area o f study.
The students for w hom this b o o k is designed will be taking first-year
degree courses in environm ental science or the various types o f m odular
degree courses involving chem istry, geology, biology, ecology and physical
geography options. In addition some second- and third-year special courses
will find m aterial o f interest, as will science sixth-form ers.
P a rt One sets the scene and provides an in tro d u ctio n to m any o f the basic
geological, geochem ical and chemical ideas th a t are essential for an
understan d in g o f geochem ical cycles. The im portance o f oxygen to the
chem istry o f reactions occurring near the E a rth ’s surface is em phasized by
dealing w ith this elem ent first. This im portance applies to bo th biologically
m ediated and inorganic reactions; systems depending upon these reaction
types are discussed in P arts Two and Three. B oth differences and sim ilarities
betw een anim ate and inanim ate systems are reviewed; above all, the
application o f general chemical concepts to w hat m ight appear to be widely
different reactions is illustrated. Because the m obility o f one elem ent
depends u p o n the other chem ical species in a p articular environm ent,
different aspects o f certain topics o f concern (such as ‘air pollu tio n ’) are
discussed in several chapters. In P a rt F o u r there is a brief exam ination of
some o f the effects o f h u m an activities on elements th a t usually cycle
n atu rally in small quantities. This final p a rt further highlights the
p e rtu rb a tio n to n atu ral cycles caused by agricultural, industrial and social
developm ents with the consequent problem s o f environm ental m anagem ent.
I w ould like to th an k all those students and staff w ho have read the
m anuscript either in full or in part. Their com m ents have proved very
helpful, as has the advice and guidance I have received from the staff o f the
publishers. H ow ever, the responsibility for the approach chosen and the
views expressed rem ains w ith me.
Peter O 'N eill
Part One The oxygen-rich planet
A lthough it could be argued th a t each planet in the solar system has its own
unique features, the dioxygen-rich atm osphere and the presence o f living
m atter m ake the E arth especially interesting. It was the presence o f w ater
rath er th an oxygen th a t was crucial to the developm ent o f life on E arth, but
the present com position o f the atm osphere ensures th at organism s th at can
m ake use o f the oxygen in energy-releasing reactions are dom inant at the
E a rth ’s surface.
In this p a rt we shall look at (a) the geological developm ent o f the E arth,
(b) the developm ent o f life-forms, and (c) the p a rt oxygen has played in
these developm ents. The presence o f free or com bined oxygen dom inates the
surface chem istry o f the E arth (Table P l.l) ; for this reason oxygen is
discussed in this in tro d u cto ry p a rt o f the book. Know ledge gained ab o u t
oxygen’s chem istry can then be applied when discussing the chem istry o f the
other m ajor elements in living systems (P art Two) and o f the other m ajor
elements in the E a rth ’s crust (P art Three).
A ny study o f environm ental chem istry soon reveals the dependence o f the
reactions o f any one elem ent on the reactions o f a num ber o f other elements.
T herefore, although some reactions o f oxygen are considered in C hapter 2,
m ore detail is often given in later chapters when other elements are being
investigated. F o r instance, the problem s o f acid rain involve the reactions of
oxygen w ith com pounds o f sulfur and nitrogen to form products th at
dissolve in w ater to form acidic solutions. These solutions can interact with
a wide variety o f soils, rocks, buildings and so on, as well as affecting plants,
anim als and fish. As a consequence, various aspects o f acid-rain production
and its effects are discussed in C hapters 2-6 and 10.
C hem ical reactions involve the pro d u ctio n o f new distributions o f the
electrons am ong the atom s taking p a rt in the reaction, or a change in the
d istribution o f the atom s (A ppendix). Lead in w ater pipes will slowly
dissolve in the w ater as the atom s o f m etallic lead lose two electrons each
(E qn P l . l ) to some chemical species in the water.
Pbsolid ^ ^ s o lu tio n + (P l-1 )
The consequence o f this simple change could be the poisoning o f people

drinking the w ater. The charged form o f lead in solution is in a lower energy
state th an the lead in the m etal. All reactions occur in such a way th at the
2 THE OXYGEN RICH PLANET
Table P l.l The ten m ajor elements in the Universe, the Earth, the E arth’s crust, the ocean, the
atm osphere as dry air and the biosphere (as weight %)
Universe Earth Crust Ocean Atmosphere Biosphere
H Fe O O N O
77 35 46.6 85.8 75.5 53
He O Si H O C
21 29 29.5 11 23.2 39
O Si A1 Cl Ar H
0.8 14 8.2 1.94 1.3 6.6
C Mg Fe Na C N
0.3 14 5.0 1.05 9.3 x 1(T3 0.5
Ne S Ca Mg Ne Ca
0.2 2.9 3.6 0.13 1.3 x 10“ 3 0.4
Fe Ni Na S Kr K
0.1 2.4 2.8 0.09 0.45 X l< r 3 0.2
Si Ca K Ca He Si
0.07 2.1 2.6 0.041 72 x 1(T6 0.1
N A1 Mg K Xe P
0.06 1.8 2.1 0.039 40 x 10"6 0.1
Mg Na Ti Br H Mg
0.06 0.3 0.57 0.007 23 x 10~6 0.1
S P H c S S
0.04 0.2 0.22 0.003 70 x 10~9 0.07
energy o f the to tal system is low ered (C h ap ter 4). O ur understanding o f the
factors controlling these changes in energy is expressed by the laws o f
therm odynam ics (Table 4.1). These laws and the consequent m athem atical
equations allow us to predict how likely it is th a t a given chem ical reaction
will occur.
U n fo rtu n ately therm odynam ics tells us n othing ab o u t how rapidly the
reaction will occur. The rate at which a reaction occurs (the kinetics o f the
change) is o f the utm ost im portance in environm ental chem istry. M any o f
the controversies ab o u t the likely im pact o f the use o f a particular process or
chem ical involve disputes ab o u t chem ical kinetics. If an insecticide is
sprayed on to an edible crop, there will be no danger to som eone eating the
crop a m o n th after spraying if the insecticide decom poses to harm less
p ro d u cts w ithin 24 h. H ow ever, if the decom position is m uch slower a health
h azard could exist. Enzymes speed up chem ical reactions and all organism s
depend u p o n enzymic reactions for their survival. M any harm ful substances,
such as lead, are toxic because they react w ith the enzymes inside organism s
and usually slow dow n or stop essential reactions. The understanding o f
n atu ral systems depends upo n an understanding o f b o th the th erm o
dynam ics and the kinetics o f the system.
1 History of the Earth
The origin o f the solar system, including the E arth, is a subject o f some
controversy. This is because the various hypotheses are based on our very
incom plete know ledge o f the solar system as it exists now. The further back
in tim e we go the greater the assum ptions and extrapolations th a t have to be
m ade ab o u t the conditions th a t existed then. The evidence we have indicates
th a t by ab o u t 4.5 billion years (4.5 x 109 a) ago there was a planet w ith a
solid crust approxim ately 150 m illion km from the Sun. Since th at time
m ajor changes have occurred at a m uch slower rate.
The m ajo r structural features o f the E arth (Figure 1.1) have probably
show n little change in the past 4 billion years. Life on E arth is confined to
the regions close to the atm o sp h ere-lan d -o cean boundaries, and these
p o rtio n s o f the globe are in a state o f continuing flux.
Thickness
Figure 1.1 Structure.

It is know ledge o f the operatio n o f this thin outer shell, which contributes
less th an 1 % o f the m ass o f the E arth , th at is o f such great im portance to us
if we are to ensure the survival o f the h u m an species and to attain a
satisfactory quality o f life.
The present surface o f the E arth is irregular, ab o u t 70% being covered
w ith w ater o f average depth 4 km (range 0-11 km). The rem ainder
com prises land masses w ith an average height o f 0.84 km (range 0-8.8 km)
above sea-level. T w o-thirds o f this land is situated in the no rth ern
hem isphere. The m ajor land m asses are called continents and they are best
defined n o t by shorelines b u t by the edges o f the deep-sea platform s, which
m ay be far o u t to sea and thus in co rp o rate the continental shelf (Figure 1.2).
This definition o f continents m eans th a t offshore islands are included as
p arts o f their nearest land masses. M ore im portantly, it agrees w ith the
geological and chem ical evidence th a t there is a com positional difference
betw een continental crustal rocks and the crustal rocks underlying the deep
oceans (Figure 1.2).
It is now th o u g h t th a t the E a rth ’s surface consists o f a num ber o f rigid
plates (100-150 km thick) m oving discontinuously over the m antle (Figure
1.3). These plates consist o f the continental and oceanic crusts plus the
up p erm o st layer o f the m antle. W here tw o adjoining plates are m oving
ap a rt, a t ocean ridges, the region is m arked by volcanism , by the addition o f
new crustal m aterial and by the form atio n o f oceanic basins, e.g. the
A tlan tic and Indian Oceans. W hen tw o plates converge, one plate passes
partially u nder the other to form either an a rc-tre n ch system, in oceanic
regions, o r a m o u n tain belt (e.g. the H im alayas), where two continental
regions collide. W hen crustal m aterial is carried dow n tow ards the m antle as
one plate rides over the other, the process is called subduction. This m aterial
becom es hotter, and the low er-m elting, lighter com ponents m ay m elt and
rise tow ards the surface again, before the denser com ponents mix in w ith the
m antle. The re-injection o f these large m asses o f lighter m olten m aterial
starts o ff a m ountain-building sequence (Figure 1.3). M o u n tain ranges are
associated w ith the convergence o f plates.
The relative direction o f the m ovem ent o f adjacent plates changes with
time. The plates themselves also change as they break up or fuse w ith
adjoining plates, b u t the overall effect is to keep the irregularity o f the
E a rth ’s surface contours. A good exam ple o f change is along the Pacific
coast o f N o rth A m erica, w here two converging plates, the collision o f which
form ed the Rocky M o u n tain ranges, are now sliding past each other. The
lateral m ovem ent has produced an extensive transform fault system, the
best-know n m em ber o f which is the San A ndreas fault. The effect o f this
m ovem ent is to separate the C alifornian coastal region from the m ainland
and m ove it north w ard s tow ards C anada.
HI ST ORY OF THE EARTH 5
Continental crust Atmosphere - - stratosphere

(av. 40 km thick) (400-500 km thick) (35 km)
Percentage of Earth’s surface occupied
Sector Major elements in order of decreasing concentration
| j atmosphen N, O
ocean O, H (Cl, Na, Mg, S)
sedimentary rocks O, Si, Al, Fe, Ca, K, Mg, C, Na
2 ] f(r“i;i,ic igneHUS O, Si. Al, K. Na . Ca. Fe. Mg
basaltic igneous
O, Si, Al, Fe, Ca, Mg
rock
mantle O, Si, Mg, Fe
Figure 1.2 A cross-section of the surface o f the Earth, indicating the m ajor elements in various
sectors.
The oldest d ated rocks are 3.8 billion years old. It seems th a t for at least
the p ast 4 billion years there have been continental areas consisting o f less
dense (approxim ately 2.7 g cm -3 ) rocks rising above the oceanic basins w ith
their m ore dense (approxim ately 3.2 g cm -3 ) rocks. D uring this long period
mountain building mid-ocean
------► <------ <«----- ------►

plates m oving together plates m oving apart
Figure 1.3 The form ation of mid-ocean ridges as plates move apart, and of subduction zones
and m ountains as plates move together.
the various plates have m oved, join ed together, broken up and thus caused
the fo rm atio n and d estruction o f b o th continents and oceans. Present-day
earth q u ak es and volcanoes are co n stan t rem inders th a t these large-scale
processes are still continuing. H ow ever, m ost o f this book is concerned w ith
processes th a t occur m uch m ore rapidly.
1.1 Development of life
If it is true th a t the E a rth ’s developm ent included a period w hen the surface
was m olten, then life-form s o f the types we know now adays could n o t have
existed a t those tem peratures. O ur know ledge o f life in the times before
there were w ritten records, o r even before there were hum ans to write,
depends u p o n a study o f the preserved rem ains o f organism s. These rem ains,
called fossils, are found in sedim entary rocks; generally only the h ard parts,
e.g. skeletons and shells, are preserved. Only under exceptional conditions,
usually associated w ith very fine sedim ents, do soft organs leave an im print.
T he oldest recognizable fossils are over 3 billion years old and are sim ilar
to some present-day bacteria an d algae, i.e. single-celled organism s. The
cells do n o t have well-developed nuclei and the organism s are, therefore,
called prokaryotes (Figure 1.4). A lhough b acteria and algae are relatively
simple life-form s, they have a high degree o f order and are capable o f
carrying o u t com plex biochem ical reactions. The processes by w hich these
p ro k ary o tes could have developed are still clouded in m ystery.
T he m ost p o p u lar view o f the developm ent o f life assum es th a t there was
a grad u al progression from simple inorganic molecules to the present-day
wide diversity o f simple and com plex life-forms (Figure 1.5). All living
things on E a rth are com posed o f com pounds containing strings o f carbon
H I ST O RY OF THE EA RTH 7
cell wall nucleoid mitochondrion
cell membrane
nucleus
ribosomes
(a) Prokaryotic cell (b) Eukaryotic cell

lacks true nucleus and internal contains true nucleus and a variety of
organelles internal structures called organelles
(e.g. mitochondria)
Figure 1.4 The two m ajor types of living cells: (a) prokaryotic cells; (b) eukaryotic cells.
atom s. Because m any o f them are essential to life, carbon-containing

com pounds and molecules are often called organic com pounds and organic
m olecules (P art Two). A large num ber o f organic com pounds can be m ade
in laboratories by reactions betw een w ater (H 20 ) , am m onia (N H 3), carbon
dioxide ( C 0 2), carb o n m onoxide (CO), m ethane (C H 4), hydrogen sulfide
(H 2S) and dihydrogen (H 2). These simple m olecules are th ought to have
been present in the atm osphere and oceans o f the prim itive E arth. It seems
reasonable to suppose th a t such reactions could have occurred and th at a
wide range o f organic m olecules could have been produced. It is the steps
from non-living systems to self-supporting, self-replicating living organism s
and the subsequent developm ent o f diverse life-forms th a t are m ost
speculative.
The success o f an organism (any living creature or life-form) is dependent
upo n the efficiency w ith which it utilizes the available sources o f food and
energy sources. The earliest organism s were dependent on the supply o f
externally synthesized organic m olecules. Like hum ans and other anim als,
they were heterotrophs. Autotrophs are capable o f synthesizing the required
organic m olecules from simple inorganic molecules. As these simple
m olecules were m uch m ore ab u n d a n t in the ocean and atm osphere th an
were the organic m olecules, the au to tro p h s m ay be expected to have
expanded a t the expense o f the first heterotrophs.
B oth types o f p ro k ary o tic organism s w ould obtain energy by fermentation
reactions (E qn 1.1).
(i.i)
THE OXYGEN RICH PLANET
Figure 1.5 A possible pattern for the development of life on Earth.

HI STO RY OF THE EA RTH 9
F erm en tatio n is n o t a very good source o f energy. The ability to utilize the
visible p a rt o f the spectrum , and so use solar radiation as an energy source
for the conversion o f carbon dioxide into organic molecules, gave the
photosynthetic bacteria a big advantage. Initially molecules such as
hydrogen sulfide, H 2S, or simple organic com pounds were used as hydrogen
d onors (E qn 1.2).
nC 02 + 2« H 2A ^ (C H 20 )„ + « H 20 + 2«A (1.2)
carbon dioxide hydrogen donor carbohydrate
T hen blue-green algae developed which could m ake use o f the alm ost
limitless w ater in the oceans as the hydrogen d o nor and which produced
dioxygen as a by-product (E qn 1.3).
nC 02 + n H 20 — + (C H 20 )„ + n 0 2 (1.3)
carbon dioxide hydrogen donor carbohydrate dioxygen
The release o f dioxygen b ro u g h t ab o u t m ajor changes to the E a rth ’s surface

(C hapter 2), including the killing o ff o f m any organism s th a t were n o t able
to p ro tect themselves against this reactive gas.
As the level o f dioxygen in the atm osphere built up, an ozone ( 0 3) layer
gradually form ed in the stratosphere (15-60 km above the E a rth ’s surface).
O zone is very good at absorbing harm ful ultraviolet (UV) radiation. As the
level o f U V rad iatio n reaching the E a rth ’s surface decreased, organism s
could begin to colonize regions close to the atm o sp h ere-w ater-lan d
interface: there was no longer the need for a protective layer o f w ater to filter
o u t the UV. The presence o f dioxygen allowed suitably modified cells to use
respiration reactions (Eqn 1.4) to obtain 18 times m ore energy than the
ferm entation reaction releases.
(C H 20 ) n Jr n 0 2 — ► nC 02 -frcH20 (1.4)
carbohydrate carbon dioxide water
The organization o f the m aterial inside the cells now underw ent a sig
nificant change, w ith the developm ent o f (a) a m em brane-bounded nucleus
containing the nucleic acids carrying the cell’s genetic inform ation, and (b) a
n um ber o f oth er distinct structural features (Figure 1.4). These new cells are
called eukaryotic cells as they contain a definite nucleus. The au to tro p h ic
single-celled eukaryotes evolved to m ulti-celled green plants which used
photosynthesis to produce organic molecules and dioxygen. The expansion
in p o p u latio n o f efficient photosynthesizing and respiring organism s
provided the basis for the resurgence o f heterotrophs. The eukaryotic
h etero tro p h s evolved into the fish, insects and anim als th a t are so ab u n d an t
today.
F o u r billion years ago the E a rth ’s atm osphere probably consisted m ainly
o f dinitrogen (N 2), and possibly carbon dioxide ( C 0 2), with m inor am ounts
o f dihydrogen (H 2), carb o n m onoxide (CO), m ethane (C H 4) and possibly
dioxygen ( 0 2). The developm ent o f life, as outlined above, has caused
dioxygen to becom e a m ajor com ponent (21% ) o f the atm osphere, w ith
carb o n dioxide being a m inor com ponent (354 ppm ; ‘p p m ’ m eans ‘p arts per
m illion’); an d dihydrogen (0.5 ppm ), m ethane (1.5 ppm ) and carbon
m onoxide (0.1 ppm ) becom ing very m in o r com ponents. E nvironm ental
change is a continuing process, and, as dioxygen-breathing heterotrophs,
m aybe we should n o t be too upset by this.
1.2 Distribution of the elements
If we wish to study the chem ical changes th a t take place in the environm ent,
it is im p o rtan t to have some sort o f reference system. This reference system
should allow us to recognize w hether a chem ical change is norm al or
abn o rm al for the p articu lar environm ent being studied and w hat will be the
size o f the effect bro u g h t ab o u t by the change. In order to recognize the
abn o rm al we m ust know w hat is norm al, and to recognize change we m ust
know w hat the original state was. These statem ents m ay appear to be self-
evident, b u t to be aw are o f the environm ent in the necessary detail is
extrem ely difficult.
A know ledge o f the chem ical com position o f a system is necessary before
we can m eaningfully study the chem ical changes going on in th a t system.
W hen we look carefully at w hat we know a b o u t the chem ical com position o f
the various com ponents o f our environm ent (Table P l .l ) , we realize how
m any estim ates m ust be included in these figures. It is very easy to see tables
o f num erical values and assum e th a t they are reliable representations of
some inform ation. If the info rm atio n has been obtained by chemical
analysis, the analysis is said to be ‘accu rate’ if it gives the true value.
The accuracy o f a m ethod is affected by errors, b o th random and
system atic. The sm aller these errors, the m ore accurate and precise the
results. Precision can be defined as the ability to obtain the same results -
right o r w rong - repeatedly. Precision is actually a m easure o f the random
errors in a system. System atic errors lead to an inaccurate result biased
tow ards one value (Figure 1.6). ‘H ig h ’ or ‘g o o d ’ precision m eans th a t there
is little variatio n in the values. The precision o f a m ethod can only be
estim ated by repeating the analysis o f the sam ple m any times. Statistical
treatm en t o f the results then allows a num erical value for the precision to be
o btained, e.g. the percentage relative variatio n at the 95% confidence limit
(this value is alm ost twice the standard deviation) is often used (Figure 1.7).
If the d eterm ination o f the iron con ten t o f a rock gives a value o f 42.0 g kg-1
w ith a precision o f ± 1 0 % , then this m eans th a t we w ould expect 95 out of
100 analyses o f the rock to give values in the range o f 3 7 .8 ^ 6 .2 g Fe k g -1 ,
and five results to be higher or lower. If the distribution o f results is normal
(Figure 1.7) then the value o f 42.0 g Fe k g -1 is the mean, or arithm etic
HIS TO RY OF THE EA RTH 11
measured values
Key
T true value
Measured values:
R l small error showing relatively high precision (i.e. good repeatability with little variation)
R2 larger errors giving relatively low precision (i.e. poor repeatability with larger variation
between single values)
SRi systematic error plus small random errors giving biased results; the bias could be due to
contamination, faulty instrumentation, etc. - high precision
SR2 systematic error plus greater random error again giving biased results - lower precision
mean of either Ri or R2 accords with T . the true value .'.R1 and R2 provide good accuracy
neither SRi nor SR2 give true values . .SRi and SR2 provide poor accuracy
Figure 1.6 The effects of random and systematic errors on measured values.
average, o f all the results. In practice it is found th at the elemental

distributions in rocks are often lognorm al, and it is the logarithmic values o f
the concentrations th a t are distributed norm ally (Figure 1.7).
A lhough m any instrum ental m easurem ent techniques will give precisions
o f the order o f 1% , pre-analysis treatm ent o f rocks involving grinding,
sieving, dissolution and so fo rth will decrease the precision, and values o f
5% —10% are often the best th a t can be attained. W hen the variability
introduced by sam ple collection and storage is included, the precision can
d ro p to 50% or less. The im portance o f determ ining precision is recognized
m uch m ore now adays, b u t results are still often reported with no indication
o f their reproducibility. H ow ever, we m ust always keep in m ind the fact th at
system atic errors will n o t be picked up by simple precision tests and th at
highly precise results m ay be very inaccurate. A ccurate results m ust be
precise, but precise results m ay n o t be accurate!
T urning our atten tio n to Table P l . l , it is obvious th a t the values given
can n o t be very precise. The concentrations o f the ten m ajor elements in the
Universe and in the whole E arth m ust be based on few analyses and m any
assum ptions; neither region is easily accessible for direct analysis. The
oceans and the atm osphere are b o th fluids, b u t are stratified and n o t as
(a) Normal distribution (b) Lognormal distribution

Number of samples
with a given
mode mean
95.45%
± 2 s.d
99.73% 3 s.d.
Proportion of results that are within Positively skewed results - if the

1,2 or 3 standard deviations (s.d.) of logarithm of x is used the distribution
mean value m becomes normal as in (a) and the
mode (the most common value)
becomes the mean (average) value
Figure 1.7 Normal and lognormal distributions o f results.
hom ogeneous as m ight a t first be thought. T he concentrations o f the m ajor

elem ents are reasonably well know n. The m inor elements are less well
q uantified because o f their very low concentrations, w ith instrum ent
sensitivity (ability to determ ine small am ounts) and co n tam ination
becom ing critical. The biosphere (all the organic m atter in the atm osphere,
oceans and crust) and the crust are b o th very heterogeneous so th at
sam pling becom es the critical factor.
The crustal figures highlight the problem s. F irst we m ust define the
boundaries o f the crust. The crust is the solid m aterial above the
Mohorovicic discontinuity, w hich is found at 5-6 km below the ocean bed
and 40-60 km below the continental surface. Is the crust hom ogeneous?
Q uite clearly it is not. The crust is com posed o f m any different rock types
such as granites, basalts, sandstones and lim estones, each o f which has its
ow n distinctive com position. In addition, each rock type will vary in
com position from place to place. A recent exam ination o f one rock outcrop
covered ab o u t 80 k m 2 and involved analysing 93 samples: this gave the
m ean concentration o f iron as being 4.75% w ith a stan d ard deviation o f
1.15% Fe, indicating th a t ab o u t 88 o f the sam ples lie in the range 2 .4 5 % -
7.05% Fe. This wide range is n o t unusual. R ocks at the surface are
accessible, b u t how do we collect samples from 40 or 50 km below the
HIST O RY OF THE EA RTH 13
surface? It is n o t surprising th a t different estim ates o f crustal abundances

give different values. The estim ates are based upon the assum ptions th at the
analyses are representative o f the various rock types and th a t the correct
distribution o f rock types, b o th in area and depth, is chosen. Values given to
m ore th an two significant figures imply a spurious degree o f precision.
1.3 Geochemical cycles
Tables such as Table P l . l , showing the distribution o f the elements, ignore

the m ovem ent o f chem ical substances from one o f the chosen divisions to
another. Rivers carry dissolved and suspended m aterial from the land to the
oceans. M ovem ent o f plates causes the uplift o f ocean sedim ents and the
form ation o f new land masses. Plants add dioxygen to the atm osphere by
photosynthesis and rem ove it by respiration. All o f these m ovem ents m ight
be described as n atu ral because they occurred before hum ans appeared on
the E arth. The presence and activities o f the hum an p o pulation have caused
changes in the rates o f m ovem ent o f m any chemical substances and it is the
possible effects o f these changed rates th a t have been causing increasing
concern. N o t only are there increases in transfer rates o f com pounds already
present (such as carb o n dioxide, which is being released by the burning of
carbon-containing fuels), b u t com pletely new chemicals (such as the
insecticide D D T ) are being distributed on land and sea. The flow o f a
chem ical elem ent between land mass, ocean and atm osphere can be
described by m eans o f a geochem ical cycle.
E ach geochem ical cycle is a m odel th a t describes the m ovem ent o f a
chem ical elem ent o r species, usually n ear the surface o f the E arth. The vast
m ajority o f m aterial now near the E a rth ’s surface - the crust, the ocean and
the atm osphere - stays in this region. T here appears to be little loss either to
the m antle or to outer space. Because the m ovem ent is bo th continuous,
even if very slow in some cases, and conservative (there are few losses or
gains), there is a repeated cycling o f the com ponents. The cycles are
described using reservoirs, physically well-defined units and tra n sp o rt paths
along which m aterial is transferred from one reservoir to another (Figure
1.8). The n um ber o f reservoirs used depends upon the degree o f detail with
w hich the system is to be studied. The degree o f detail th a t is actually
possible is determ ined by the am o u n t and quality o f the d ata available on
the reservoir contents and tra n sp o rt pathw ays. One o f the m ajor
consequences o f the attem pts to co nstruct balanced geochemical cycles has
been the highlighting o f those p arts o f the cycle ab o u t which we have very
little knowledge.
In quantitative geochem ical cycles, estim ates are m ade o f both the
am o u n t o f an elem ent in each reservoir and the flux betw een the reservoirs.
The flux is defined as the am o u n t o f m aterial passing along a particular
tra n sp o rt pathw ay in a fixed period o f tim e, usually 1 year (Figure 1.8). If

the concen tration o f an elem ent rem ains co n stan t in a reservoir this m eans
th a t there is a balance betw een the am o u n t o f elem ent entering the reservoir
an d the am o u n t leaving. A steady-state has been reached. M ost n atu ral
cycles, i.e. those n o t influenced by h u m an technology, ap pear on a global
basis to be in a steady-state. This conclusion has been reached because there
is little geological evidence to show th a t there has been any great change in
the global chem ical environm ent over the p ast few hundred m illion years.
If we know th a t a system is in a steady-state, we can determ ine the
residence tim es for individual elem ents in p articu lar reservoirs (E qn 1.5).
am o u n t o f elem ent in reservoir .

residence tim e = -------- -— — ----- 7--------------- 77— ^ --------------- (1.5)
rate o f addition (or rem oval) o f the elem ent
F o r example, if the am o un t o f sodium dissolved in the ocean is 15 x 1018 kg,

and the am ou nt added each year is 100 x 109 kg, then the residence time
Key
□ reservoirs ------------►
------------- transport pathway
1 precipitation (rain, snow) 5 gas evolution

2 dust 6 rivers - dissolved and
3 sea spray suspended material
4 degassing 7 sedimentation
8 uplift
Figure 1.8 A general model of the geochemical cycle.

H IS TO RY OF THE EARTH 15
fro m mantle
Figure 1.9 Geological processes involved in geochemical cycles.

will be 150 m illion years. (Sodium actually has a residence time o f 210
m illion years.) M ost o f the elem ents have residence times in the ocean o f a
few m illion years or less. Residence tim es in the crust are usually m uch
longer and residence tim es in the atm osphere are shorter, reflecting the
m obility o f the systems.
Possibly the largest im pact hum ans have had on general geochem ical
cycling processes has been the increase in the rate o f transfer o f solids from
land to sea. This has m ainly occurred by disturbing the plants th a t hold soil
in place. In forest areas the cutting dow n o f trees has allowed the rapid
w ashing aw ay o f soil and loose rock, w hereas in other areas bad agricultural
practices have caused soil to be w ashed or blow n away. It is th o u g h t th a t
land-erosion rates are now at least double w hat they were 5000 years ago.
This degree o f interference w ith the system we are m easuring m akes
m onitoring hum an im pact very difficult as we cannot be certain a b o u t w hat
o u r base-line concentrations and fluxes should be.
T he general geological processes involved in the geochem ical cycling o f
the elem ents are indicated in F igure 1.9. The changes in rock types are
b ro u g h t ab o u t by the changes in stability o f the individual chemical
com ponents und er different conditions o f tem perature and pressure. In
addition, the presence or absence o f a p articu lar chem ical species influences
the chem ical reactions th a t occur. The presence o f b o th w ater and dioxygen
at the E a rth ’s surface has a d om inating effect on the reactions occurring in
this zone. M any o f these reactions are also influenced by biological activity,
an d the in teraction o f chem ical and biological systems will be a m ajor them e
in the follow ing chapters.
A lhough a know ledge o f global geochem ical cycles is im p o rtan t we are
also interested in w hat happens on a m uch sm aller scale. The global average
can hide very wide local fluctuations. The leaching o f cadm ium from a mine
dum p, which m ay cause fish dow nstream to be killed, is an event o f local
im portance; b u t this extra flow o f cadm ium is negligible in com parison w ith
the to tal global cycle. W e, therefore, need m odels th a t will allow us to
illustrate and predict w hat will h appen in local landscape units.
Landscape geochem istry is an holistic ap p ro ach th a t looks at local events.
It has been described as ‘the study o f the role chem ical elem ents play in the
syntheses and decom position o f n atu ral m aterial o f all kinds’ (J. A. C.
F ortescue). If we add, ‘the study o f the changes specifically b ro u g h t ab o u t
by h u m an actio n s’, we have a good definition o f environm ental chem istry.
In the ecosystem approach, the living biosphere is the central them e and the
behaviour o f chem ical elem ents in the environm ent is o f secondary
im portance. In environm ental chem istry, the behaviour o f the chemical
entities is o f central im portance. Living or dead m atter, along w ith
pedological (affecting soils) and geological (affecting rocks) processes, are
considered as co ntributing factors to the circulation o f chem ical elements.
2 Oxygen
Oxygen A bundance by weight (the relative abundance is given in

parentheses): E arth, 28.5% (2); crust, 46.6% (1); ocean, total
85.8% (1), dissolved 0 2 6 ppm at 15 °C (13); atm osphere, 23.2%
(2). ppm = mg kg-1 .
Oxygen has an uniquely im p o rtan t place in the com position o f both the
anim ate and inanim ate world. It is the only elem ent th a t is present in high
concentrations in the crust, atm osphere, hydrosphere and biosphere. F o r
this reason oxygen deserves special consideration.
The m ajor rock-form ing m inerals in the E a rth ’s crust are silicates, whose
m ain structural unit is the [S i0 4] tetrah ed ro n (C hapter 8). A bout 95% o f all
crustal rocks are com posed o f silicate m inerals and m ost o f the rem aining
5% is com posed o f m inerals containing oxygen, e.g. as carbonate ( C 0 2~) in
lim estones, as sulfate (S 0 4“ ) in evaporites and as phosphate ( P 0 4~) in
ph osphate rock. The oxygen when com bined in these m inerals has an ionic
radius o f 140 pm (pm = picom etre = 10~ 12 m), whereas the silicon has a
radius o f 26 pm , and all the other m ajor elements, ap art from calcium (100
pm ), sodium (102 pm ) and potassium (138 pm), have radii below 80 pm. As
a consequence o f the relatively large size o f oxygen ions, ab o u t 94% by
volum e o f the E a rth ’s crust is oxygen.
The various oxygen-containing species such as silicates (SiO^- ) and
carbonates (C O 2 -) are called ‘oxyanions’ because they have a negative
charge (a p ro p erty o f anions) and contain oxygen. Even when the m ineral
breaks dow n during w eathering, the oxyanion usually rem ains as an
un b ro k en unit th a t is tran sp o rted to the ocean, incorporated into sediments
and returned to the land unaltered. The m ajority o f the oxygen in the
E a rth ’s crust can be considered to be chemically inert, as it rem ains bound
to the same central atom in an oxyanion and undergoes the m inim um o f
chemical change as it passes thro u g h the geochemical cycle (Figure 2.1).
In contrast, the oxygen in the atm osphere is chemically reactive. The
oxygen is m ainly present as the free element, in the form o f the dioxygen
molecule, 0 2. The reactivity o f dioxygen is great enough to have a
controlling influence on the geochem ical cycles o f m any other elements, such
as carbon, hydrogen, nitrogen, sulfur and iron. As has already been
m entioned, the m ajority o f the dioxygen in the atm osphere has been
>H N O ;
photosynthesis
combustion o f
fossil fuels
river
* \ s Q 4 ~ - > H 2S + C 0 2 H C 0 j /C 0 23
causing increased solubility
Figure 2.1 Chemical species found in the oxygen cycle.
p roduced by photosynthesis. In addition, a sm all am o u n t is produced by the

action o f U V light on w ater molecules in the upper regions o f the
atm osphere. This reaction (E qn 2.1) is called photodissociation, and the
hydrogen produced escapes into space.
2 H 20 u L!lfht 2 H 2 + O 2 (2.1)
U V rad iatio n is also involved in the conversion o f dioxygen into the

triatom ic m olecule ozone, 0 3. This reaction (E qn 2.2) is called photolysis
and is o f p articu lar im portance because o f the ability o f ozone to absorb UV
radiation.
0 2 u Xi!fht O + O (atom ic oxygen) (2 .2)
O+ 02— 03 (2.3)
This ab so rp tio n prevents the m ajority o f the energetic UV rad iation th a t is

lethal to m ost life-forms from reaching the E a rth ’s surface.
Respiration (E qn 2.4) is used by the m ajority o f organism s as a m eans o f
p roducing energy; this reaction, together w ith the oxidation o f dead organic
m a tte r (a chem ically sim ilar reaction) reverses the photosynthetic process.
(C H 20 ) n + n 0 2 —> nC 0 2 + «H 20 (2.4)
carbohydrate dioxygen carbon dioxide water
OXYGEN 19
The burning o f fossil fuels also produces carbon dioxide and w ater at the
expense o f dioxygen, b u t this is ju st a delayed oxidation o f dead organic
m atter. H ydrogen sulfide, H 2S, from volcanoes and organic decay, is
converted to sulfur dioxide, S 0 2, in the atm osphere. This sulfur dioxide,
plus th a t produced by the com bustion o f fossil fuels and the extraction o f
m etals from sulfide ores, is eventually converted to sulfate, SO4” (Figure
2.1), and returns to the E a rth ’s surface, often as acid rain. Similarly, the
various oxides o f nitrogen, w hether produced by m icroorganism s or by
hum an activities, are eventually converted to nitrate, N O ~, and m ay also
produce acid rain. The phrase ‘anthropogenic sources’ is often used to
indicate th at som ething has been produced by hum an activities. O n land,
and to a lesser extent in the oceans, m any m etals are converted to insoluble
oxides (E qn 2.5) by atm ospheric dioxygen, b ut some other reduced species
(usually com pounds o f non-m etals) are oxidized to m ore soluble form s (Eqn
2 .6).
4Fe2+ + 3 0 2 —+ 2Fe20 3 .. (2.5)
reduced iron (II) iron(III) oxide oxidized
f° rms (soluble) (insoluble) f° rmS
S2~ + 2 0 2 — > SO2- (2.6)

sulfide sulfate
(insoluble) (soluble)
A t present there seems to be a state o f equilibrium between the rate o f

form ation and the rate o f utilization o f dioxygen in the atm osphere. This
implies th a t there are fairly rapid feedback m echanism s in the system which
counterbalance any changes in rates o f form ation or rem oval. The feedback
m echanism is prob ab ly linked to the carbon cycle and the am ount o f organic
m atter inco rp o rated in the ocean sediments. If the concentration o f
dioxygen drops, m ore carbon is in corporated in the sediments, i.e. p h o to
synthesis is increased com pared to rem oval processes; if the concentration of
dioxygen rises, less carbon is in corporated in the sedim ents, i.e. rem oval
processes are increased relative to photosynthesis.
2.1 Molecular oxygen in the atmosphere
L ooking at Figure 2.1, we see th a t carbon dioxide ( C 0 2), sulfur dioxide

( S 0 2) and nitric oxide (N O ) form com ponents that, like elem ental oxygen,
are gases at room tem peratures and atm ospheric pressures. These gases are
all com posed o f small molecules. A molecule contains a fixed num ber o f
specific types o f atom s. It has characteristic properties: if there is a change in
the num ber, or type, o f any o f the com ponent atom s, there will be a change
in the properties and it will have becom e a different molecule. M olecules
have very strong internal forces holding together the atom s o f which they
are m ade (i.e. strong in teratom ic forces), b u t the forces between one
m olecule an d the next are m uch w eaker (i.e. w eak interm olecular forces). In
general we find th a t the greater the m ass o f the m olecule, the greater the
energy required to break up the ordered structure o f a solid (to form first a
liquid, then a gas). The gases m entioned above are all com posed o f
m olecules containing a small nu m b er o f light atom s and thus they have
sm all relative m olecular m ass, e.g. C 0 2 = 44, N O = 30, 0 2 = 32, S 0 2 =
64. One outstan d in g exception is w ater, w hich has a lower relative m olecular
m ass (18) th an these gaseous com pounds, yet exists as a liquid under
tem perature conditions on the E a rth ’s surface. The reasons for this
fo rtu n ate divergence from the n o rm will be considered in C h apter 3.
D ioxygen
The presence o f dioxygen in the atm osphere m eans th a t the reactions
occurring on the E a rth ’s surface are m ainly carried o u t under oxidizing
conditions. One o f the pieces o f evidence th a t suggests th a t the early
atm osphere did n o t contain dioxygen is the presence o f pyrites, FeS2, in
sedim entary rocks form ed by deposition in contact w ith the atm osphere.
N ow adays oxidation reactions (Eqns 2.7 and 2.8) tend to occur. These two
eq uations could be com bined into one (Eqn. 2.9) to give the overall reaction.
2FeS2 + 7 0 2 + 2 H 20 —■* 2F e2+ + 4 S O ^ ' + 4H+ (2.7)
4 F e2+ + 0 2 + 4H+ — > 4F e3+ + 2H 20 (2.8)
4FeS2 + 1 5 0 2 + 2 H zO — ►4 F e3+ + 8 S 0 2” + 4H+ (2.9)
A n early definition o f oxidation was th a t it involved the addition of

oxygen to the substance being oxidized. In E q u atio n 2.7 we see th a t the
sulfur in the pyrites becom es oxidized to sulfate. How ever, it becam e
a p p aren t th a t the addition o f oxygen was only one type o f a m uch larger
group o f reactions th a t involved the transfer o f electrons from one substance
to another. In all these reactions the species th a t donates the electrons is
described as being oxidized. In E q u atio n 2.8, the iron(II), or ferrous iron
(F e2 + ) loses an electron to becom e iron(III), or ferric iron (F e3 + ). The iron
is said to have been oxidized.
If electrons are being lost by some atom s during oxidation, then other
atom s m ust be taking up these electrons. A tom s th a t gain electrons are said
to be reduced. O xidation and reduction m ust occur in association, so th at
one set o f atom s donates electrons and an o th er set o f atom s accepts
electrons. Therefore, there can only be com bined reductio n -o x id atio n
OXYGEN 21
reactions, which are usually called redox reactions. Sometimes it is

convenient to consider only the oxidation half-reaction (Eqn 2.10) or the
reduction half-reaction (Eqn 2.11), b u t neither o f these half-reactions can
occur by itself.
oxidation half-reaction F e2+ — > F e3+ + e~ (2.10)

electron released
reduction half-reaction O 2 + 4e- — ►2 0 2~ (2 . 11)

electron accepted
The oxidation half-reaction m ust be paired up w ith an electron acceptor and

the reduction half-reaction m ust be paired up w ith an electron donor.
A redox reaction will occur when there is b oth a substance th a t will accept
electrons (an oxidizing agent) and a substance th a t will donate electrons (a
reducing agent). T he greater its ability to a ttra ct electrons, the stronger the
oxidizing agent is and the greater the likelihood th a t a redox reaction will
occur. Similarly, the greater the ability to d onate electrons, the stronger the
reducing agent. The tendency to accept electrons can be m easured, and this
m easured electrode p o tential is often expressed as the standard reduction
potential, EP. The electrode potentials allow us to com pare oxidizing and
reducing agents, and gives a m easure o f their relative strengths. The actual
reduction potential varies w ith the tem perature and concentration o f
reactants, so this m ust be taken into account when investigating environ
m ental reactions.
A draw back to lists o f reduction potentials is th a t they indicate w hether a
reaction is theoretically possible, b u t they do n o t indicate the rate o f the
reaction. This kinetic problem is the reason for the controversy over the
in terp retatio n to be p u t on the presence o f pyrites in ancient sediments. The
electrode potentials and experim ental evidence indicate th a t pyrites will be
oxidized by m oist dioxygen, b u t we also know th at samples o f pyrites m ay
be preserved unaltered by dioxygen for long periods if kept dry. W as there
no dioxygen present when the sedim ents were deposited, or was dioxygen
present b u t w ithout the other conditions required for rapid oxidation?
There has been an intern atio n al agreem ent to express electrode potentials
in term s o f the stan d ard reduction potentials, but for m any environm ental
problem s the term oxidation potential is used. The oxidation potential is ju st
the reverse o f the reduction potential. The signs o f the potential are also
reversed, e.g. the stan d ard reduction p o tential for lead (Pb2+ + 2e“ — >•Pb)
is —0.126 V and the oxidation p o tential is + 0.126 V (Pb — > P b 2+ + 2e“ ).
W e shall come across m any redox reactions in the study o f environm ental
systems. The changes in solubility th a t often accom pany these changes in
oxidation state can play a m ajor p a rt in controlling the m obility o f m any
elements.
Photosynthesis
P hotosynthesis is arguably the m ost im p o rtan t step in the oxygen cycle. N o t

only is dioxygen produced - dioxygen w hich is used by hum ans and other
anim als to liberate the energy necessary for life by oxidizing organic
chem icals - b u t the organic chem icals themselves are derived from the
carb o n consum ed in the photosynthesis reaction (Eqn 2.12).
«C 02 + « H 20 ^ (C H 20 ) « + n02 (2.12)
carbon dioxide water carbohydrate dioxygen
W ater is the m ost com m on hydrogen d o nor, w ith the hydrogen being
transferred to the carbon atom s obtained from the carbon dioxide, and the
oxygen from the w ater being liberated as dioxygen. The photosynthetic
reaction only occurs in the presence o f light. The light energy is absorbed by
green plants and converted into chem ical energy which is stored in the bonds
o f the organic chemicals form ed. F o r instance, the production o f 180 g of
glucose (1 m ole o f glucose) requires an energy in p u t o f 2880 kJ at 25 °C and
1 atm osphere pressure. This energy can be released by breaking dow n the
glucose by reaction w ith dioxygen (E qn 2.13). The process is called aerobic
respiration.
C 6H i20 6 + 6 0 2 — > 6 C 0 2 + 6H 20 + energy (2.13)

glucose
The light em itted from the Sun form s the visible p a rt o f the electro
m agnetic rad iatio n spectrum (Figure 2.2). E lectrom agnetic rad iatio n can be
considered to consist o f waves o f electrom agnetic force whose energy is
p ro p o rtio n a l to their frequency (num ber o f vibrations in a fixed time) and
inversely p ro p o rtio n al to their w avelength (distance betw een corresponding
p arts o f adjoining waves, e.g. crest to crest). The relationships between
1022 1019 1017 0.75-0.43 x 1015 1011 109 Frequency (H z = s ')

IQ- 4 10-i 10 400 v 700 104 109 W avelength (nm )
gam
co sm ic infra m icro
ma X-rays ultraviolet radio waves
rays
rays red waves
10 “ 109 107 x 40 10-1 Energy (J mol )

3 x 105 1.6 x 105
energy = N h v J mol 1 — 4 x 10 10 x v J m ol-1

3 x 1017
frequency — Hz
wavelength (nm)
Figure 2.2 The electromagnetic spectrum, showing frequencies, wavelengths and energy ranges
for different radiation types.
OXYGEN 23
energy and wave properties are expressed by E quations 2.14 and 2.15.
energy, E = N h v J m ol-1 (2.14)
E = N h { ^ J m o l" 1 (2.15)
w here N is A v ag ad ro ’s num ber = 6.023 x 1023 m o l-1 ; h is P lanck’s con

stan t = 6.626 x 10-34 J s-1 ; v (nu) is the frequency in cycles per s (s-1 , or
hertz, Hz); c is the velocity o f light in a vacuum = 2.998 x 108 m s_1; A
(lam bda) is the w avelength, in m (or often nm = nanom etre = 10-9 m).
Visible light has a w avelength range o f ab o u t 400 (violet light) to 750 nm
(red light); this is a frequency range o f ab o u t 8 x 1014- 4 x 1014 Hz. By
substituting these values in E quations 2.14 or 2.15 we obtain values for the
energy o f visible light from 320 kJ m o l-1 (violet) to 160 kJ m ol-1 (red).
G reen p lants contain chlorophyll molecules w hich are capable o f
absorbing some o f the visible p a rt o f the electrom agnetic radiation em itted
by the Sun. The energy in this absorbed radiation raises the energy o f some
electrons in the chlorophyll m olecules (Figure 2.3). These excited electrons
light in
11 electroifr8y carbohydrates
reactions
absorption o f solar
energy by
chlorophyll
low-energy
stage I electron
most absorption
at about 270 kJ mol-1
and 180 kJ mol-1
provides electrons
and H +
o2
light out
Figure 2.3 The absorption o f visible light by chlorophyll during photosynthesis.

are d o n ated to an electron acceptor th a t initiates a series o f electron-transfer

reactions leading eventually to the fo rm ation o f carbohydrates, such as
glucose. The light energy is absorbed a t tw o stages in the photosynthesis
system and raises the energy o f electrons. The electrons can n o t be con
tinuously rem oved from the chlorophyll molecules w ithout being replaced.
In p lants and blue-green algae, w ater provides the replacem ent electrons
(E qn 2.16), dioxygen is released and the p ro to n s eventually com bine w ith
carbon.
(2.16)
C hlorophyll absorbs m ainly red and blue light; therefore the light
reflected contains m ainly the unab so rb ed green light - this is why leaves
containing chlorophyll ap p ear green.
Stratospheric ozone and the ozone layer

The electrom agnetic rad iatio n from the Sun th a t falls on the upper layers of
the atm osphere contains m uch m ore U V light (i.e. higher-energy radiation)
th a n does the rad iatio n reaching the land and w ater surface o f the E arth
(Figure 2.4). This UV p a rt o f the electrom agnetic spectrum is often
subdivided into three regions o f different energy (wavelength, A). These
regions are called U V -C (A < 290 nm; highest energy), UV-B (A = 290-320
nm; interm ediate energy) and U V -A (A = 320-400 nm; lowest energy).
T he bonds in the dioxygen m olecule m ay be broken (Figure 2.4, reaction
A) by U V -C to form free oxygen atom s. A t altitudes above 400 km the
m ajority o f the oxygen is atom ic. A t lower altitudes, as the num ber o f
dioxygen and dinitrogen m olecules increases, ozone, 0 3, is form ed (Figure
2.4). The m olecular species, M (usually N 2 or 0 2), rem oves the excess energy
p roduced w hen ozone is form ed and so prevents the ozone decom posing
im m ediately. As reaction B (Figure 2.4) indicates, ozone is destroyed by the
ab so rp tio n o f the lower energy end o f the U V -C ban d plus all o f the
w avelengths in the UV-B band. H ow ever, the equilibrium concentration o f
ozone w ould be m uch higher th a n it actually is if the only reactions involved
in its d estruction were initiated by U V rad iatio n and by atom ic oxygen
(Figure 2.4, reaction F). Some other chem ical species in the stratosphere are
also able to break dow n ozone by a reaction sequence th a t regenerates these
species so th a t they can react again, i.e.
o 3 + x —-♦ o 2 + x o (2.17)
x o + o — >o 2 + x (2.18)
XO + O3 — > 2 0 2 + X (2.19)
OXYGEN 25
solar radiation above atmosphere

UV V IR
50
o2 Ja L 20
Height above surface (km )
25
o3 JH . -*■ o + o 2
h 2o
CO-)
Key
ultraviolet absorbed, < 242 nm (i) HO + 0 3 h o 2 + o2

0
(ii) H 0 2 + O -> OH + 0 2
ultraviolet absorbed, 200-325 nm (iii) H 0 2 + 0 3 - > OH + 2 0 2
0
O + 03 202
infrared absorbed
0
G (i) Cl + 0 3 -> CIO + 0 2

(ii) CIO + O —» Cl + 0 2
(i) NO + 0 3 —» n o 2 + o 2 ___ (iii) CIO + 0 3 -> Cl + 2 0 2
(ii) N 0 2 + O - NO + 0 2
f n°/o J percentage of natural removal rate:
(iii)N 0 2 + 0 3 - * NO + 2 0 2
M i molecular species
Figure 2.4 The absorption of ultraviolet radiation by ozone in the E arth’s atmosphere.
N atural ozone-removal mechanisms are also shown. The ozone layer is at a height of 20-40 km,
depending on latitude.
26 THE OX YGEN RICH PLANET
The m ost com m on naturally occurring species represented by X in reactions

2.17 and 2.18 or 2.19 are N O (nitric oxide) and H O (hydroxyl radical), but
recently there have been significant increases in the concentrations o f Cl
(chlorine) and Br (brom ine) in the stratosphere. R eaction 2.18 is m ore
favoured in the upper stratosphere and reaction 2.19 is m ore com m on at the
base o f the stratosphere, in line w ith the relative availability o f atom ic
oxygen, O, and ozone, 0 3. F o rtu n ately the reaction sequence 2.17 plus 2.18
(or 2.19) can be broken by other chem icals reacting w ith ‘X ’ or ‘X O ’. Even
so, it has been estim ated th a t one ato m o f chlorine can destroy 100 000
molecules o f ozone. The brom ine cycle is even less easily broken and
brom ine is th o ug h t to be 50 times m ore destructive than chlorine. N O and
H O generally destroy fewer ozone m olecules before their cycles are
interrupted.
T he concentration o f ozone in the stratosphere varies w ith altitude. It
reaches a m axim um o f ab o u t ten p arts per m illion by volum e (10 ppm v) in
the lower stratosphere, above the b o u n d ary betw een the stratosphere and
the troposphere. This is the ozone layer.
M ost ozone is form ed above equatorial regions where the incidence of
U V-C is greatest. Once form ed, the ozone m oves tow ards the poles and also
to lower altitudes. T here is generally a higher concentration o f ozone above
p o lar regions because the rate o f rem oval is slower (less UV-B) th an near the
equato r. The absorp tio n o f UV and infrared (IR ) radiation (see C h apter 4)
in the stratosphere m eans th a t the tem perature in the stratosphere is higher
th an at the top o f the troposphere. This tem perature inversion stabilizes air
m ovem ents in the stratosphere and controls w eather p atterns in the
troposphere. A reduction in the q u an tity o f ozone in the stratosphere will
change the energy ab so rp tio n properties and m ay have knock-on effects on
the clim ate at the E a rth ’s surface.
The co n centration o f ozone in the stratosphere shows daily, seasonal and
annual variations o f several per cent. Therefore, it is difficult to identify
changes in concentration caused by anthropogenic effects unless these are
large. Very large reductions have been identified in the spring above the
A ntarctic - the so-called ‘ozone h ole’. W hilst the term ‘ozone hole’ is
atten tio n grabbing, it is a m isnom er. The term implies an absence o f ozone
w hereas the q uantity has rarely been reduced by m ore th an 70% .
M easurem ents o f ozone levels have been m ade at Hailey Bay, in A ntarctica,
since the 1950s. These m easurem ents show th a t values for O ctober each year
were above 300 Dobson units (D U ) up to the early 1960s. There were then
increasingly wide variations and a general decline, so th a t by 1980 m inim um
values h ad decreased to 230 D U . By 1985 values o f 150 D U were recorded in
O ctober and by 1996 the m ean values were dow n to 130-140 D U w ith single
day m easurem ents close to 100 D U . It is clear that:
(a) the lowest values always occur in the spring;

OXYGEN 27
(b) at some altitudes (15-20 km) over 90% o f the ozone m ay be removed;
(c) the ozone abundance levels recover in early sum m er, but now rarely
reach 300 D U com pared to the 350 D U o f the pre-1980s;
(d) year-on-year pattern s can differ quite m arkedly. V ariations in
stratospheric tem peratures appears to be the m ain controlling factor,
w ith lower tem peratures leading to lower ozone concentrations.
The detailed explanation o f these observations is complex, but the outline

features are relatively clear. The p attern o f events over the A ntarctic is
unique in its regularity. Similar events occur over the A rctic on a m ore
irregular basis. The im p o rtan t requirem ents for extrem e ozone depletion
are:
(a) the very low tem peratures developed in the atm osphere during the
A ntarctic winter;
(b) the form ation o f a stable stratospheric circulation p attern called the
A ntarctic p o lar vortex (Figure 2.5);
(c) the increased concentration o f chlorine- and brom ine-containing species
trap p ed inside this polar vortex.
The stratospheric air above the A ntarctic contains very little w ater vapour
(4-6 ppm v); as a consequence nucleation and condensation to form clouds
only occurs at very low tem peratures. W hen the tem perature drops below
198 K (—75 °C) nitric acid trihydrate (N A T) particles, H N 0 3-3H20 , start to
(a) Plan (b) Elevation
Figure 2.5 Diagram atic representation of the Antarctic polar vortex system that exists in the
winter and early spring, (a) Plan view of the winds circulating above the Antarctic continent and
indicating some of the reactions that occur on the surfaces of the polar stratosphere clouds,
PSCs. (b) Elevation showing that the vortex occurs mainly in the stratosphere. The zone of
strong winds virtually isolates the inner zone from the rest of the atmosphere.
condense to form Type 1 p o lar stratospheric clouds (Type 1 PSCs). These

clouds consist o f small particles, sim ilar to ice crystals, w ith an average
diam eter o f 10-6 m and a high surface area. Their form ation removes
nitrogen oxide species from the gas phase and traps them in the clouds as
solid nitric acid. This m eans th a t nitrogen dioxide, which can break the
ozone destruction cycle initiated by chlorine by reacting with the chlorine
m onoxide,
CIO + N 0 2 — ■» C 1 0 N 0 2 (2.20)
is rem oved when the nitrogen species becom e locked up in the clouds. To
m ake things worse, any chlorine n itrate, C 1 0 N 0 2, th a t is already present in
the stratosphere can be destroyed by reactions th a t occur on the surface o f
the solid particles, b u t do n o t occur in the gas phase, e.g.
C 1 0 N 0 2 + H 20 — ►HOC1 + H N O 3 (2.21)
C 1 0 N 0 2 + HC1 — ►Cl2 f H N O 3 (2.22)
These reactions increase the q u an tity o f the potentially reactive chlorine

species Cl (from C l2) and HOC1. The tem peratures in the A rctic are not
norm ally as low as in the A ntarctic. Therefore, p o lar stratospheric clouds
are form ed less frequently and are shorter lived. In 1995 the A rctic
stratospheric tem perature was the lowest for the 29 years th at records have
been kept. This coincided w ith an overall reduction in ozone o f 2 0 % -3 0 % in
M arch, w ith a 50% depletion at some altitudes.
The circulation o f air currents th a t arises because o f tem perature
differences between the p o lar regions and lower latitudes, plus the effect of
the E a rth ’s ro tatio n , leads to the form atio n o f a m ass o f air above the
A ntarctic th a t is essentially isolated from the rest o f the stratosphere (Figure
2.5). The A n tarctic land and ice m ass is surrounded by oceans and this
favours the setting up o f a relatively stable vortex system th a t can last for
several m onths before breaking up in the spring. The air circulation p attern
over the A rctic region is disturbed by the effects o f the land masses th at
radiate out from the N o rth Pole. Therefore, the A rctic vortex system tends
to be unstable and rarely lasts for long. T here is little mixing o f the air inside
the vortex w ith th a t outside. The p o lar stratospheric clouds trapped w ithin
the vortex rem ove nitrogen oxide species from this air and increase the
quantities o f potentially reactive chlorine species such as HOC1, C 1N 02 and
C l2 and brom ine species such as BrO. W ith the arrival o f spring there is an
increase in UV rad iatio n reaching the stratosphere. The chlorine and
brom ine species are broken dow n to release free radicals which then rapidly
destroy the ozone in the vortex system by the reaction sequence G in Figure
2.4. As the vortex breaks up and fresh air enters the region the
decom position cycle is quenched (E qn 2.20) by the new nitrogen oxides th at
OXYGEN 29
have been bro u g h t in. A t the same tim e the ozone is gradually replaced.
Before it is finally filled in, the zone o f ozone deficiency m ay m ove well away
from the A ntarctic and pass over A ustralia or South Am erica.
The increased use o f chlorine com pounds as refrigerants, foam ing agents,
solvents and in aerosol-spray cans has produced a rapid rise in the
concentration o f chlorine in the atm osphere. N atu ral levels o f chlorine are
ab o u t 0.6 p arts per billion by volum e (ppbv). In 1992, concentrations had
reached 3.5 ppbv, and are expected to rise to well over 4 ppbv before a
decline m ight occur. The halting o f the present rise and the size o f the peak
value depend upon how effectively emissions o f the chlorine com pounds are
controlled.
The chlorofiuorocarbons (C FCs) such as CC13F (CFC-11) and CC12F 2
(CFC-12) were developed as inert, non-toxic com pounds th a t could be
safely used by industry and in the hom e. U nfortunately they are so inert th at
when they escape into the atm osphere they slowly pass unchanged through
the troposphere and enter the stratosphere. Here UV-C causes
photochem ical decom position, yielding free chlorine atom s th at catalyse the
decom position o f ozone, e.g.
CC12F 2 U^ ht Cl 0 2 + CIO Oz + Cl (2.23)

dichloro- activated chlorine can react
difluorom ethane chlorine oxide again
atom
The C FC s have long atm ospheric lifetimes (65 years for CFC-11 and 130
years for CFC-12). There are already enough of these com pounds present in
the atm osphere to continue to give elevated stratospheric chlorine
concentrations until 2100.
The com pounds th a t have been proposed to replace the C FC s
im m ediately are the hydrochlorofiuorocarbons (H C FC s) containing
hydrogen atom s, which m akes them m ore likely to break dow n in the
troposphere. Therefore, only a small p ro p o rtio n o f the em itted com pounds
should reach the stratosphere. C om pounds being m anufactured include
C H F 2C1 (H C FC -22) and CC12F C H 3 (H C FC-141b). The ultim ate goal is
fully to replace these chlorinated com pounds with chemicals th a t do not
release any ozone-destroying species.
The phasing o u t o f the C F C -type com pounds is difficult because
replacem ents are either poisonous (am m onia) or m ore expensive (H C FC s)
which causes problem s to poo rer countries such as India and China. These
countries w ant to provide refrigerators to m ost o f their people but the higher
costs w ould hold back this program m e.
The H alons are sim ilar to the C FC s b u t contain brom ine, e.g. H alon-
1301, C B rF 3, and H alon-1211, C B rC lF 2. They are widely used in fire
extinguishers, especially in areas where w ater cannot be safely used. Finding
suitable alternatives for these brom ine-containing com pounds m ay well be
30 THE OX YGEN RICH PLANET
even m ore difficult th an finding alternatives for CFC s. M ethyl brom ide,
C H 3Br, is produced n aturally in ocean systems and anthropogenically by
biom ass burning, use as a soil fum igant and from exhausts o f cars using
unleaded petrol. The size o f the n atu ral flux is not well characterized, but
probably accounts for ab o u t h alf o f all m ethyl brom ide emissions.
T here is increasing evidence th a t there are general reductions in ozone
concentrations in the stratosphere. By 1997 there has been a decrease o f
5% —10% in m id-latitudes, w ith sm aller reductions in equatorial zones and
larger reductions near the poles, especially A ntarctica. The high n atu ral
variability in ozone concentration m akes confirm ation o f these reductions
and the identification o f harm ful effects difficult. The position is further
com plicated by n atu ral p ertu rb atio n s introduced by large volcanic
eruptions. If there is a large am o u n t o f sulfate aerosol injected into the
stratosphere (M o u n t P in atu b o em itted 17 M t S 0 2 into the stratosphere in
1991, increasing particulates at least tenfold), these particles can behave like
the p o lar stratospheric clouds and increase the relative availability o f ozone
destroying species such as chlorine. The rates o f ozone rem oval in 1992 are
th o u g h t to have been enhanced by volcanic eruptions in 1991 and 1992. A n
extra l% - 2 % o f ozone is estim ated to have been rem oved in 1992 and 1993.
Because anthropogenically introduced chlorine and brom ine levels will
rem ain high for so long, it is expected th a t there will be m ore and m ore UV-
B reaching the E a rth ’s surface. Before ozone depletion began 7 0 % -8 0 % o f
the UV-B was absorbed before reaching the E a rth ’s surface. A 10%
reduction in stratospheric ozone co ncentration w ould reduce the am ount of
UV-B being absorbed to 5 5 % -6 5 % . This could have m ajor effects on
susceptible organism s such as p lan k to n and land plants. Effects on hum ans
w ould include increased risk o f skin cancer and eye cataracts. These direct
effects on hum ans are less w orrying th an the interference w ith food
pro d u ctio n th a t could occur.
The increased use o f fertilizers is causing an increase (0.25% per year) in
the quantities o f dinitrogen oxide, N 20 , being produced by m icroorganism s
(see C h ap ter 5). N 20 , like C FC s, is very stable and passes up through the
troposphere and enters the stratosphere. In the stratosphere it is broken
dow n u nder the influence o f UV rad iatio n into a m ixture containing ab o u t
95% dinitrogen and 5% N O , one o f the ozone-destroying com pounds
(Figure 2.4). The effects o f increased N 20 concentrations are at present
th o u g h t to be relatively small and m ay well be balanced by increases in
m ethane, C H 4, which should increase ozone concentrations by reacting with
chlorine in the stratosphere.
There is still a lot to be learnt ab o u t stratospheric chem istry and the
balance betw een p ro d u ctio n and destruction o f ozone. The long lifetimes of
m any o f the chemicals th a t have been released into the atm osphere are a
m ajo r source o f concern as rem edial action will take a long time to becom e
effective.
OXYGEN 31
Tropospheric ozone
The concentration o f ozone in the troposphere is very m uch lower than in
the stratosphere. This is ju st as well, because ozone is toxic to plants (as little
as 80 ppbv can reduce grow th) and to hum ans (1 ppm v is fatal and 120 ppbv
can cause breathing difficulties). The n atu ral background concentration is in
the range 20-60 ppbv. However, there is some evidence th at in the
nineteenth century concentrations were only 10 ppbv.
A lthough a very small p a rt o f the tropospheric ozone is brought down
from the stratosphere, m ost is produced near ground level. This ozone is
form ed by the action o f UV-A (A < 400 nm) on nitrogen dioxide:
N 0 2 — >NO + O (2.24)
O + O2 + M — > 0 3 + M (2.25)
(M is a third body, usually N 2 or 0 2, th at removes energy released in the

reaction.)
Because ozone is also destroyed by nitric oxide the build-up of ozone is
dependent on a large num ber o f linked reactions. Some o f these will be
discussed later in C h ap ter 5. The im p o rtant features are th at ozone
p ro d u ctio n is favoured by the presence o f nitrogen oxides from com bustion
processes, e.g. petrol engines, industrial furnaces, forest fires, together with
h ydrocarbons and sunlight. The hydrocarbons m ay be introduced into the
atm osphere from u n b u rn t fuel or m ay be there naturally (e.g. volcanic or
agricultural em issions o f m ethane or emissions o f terpenes and isoprene
from trees and other plants). O zone levels in m any countries appear to be
steadily rising and concentrations greater than 120 ppbv are becom ing
increasingly com m on, especially in the spring and summer.
These high tropospheric ozone concentrations are being linked to
increasing levels o f asthm a and bronchial problem s am ongst urban
populations. Similarly, the decline in forest grow th th at was initially blam ed
on ‘acid ra in ’ is now recognized as being partially due to the detrim ental
effects o f ozone. H um an activities th at reduce stratospheric ozone
concentrations and thus increase UV-B radiation levels are helping to
increase ground-level ozone concentrations. The m ore UV-B th at reaches
the lower levels o f the troposphere, the m ore likely th a t harm ful ozone will
be produced in th a t region o f the atm osphere where it can do m axim um
dam age to crops and hum ans.
Part Two Major elements found in living matter
T here are 90 n aturally occurring elements on E arth and, provided sensitive-

enough analytical m ethods are used, all 90 elements are likely to be detected
in living organism s. H ow ever, in hum ans 99.3% o f all atom s are carbon,
hydrogen, nitrogen and oxygen. O ther organism s have a similar over
whelm ing preponderance o f these four elements. W e shall study the
chem istry o f hydrogen, carbon and nitrogen in this section of the book. In
addition, the chem istry o f sulfur and p h o sphorus will be considered. Sulfur
is an im p o rtan t m inor com ponent o f m any o f the molecules found in
organism s. P h osphorus is also found in some biologically im portant
m olecules, b u t the chem ical changes th a t it undergoes in n atu ral systems are
relatively limited.
Living organism s are characterized by the presence o f cells - ‘the smallest
unit o f life’ (Figure 1.4). In cells occur the m any reactions th at are necessary
for the energy p ro d u ctio n and continuing m aintenance o f the organism . The
cell has an outer m em brane which acts as a container for the internal
com ponents and also regulates the passage o f chemicals into and out o f the
cell. Cells consist o f ab o u t 70% w ater, by weight, and 28.5% organic
molecules. M o st o f the wide variety o f organic com pounds m aking up the
cells can be arranged into four groups. These groups are (a) carbohydrates,
(b) lipids, (c) nucleic acids and (d) proteins.
As Figure P2.1 illustrates, the organic molecules found in cells are
actually produced by the linking together o f smaller molecules. In each case,
when two o f the sm aller molecules com bine a molecule o f w ater is released.
This is called a condensation reaction. The reverse reaction, which breaks
dow n the large molecules into their constituent smaller molecules, occurs in
the presence o f w ater, usually requires a catalyst and is called hydrolysis. If a
large num ber o f small molecules are used, as in the production o f starch,
cellulose, proteins and nucleic acids, the large molecules are called polymers
and the small m olecules are monomers.
Carbohydrates
Carbohydrates generally have the com m on form ula C A(H 20 ) v. The simplest
carbohydrates are the m onosaccharides which usually contain either five
34 MAJOR ELEMENTS F O U N D IN L I V I N G M A T T E R
sta rch cellu lo se
Figure P2.1 Inter-relationships between some organic molecules and their constituent
elements.
carb o n atom s, e.g. ribose, C 5H 10O 5, or six carbon atom s, e.g. glucose and
fructose, C 6H i20 6. These com pounds consist o f either five- or six-m em bered
rings containing one oxygen ato m and four or five carbon atom s,
respectively. These simple units can be cross-linked to form disaccharides
(two units), e.g. sucrose (1 glucose + 1 fructose: C ^ I - ^ O n ) ; or poly
saccharides (up to several th o u san d units), e.g. starch and cellulose. Starch is
used as a reserve foo d stu ff in plants and to a lesser extent in anim als.
Cellulose acts as a supporting structure for the cells o f plants and is the m ost
ab u n d a n t type o f organic com pound on the E arth. U nfortunately, hum ans
can n o t digest cellulose so it can n o t be directly used as a food.
Lipids
Lipids are a rath er diverse group o f com pounds th at are soluble in organic
(non-polar) solvents - such as trichlorom ethane (chloroform , CHC13),
benzene (C 6H 6) and ethoxyethane (ether, C 2H 5O C 2H 5) - but insoluble in
M A J O R E L E M E N T S F O U N D IN L I VI N G M A T T E R 35
(a)
H 2COH HOOCR H 2COOCR h 2o
HCOH + HOOCR' -> HCOOCR' + H 20
H 2COH HOOCR" H 2COOCR" h 2o

glycerol three fatty triglyceride
acids
(b) Saturated fatty acids

COOH
stearic acid C H 3(C H 2) lfiCOOH A A A A A A /W
COOH
palmitic acid C H 3(C H 2) l4COOH A /V W V W
(c) Unsaturated fatty acids
oleic acid C H 3(C H 2) 7CH = C H (C H 2) 7COOH A A A A = / V W COOH

arachidonic acid (a polyunsaturated acid)
COOH
C H 3(C H 2) 4 (CH = C H C H 2) 4(C H 2) 2COOH
(d) Phospholipids, e.g. lecithin
h 2c o o c r
I
HCOOCR'
I o
! it
H 2C O - p - O - C H 2 C H 2 N (C H 3) 3
+
o
Figure P2.2 Lipids, (a) Form ation of a triglyceride. Structures of (b) saturated fatty acids,
(c) unsaturated fatty acids and (d) phospholipids.
w ater. If the lipid is solid at room tem perature it is called a fat (m ost anim al-
derived lipids), and if it is liquid it is called an oil (m ost vegetable-derived
lipids). The m ajority o f the com m only found lipids are form ed by the
com bination o f glycerol (an alcohol w ith three hydroxyl, O H , groups) and
fatty acids (hydrocarbons with a carboxylic acid, -C O O H , group; Figure
P 2 .2).
The letter ‘R ’ in a form ula is used to indicate any organic group, usually
only containing carb o n and hydrogen. If the carbon atom s in the group R
are joined to each other by single bonds, both the acid and the lipid it form s
are described as being saturated. Unsaturated acids and fats have double
bonds between some o f the carb o n atom s. The greater the degree o f
u n satu ratio n , i.e. the larger the num ber o f c a rb o n -c arb o n double bonds, the
lower the melting poin t o f the lipid.
It should be noted th at the oil (‘m ineral oil’) th at is extracted from the
ground and used as the basis o f the petrochem ical industry is m ainly
36 MAJOR ELEMENTS FOUND IN L I V I N G MATTER
com posed o f hydrocarbons rath er th an triglycerides. Chem ically m ineral

oils and lipid oils are quite different.
In phospholipids, the glycerol is com bined w ith two fatty acids and a
substituted phosphoric acid occupies the third position (Figure P2.2). The
p hosp h ate group is relatively polar (w ater soluble). Cell walls are com posed
o f double layers o f the phospholipids, w ith the p o lar group as the exterior o f
the wall (in contact w ith aqueous m edia) and the fatty-acid, non-polar,
groups m aking up the interior o f the wall.
Nucleic acids
Nucleic acids are polym ers com posed o f an arom atic base (e.g. adenine),
plus a pentose sugar (e.g. ribose or 2-deoxyribose) and phosphate groups
(a)
H H O H H o
\ I ^ I
N — C— C -C —C
/ I \ / I \
H H OH H H S -C -H OH
I
H
Cy
H H O O
I II //
N -C 1 C — N- -c—c H .O
/ I
H H H OH
H S - C —H
I
H
<~?L~
Figure P2.3 The form ation of peptide linkages between amino acids to produce proteins,
(a) Form ation of peptide linkage (PL) between glycine (G) and cysteine (Cy), producing a
dipeptide, (b) Diagram matic representation of a protein, a polypeptide, showing peptide
linkages between amino acid residues.
MAJOR E L E M E N T S F O U N D IN L I VI N G M A T T E R 37
(PC>4~) which, together, form a nucleotide unit. The nucleotide units are
then linked together to form the nucleic acid, e.g. ribonucleic acid (R N A ) or
deoxyribonucleic acid (D N A ). The nucleic acids store and transm it genetic
inform ation.
Proteins
Proteins are polym ers o f am ino acids form ed by the com bination o f the
acidic ( C O O H ) group o f one am ino acid with the basic am ino (-N H 2)
group o f an o th er am ino acid (Figure P2.3) to form a peptide bond. Proteins
are large polypeptides with m olecular weights greater th an 10 000.
Proteins m ay be soluble or insoluble in water. The latter group are utilized
in anim als for b o th structural and connective tissue. They are also im portant
com ponents o f enzymes, which are catalysts.
3 Hydrogen
Hydrogen A bundance by weight (the relative abundance is given in

parentheses): E arth , 78 ppm (18); crust, 0.22% (10); ocean,
11% (2); atm osphere as H 2, 0.5 ppm (9). ppm = mg k g -1 .
H ydrogen is by far the m ost a b u n d a n t elem ent in the Universe. Over 90% of
all atom s are hydrogen. The next m ost com m on elem ent is helium , He, with
an abundance o f 8% or 9% . All the other atom s taken together constitute
less th an 1% o f the m aterial in the U niverse. In contrast, hydrogen is only a
m inor com ponent o f the E arth , although its presence in w ater on the E a rth ’s
surface has been critical in providing the right conditions for the develop
m ent o f life on the planet.
It is th o u g h t th a t all the elem ents were originally derived from hydrogen,
being form ed by nuclear reactions occurring in stars. These reactions are
still continuing and the original hydrogen is gradually being consum ed.
Stars form when the g ravitational collapse o f a hydrogen gas cloud releases
energy to produce a co ncentration o f ho tter, denser m aterial. W hen the
tem perature rises to ab o u t 10 m illion degrees kelvin (K), the hydrogen
nuclei can com bine to form helium (E qn 3.1).
2]H —> jH -A ^He ^ jH e + 2]H (3.1)

hydrogen deuterium helium-3 helium -4
The co m bination o f two lighter nuclei to form a heavier nucleus is called

nuclear fusion and this series o f nuclear-fusion reactions liberates
2.5 x 1012 J for each 4 g o f 2He produced. (As a com parison 1 gallon o f
p etroleum - ab o u t 4 kg - liberates 1.2 x 108 J when burnt.) W hen the
concen tratio n o f 2He becomes high enough, further nuclear reactions can
occur leading to the form ation o f carbon, (Eqn 3.2).
I j H q — > 4 Be ^ n6C (3.2)

beryllium carbon
Once 12C has been produced a num ber o f reactions can occur th a t involve
the conversion o f m ore |H to and the addition o f n6C to larger nuclei
to produce oxygen ( ^ O ) , neon (jJjNe), m agnesium (24M g), silicon (f4Si)
and so on up to iron ( ^ F e ) . The ^ F e nucleus is the m ost stable o f all nuclei,
HYDROGEN 39
at tem peratures below 30 x 109 K. H eavier nuclei, and those w ith odd
num bers o f pro to n s, are m ainly produced in stars by neutron-capture
reactions (E qn 3.3), the same process is used to produce isotopes com
m ercially in nuclear reactors on E arth.
^Fe + 3^n — ►^ C o + J}e (3.3)

iron-56 neutrons cobalt-59 electron
Because neutrons have no charge they can penetrate the nucleus of atom s
relatively easily and m ay induce instability th at leads to the form ation of
new elements.
The stability o f a nucleus depends upo n the balance between the attractive
forces and the repulsive forces. The m ajor repulsive force is due to the
electrostatic interaction between the positive charges o f the protons. The
attractive forces are o f very sho rt range and depend upon the total num ber
o f nucleons, i.e. p ro to n s plus neutrons. As the num ber o f p rotons increases,
the repulsive forces increase m ore rapidly than the attractive forces unless
extra neutrons are added to counterbalance this effect. W ith the lighter
elem ents the n eu tro n :p ro to n ratio for stable nuclei is ab o u t 1:1 —e.g.
(2p + 2n), !gO (8p + 8n) - but w ith the heavier nuclei the pro p o rtio n o f
neutrons required for stability becomes greater - e.g. nickel, | N i (28p +
30n), lead, 28°26Pb (82p + 124n) — as show n in Figure 3.1. M any elements
have m ore th an one stable isotope. F o r instance, oxygen has three stable
isotopes, ’gO, ]gO and 180 . Tin has ten stable isotopes - the largest num ber
o f any element.
U nstable nuclei becom e stable when the n eu tro n :p ro to n ratio is adjusted
so th a t the attractive forces becom e stronger than the repulsive forces. The
unstable nuclei are said to be radioactive. There are four m echanism s by
which unstable nuclei achieve stability (Figure 3.1).
Neutrons in excess: (3 (beta m inus) emission
on > iP + /? (-^ e ) + 7 P -4 )
neutron proton electron gamma rays
One o f the neutrons is converted into a p roton, and an electron is ejected

from the nucleus. T here is an increase in atom ic num ber and a new element
is produced (Eqn 3.5).
]H — > 23He + _ <Je (3.5)

hydrogen-3 helium
F u rth er lowering o f energy is achieved by the emission o f gamma radiation

or neutrinos. G am m a rays are very short-w avelength, high frequency,
electrom agnetic radiatio n (Figure 2.2), and neutrinos are small neutral
particles. W hen radioactivity was first discovered, various types o f radiation
EXCESS
NEUTRONS
Key
xxxxxxx p o s itio n o f sta b le nuclei
-------------- line o f 1 : 1 n : p ratio
( ) m o d e o f d eca y
/ /
/ /
(/ EXCESS
E 60
=3 PR O TO N S
X/ / ( P +)
( m xxX>/'
20 J * ( k -electron capture)
£ ___ I_____ i_____ I_____ i_____ L

20 60 1(H)
N um ber of protons
Figure 3.1 The neutron:proton ratio of nuclides, and its relationship to nuclear stability and
radioactive display mechanisms.
were recognized and nam ed a (alpha), (5 (beta) and 7 (gam m a) after the first
three letters o f the G reek alphabet. The nam es are still used today even
tho u g h the co nstitution o f the rad iatio n is know n.
Protons in excess: (3+ (beta-plus or positron) emission
|p — >■ in +/3+ (°e) (3.6)

proton neutron positron
A positron has the same properties as an electron except th a t it has a positive

charge rath er than a negative charge. The em itted positron collides with an
electron and they are b o th destroyed, giving out gam m a radiation. P ositron
em ission is often found w ith artificially produced radioisotopes. The atom ic
num ber decreases and a new elem ent is form ed (Eqn 3.7).
29CU — >^ N i + ?e (3.7)

copper nickel positron
Protons in excess: a (alpha) emission
A n alpha particle, which is a helium -4 nucleus (2H e2+), is em itted from

heavy unstable nuclei causing the loss o f two neutrons and two protons.
This type o f decay is only effective for elem ents th a t have m ore neutrons
th an pro to n s, i.e. lie above the 1:1 line (Figure 3.1) so th a t the p ro p o rtio n of
HYDROGEN 41
p ro to n s is reduced (E qn 3.8).
92^ 90T h ^He (3.8)

ranium thorium alpha particle
11 146 = 1 . 5 9 ^ ^ = ^ = 1.60
p 92 / \P
Protons in excess: electron capture

The nucleus captures an electron from the lowest-energy group o f electrons
(the Is or ‘K shell’), converting a p ro to n into a neutron (Eqn 3.9). A nother,
higher-energy, electron drops into the 4K shell’, and X-rays, short-
w avelength electrom agnetic rad iatio n (Figure 2.2), are emitted.
|P + _®e — > in (3.9)

proton electron neutron
A gain a new elem ent is produced (E qn 3.10).

“ ~ - 4 0 Ar+ ^ + x ( 3 J 0)
potassium argon gamma rays X -rays
3.1 Isotopes of hydrogen
N aturally occurring hydrogen, on the E arth, consists o f 99.985% ]H,

0.015% 2H, and the radioactive 3H , whose concentration in surface ocean
w ater has been estim ated as 1 x 10~18%. H ydrogen is the only element
whose isotopes are given specific nam es - }H, protium (symbol P); 2H,
deuterium (symbol D); jH , tritium (T).
As we have already seen, nuclear-fusion reactions can liberate very large
am ounts o f energy. The uncontrolled release of this energy occurs when
hydrogen bom bs are exploded. N uclear-fusion reactions only occur at very
high tem peratures (5 x 106-100 x 106 K), so a very large am ount o f energy
m ust be p u t into the system before the greater am ount o f energy that
nuclear-fusion reactions produce can be released. The problem s are how to
achieve and m aintain the initiating tem perature and then how to extract the
energy in a controlled m anner from this hot mass. In the hydrogen bom b an
explosion is used to raise the tem perature to the required value: no attem pt
is m ade to control the subsequent release o f energy from the fusion reaction.
The advantage o f nuclear-fusion reactions as an energy source is that, if
deuterium can be utilized as the fuel, existing fuel reserves should last for at
least 1 million years, as com pared with the 400 years th at fossil fuels (coal,
oil and n atu ral gas) are forecast to last. Two o f the possible nuclear-fusion
42 MAJOR ELEMENTS FOUND IN L I V I N G M A T T E R
reactions, all o f which involve isotopes o f hydrogen, are given in E quations

3.11 and 3.12.
2jH — > ’ He + in (3.11)
2 ? H — >]H + l H (3.12)
The environm ental problem s associated w ith nuclear-fusion reactors, if they
are ever built, appear to be less th an the problem s of present-day nuclear-
fission reactors, but until we are m uch closer to seeing how the reactor will
actually operate the problem s can n o t be com pletely identified. Nuclear
fission involves the breaking up o f large nuclei, such as 235U , by bom barding
them w ith neutrons. This break-up releases less energy th an nuclear-fusion
reactions, but m ore energy th an chemical reactions, for a given mass o f fuel.
U n fortunately, the initial p roducts o f nuclear-fission reactions are
radioactive and the disposal o f this dangerous waste presents a m ajor
problem .
T ritium is produced naturally by the interaction o f cosmic rays (protons,
electrons, various nuclei and nuclear particles com ing from outer space)
w ith gas in the upper atm osphere. The tritium gradually changes into stable
^He by a radioactive-decay process (E qn 3.5) with (3~ emission. The decay
reactions are governed by statistical laws and the decay is a first-order
reaction (E qn 3.13). This m eans th a t the num ber o f disintegrations in a fixed
time period from a group o f radioactive atom s is p ro p o rtio n al to the
num ber o f radioactive atom s present (E qn 3.14). As the disintegrations
occur, the num ber o f radioactive atom s rem aining becomes smaller and thus
the num ber o f disintegrations in the given tim e period also decreases - a
typical exponential relationship.
dN
rate o f disintegration, = —AN (3.13)
N = N(,e~Xl (3.14)
where N is the num ber o f atom s present at tim e t\ A is the decay constant, i.e.
the probability o f a nucleus disintegrating in unit time; N 0 = num ber o f
atom s originally present, i.e. when t = 0 .
A convenient expression for com paring rates o f decay is the half-life, / 1/2,
i.e. the tim e taken for an initial num ber o f atom s (7V0) to be reduced to half
th at num ber: N = J^V0 when t = t\/2. The half-life for tritium is 12.5 years. If
we start with a fixed num ber o f tritium nuclei, say 2000, then after 12.5 years
there will be 1000 nuclei, after 25 years 500 nuclei, and after 37.5 years 250
nuclei. In practice, because the decay process is random , there w ould not be
exactly 1000, 500, 250, etc., b u t 95.4% p ro bability th at the value w ould be
1000, 500, etc., plus or m inus tw o times the stan d ard deviation. The half-life
HYDROGEN 43
o f tritium is so short com pared to the age o f the E arth th a t the only way th at
there can be any tritium present now is for the supply to be continuously
replenished. (Even if the whole m ass o f the E arth had been tritium , i.e.
contained ab o u t 1051 atom s o f ^H, after 169.4 half-lives, or 2117 years, there
w ould be no atom s o f 3H left.) In addition to n atural sources, tritium is now
p roduced by nuclear explosions, in nuclear reactors and in nuclear-fuel
reprocessing plants. Because o f tritiu m ’s short half-life the stopping o f these
m ilitary and industrial activities w ould allow the reduction back to natural
levels to occur relatively quickly. The tritium released, usually as a gas,
exchanges w ith hydrogen in w ater and the tritiated w ater can enter living
organism s as p a rt o f the ingested w ater. W hen a tritium nucleus decays it
emits a (3~ particle (on average these each have an energy o f 3 x 10—15 J).
This energy is so low th at the electron will not penetrate m ore th an a few
m illim etres o f air and w ould be stopped, for example, by hum an skin.
H ow ever, the tritiated w ater can enter cells and even low-energy (3 particles
are capable o f causing disruption to m etabolic processes. (3 particles are
ejected from the atom ic nucleus w ith a high velocity: w hen they collide with
an ato m they give up some o f their energy to th at atom , often causing one of
the outer electrons to be lost and so producing a positive ion. The particle
continues to collide w ith atom s, causing further ionization, until it loses its
kinetic energy and comes to a stop. The higher the initial energy o f the (3
particle, the m ore penetrating it is and the greater the am ount o f ionization
it can cause. It is the transfer o f energy to molecules in living cells th at causes
m alfunctioning and hence the concern ab o u t the health effects o f radioactive
m aterials.
3.2 Water
H ydrogen is only a m inor com ponent o f the E arth as a whole, but w ater is
o f m ajor im portance to the survival o f life on the planet. W ater covers about
70% o f the E a rth ’s surface and the properties o f this liquid and its vapour
control the clim atic conditions th a t m ake life possible on E arth. In addition,
w ater’s solvent properties control the chemical w eathering o f rocks, the
transfer o f nutrients to plants and the transfer o f chemicals inside
organism s.
O f all w ater w ithin the surface zone o f the E arth, 97% is in the oceans
(Figure 3.2), ab o u t 2% is in ice caps and glaciers, which cover 10% o f the
present land surface, and only 0 .6 % is fresh w ater o f direct use to hum ans.
The w ater cycle is driven by the absorp tio n o f solar energy, m ost o f which
causes evaporation o f w ater from the oceans and land although a small
p ro p o rtio n generates the winds, waves and currents th a t aid the circulation
in b oth the atm osphere and w ater masses; 86% o f the w ater evaporated
comes from the oceans, but only 78% o f the rain and snow th at falls comes
44 MAJOR ELEMENTS F O U N D IN L I V I N G M A T T E R
ATMOSPHERE
Figure 3.2 The water cycle, in simplified form.
dow n on the oceans. There is a net transfer o f w ater from the oceans to the
land so th a t the precipitation on to the land is 57% greater th an the
evap o ratio n from the land. The extra w ater added to the land eventually
returns to the oceans via surface ru n o ff in rivers or direct seepage o f ground
w ater into the oceans. The average ‘residence tim e’ for w ater in the
atm osphere is 11 days. The evap o ratio n o f w ater requires the ab sorption of
energy and tends to reduce the tem perature at the a ir-w a te r interface.
This energy is released again w hen the w ater v apour condenses, so the
m ovem ent o f w ater v apour transfers heat energy from one area to another.
As w ater evaporates m ost rapidly w herever the tem perature is highest and
condenses when the tem perature drops, the w ater cycle is effective in
reducing the tem perature differences betw een areas. A lthough the average
p recipitation over all land masses is equivalent to ab out 700 m m a year,
there are vast differences between different areas bo th in total am ount and
in seasonal variations - com pare the A tacam a D esert, Chile, which has 0
m m a""1, w ith C herrapunji, India, which has 26 x 103 m m a -1 . In B ritain
the m ean value for low lands is 500 m m a -1 , w ith 2500 m m a -1 in western
hill areas.
The w ater th a t enters the atm osphere is com posed o f w ater th a t has
evaporated from salt- or fresh-w ater sources leaving the dissolved
com ponents behind. H ow ever, small sea-spray droplets throw n into the air
undergo rapid evaporation, leaving fine salt particles suspended in the
HYDROGEN 45
atm osphere. The m ajority o f these particles return to the ocean, but
sufficient are carried over the land to be washed out by rain, or snow, and to
m ake a significant addition o f sodium , N a + , and chloride, C P , ions,
especially to those areas close to the sea. The rain also dissolves other
soluble com ponents present in the atm osphere, such as dioxygen, di
nitrogen, carbon dioxide and the oxides o f sulfur and nitrogen. In addition,
dust and other insoluble particulate m atter is washed out. In areas where
there are large inputs o f sulfur oxides and nitrogen oxides, particularly
associated w ith industrial processes and fossil-fuel com bustion, the rain may
becom e between ten and a hundred times m ore acidic than norm al.
The rain w ater th a t runs over and thro ugh the surface o f the land
dissolves soluble species. The w eathering process is speeded up by bringing
reactive species, such as acids, into contact w ith the m inerals o f the soil and
rocks, and by the rem oval o f the reaction products. This results in the w ater
entering rivers having m ore dissolved solids than the rain. The residence
time o f the w ater on land varies from a few days w ith surface run o ff to
hundreds or thousands o f years for ground w ater and ice caps. On entering
the sea there is a region o f mixing o f river and sea water, often in an estuary,
which is very com plex chemically. As well as there being rapid changes in
the to tal co n centration o f all dissolved solids, individual soluble species m ay
becom e insoluble and previously insoluble com ponents o f the suspended
solids carried by the rivers m ay becom e soluble as the chemical conditions
alter in the zone o f mixing. The levels o f dissolved species in the oceans
app ear to be in equilibrium although there are local variations. The
residence time o f w ater in the oceans is ab o u t 4000 years.
The soluble com ponents in river w ater are derived partly from
atm ospherically recycled m arine salts deposited on the land by rain or snow
and partly from the w eathering o f rocks and soils. The characteristic cation
in sea w ater is sodium , w hereas in fresh w ater it is calcium. If the total
dissolved-solids content o f n atu ral w aters is plotted against the weight ratio
o f dissolved sodium :dissolved sodium plus calcium (Figure 3.3), a clear
relationship between the three factors can be seen. The rivers with the lowest
dissolved-solids content have a high p ro p o rtio n o f sodium , indicating th at
m ost o f the dissolved ions cam e from precipitation (rain or snow). A
com parison (Figure 3.4) o f the concentrations o f the m ajor dissolved cations
in rain w ater falling on the catchm ent o f the Rio Tefe (1 in Figure 3.3a) and
the ions in the river w ater shows th a t a p a rt from an increase in potassium
and silicon there is little difference. Rivers with these types o f dissolved
solids are described as being precipitation dom inated (Figure 3.3b). They
are usually in areas w ith low relief where w eathering has alm ost reached the
end o f its cycle and the soils contain only the m ost stable m ineral
com ponents.
AJOR ELEMENTS FOUND IN L I V I N G M A T T E R
m ajor oceans / * j
(a) *I
x | Black
^Caspian x
1()4 Jordan
x / Baltic
/
10 -'
/
C olorado
/
M ississip p i/
10; C o lu m b ia *
• X \
\
C on go
V O rinoco
\
10
1 R io Tefe
2 Rio Grande
J ____ I____ I____ L J ____ I____1
10J
10
10
10
J ____ L
0.1 0.2 0.3 0.4 0.5 0 .6 0.7 0 .8 0.9 1.0
Weight N a+
Weight (N a+ + Ca24)
:hei listry of the E arth’s surface waters: (a) variations in proportions of sodium
par d to total dissolved solids; (b) processes controlling the chemistry of the
ate! >. (After Gibbs, R.J. 1970. Mechanisms controlling world water chemistry.
\-9i . Copyright © 1970 AAAS.)
HYDROGEN 47
E (a) Sea water
1COr*1-.
iz ©
c —
<
oU ,|II
OI
U E
•a
JZL
(b) Rain (c) River
10 -
s<L>!
o oc
c E
Na Ca K Mg Si Cl HCO;, Na Ca K Mg Si Cl H C 0 3
Figure 3.4 Com parison of the major dissolved components in (a) sea water, (b) rain water
falling on the Rio Tefe basin, and (c) the Rio Tefe (1 in Figure 3.3a). (After Gibbs, R.J. 1970.
Mechanisms controlling world water chemistry. Science 170, 1088 90. Copyright © 1970
AAAS.)
The w ater running o ff the land picks up m ore soluble species in areas
where w eathering is still in its earlier stages, so the total dissolved-solids
content rises and the p ro p o rtio n o f calcium increases. The actual p ro p o rtio n
o f calcium to sodium will depend upon the rock types being w eathered.
C atchm ents w ith high p ro p o rtio n s o f lim estones (31% Ca) or basic igneous
rocks (7% Ca) will obviously have m uch higher p roportions o f calcium than
catchm ents draining acid igneous rocks (1.6% Ca) or sandstones ( l% -2 %
Ca). (See P art Three.) As rivers flow tow ards the sea there is some
evaporation o f the w ater. In arid areas, where evaporation exceeds rainfall,
the co n centration o f dissolved species will be m arkedly increased as the
w ater evaporates. If the concentration o f calcium rises sufficiently for the
solubility o f calcium carbonate (6.7 x 10“ 3 g d irT 3) to be exceeded,
precipitation o f calcium carbonate will occur and the p ro p o rtio n of sodium
will correspondingly increase. The ultim ate product o f this process is sea
w ater. Rivers appearing on this p art o f the diagram are dom inated by
evaporatio n -cry stallizatio n processes, and their concentration relationships
change along their length, e.g. the Rio G rande (2 in Figure 3.3a). The use of
river w ater for irrigation will increase its dissolved load by passing it
thro u g h the soil, allowing m ore soluble com ponents to be picked up and
also increasing the time for evaporation to occur. This can be a m ajor
problem as the higher the dissolved-species content, the less suitable the
w ater becomes for drinking, irrigation and industrial usage.
Properties o f water
All three phases o f w ater (solid, liquid and gas) are found on the E a rth ’s
surface. The form ula for w ater, H 20 , indicates a m olecular weight o f 18. If
we look at other covalently bonded molecules with sim ilar m olecular
weights (e.g. CO and N O ) we find th a t they have boiling points below the
norm al tem perature range, say 258-323 K (—15 to 50 °C), found on the
E arth. The tem perature o f the m elting p o in t indicates the strength o f the
forces holding the particles together in the solid. Similarly, the boiling-point
tem perature indicates the strength o f the forces holding the molecules
together in the liquid. Ice and w ater have relatively strong attractive forces
betw een the molecules.
The w ater m olecule consists o f an oxygen atom surrounded by four pairs
o f electrons (Figure 3.5a). Two o f the pairs are shared w ith hydrogen atom s
to form covalent bonds between the oxygen and hydrogens. The other two
pairs are called lone pairs because they are n o t shared w ith an other atom .
The pairs o f electrons, with their associated negative charges, tend to repel
each other and they m ove as far a p a rt as possible (Figure 3.5b). The
m axim um separation is achieved if the four pairs are arranged tetrahedrally
(Figure 3.5c). How ever, the lone pairs o f electrons occupy a sm aller volum e
an d have a greater repulsive effect th an the shared pairs o f electrons, thus
the H - O - H b ond angle is reduced from 109.5° to 104.5° (Figure 3.5).
Oxygen is m ore electronegative th an hydrogen and attracts the shared
bonding p air o f electrons m ore strongly th an does the hydrogen. This results
in the oxygen having a slight negative charge and each o f the hydrogens
having a small positive charge (Figure 3.6b). The extra negative charge is
concentrated on the two lone pairs o f electrons (Figure 3.6c). The w ater
m olecule is described as being dipolar, as it has one end negative and the
o th er end positive. The negative end o f one m olecule is electrostatically
attracted to the positive end o f a neighbouring molecule. Because there are
effectively two negative charges, one on each lone pair, each oxygen can be
electrostatically attached to two hydrogen atom s from other w ater
m olecules (Figure 3.7). This electrostatic bon d is called a hydrogen bond. The
interm olecular hydrogen bon d is ab o u t one-tenth as strong as the norm al
covalent oxygen-hydrogen bond. It is the need to break these hydrogen
bonds th a t is responsible for the high m elting and boiling points o f w ater.
E ach w ater molecule can be involved in four hydrogen bonds: two
hydrogen bonds to the oxygen via its lone pairs and a hydrogen bond
between each hydrogen and the oxygen in an o th er w ater molecule. In ice all
the possible hydrogen bonds are form ed, and this gives an extended, open,
three-dim ensional structure.
W hen ice melts to form w ater only a b o u t 15% o f the hydrogen bonds are
broken. The open crystalline structure collapses and the volum e occupied by
the same m ass o f w ater m olecules is reduced, i.e. the density increases. As
HYDROGEN 49
(a) Four pairs of electrons (b) The repulsive forces between

surrounding the oxygen - the electron pairs
two bonding pairs shared with
hydrogens plus two lone pairs
s \
\ # •/
\ /
\ /
^ o
/ \ ^
/
H * / \
/ \
(c) A tetrahedral arrangement - (d) The H— O— H bond angle,

all angles A, B, C, D are 109.5° 104.5°, is less than the
tetrahedral angle
Figure 3.5 Structure of the water molecule.
m ore therm al energy is p u t into the system, (a) the tem perature begins to
rise, (b) m ore hydrogen bonds are broken and the structure collapses even
further, so increasing the density, and (c) the molecules vibrate m ore as their
kinetic energy increases and so they occupy a greater volume. The changes
(b) and (c) produce opposite effects and the result is th a t fresh w ater has a
density m axim um at 3.98 °C. A t higher tem peratures the vibrational effects
are greater th an the collapse effect.
Because o f these density changes, the behaviour o f w ater is particularly
suited to the preservation o f aquatic life-forms. A lake in summer, if deep
enough, becomes stratified (Figure 3.8) due to the p o o r conductivity o f
w ater, allow ing the w arm ing up o f the surface layers which become less
dense th an the cooler lower layers. As the two layers do n o t mix, the lower
50 M A J O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
(a) Even sharing of bonding electrons (b) Oxygen is more electronegative,

between oxygen and hydrogen so electrons spend more time
closer to oxygen than hydrogen
giving small time-averaged
negative, 6 - , and positive,
8+ , charges
(c) The small negative charges, 8 - ,

on the oxygen tend to be associated
with the lone pairs
5- _ 8-
x x / \
1 * \ / • . 1
v* \ / V
\ ;
^'O
/\
I H / \ H j
Figure 3.6 The dipole structure of water molecules.
layer (hypolimnion) will tend to become oxygen deficient as the organic

matter is oxidized. At the same time the upper layer (epilimnion) can
become deficient in nutrients, as the living organisms remove the nutrients
from the water and then, on dying, fall to the lake bottom, taking the
consumed nutrients with them. In the autumn, air temperatures drop and
the surface layers of the lake cool down. When the epilimnion temperature
drops to that of the hypolimnion, the stratification disappears and vertical
mixing, or turnover, occurs (Figure 3.8b). This allows oxygenation of all the
water and carries nutrients up from the lower levels to the surface. As the air
temperature continues to fall, the surface water temperature drops below 4
°C and the surface layer is again less dense than the bottom layer at 4 °C.
HYDROGEN 51
(a) The formation of hydrogen (b) The four hydrogen bonds

bonds between lone pairs on the from one water molecule
oxygen and the hydrogens of - this creates an open
neighbouring molecules structure by holding the
water molecules apart in
fixed positions
O O
5+
H H 8+ H H
\ /
O O
r 8\-
-
\
\ / y / \ / \H
H H H
'O '
H
/ \ H
f
/
/ \
\
\
H /6 +
O O
5+ 'v H
/ \ / \H
H H H
------- hydrogen bond
Figure 3.7 The formation of hydrogen bonds between water molecules.
When the surface temperature becomes 0 °C, ice will form on the surface,
leading to the release of energy as the extra hydrogen bonds are formed: this
energy raises the temperature of the water below the ice. Once the ice covers
the surface it acts as an insulating layer, reducing the heat loss from the
water under the ice to the air above. The rate of freezing is reduced: the
thicker the ice, the lower the rate of freezing. Unless a lake is very shallow or
the air temperature remains below 0 °C all year, the water never completely
freezes and aquatic life can continue below the surface. In spring, the air
temperature rises and the ice that is in contact with the warmer air melts.
The water then warms up and again there is the possibility of complete
mixing when the surface and bottom temperatures become the same. The
stratified structure then gradually develops in the late spring and summer.
Physical weathering of rocks and soils is helped by the expansion of water
when it freezes. Water trapped in cracks builds up very large forces when it
freezes and attempts to expand. These forces can cause the rocks to shatter
in the same way that water pipes burst when the water in them becomes
frozen.
When thermal energy is added to a substance, the kinetic energy of the
component molecules increases. This means that the molecules vibrate and
in liquids and gases they also move more rapidly from place to place. The
amount of energy needed (a) to break enough hydrogen bonds to convert ice
to liquid water is 320 J g_1; (b) to raise the temperature from the melting
52 MAJ OR E L EMEN TS F O U N D IN LIVING MATTER
(a) Summer (b) Autumn
temperature gradient even temperature leads

to vertical mixing
(c) Winter (d) Spring
temperature gradient even temperature leads

to vertical mixing
Figure 3.8 The thermal stratification and mixing of lakes at different times of the year.
point, 273 K, to the boiling point, 373 K, is 420 J g-1; (c) to break enough
hydrogen bonds to convert liquid water to water vapour is 2260 J g_1. In
each case the amount of heat required to bring about the changes (a), (b)
and (c) is very much larger than for most substances. Therefore, water is a
very good medium for controlling temperature changes and transferring
heat. In living organisms the chemical reactions occurring in cells often
generate a large amount of heat that can be absorbed by the water with only
a small temperature increase. If external heat sources, particularly solar
energy, are providing too much energy to be accommodated by an animal or
plant, the vaporization of a small amount of water, called ‘transpiration’ in
plants and ‘perspiration’ in animals, provides an effective cooling system.
The vaporization of water absorbs over 500 times as much heat as does
HYDROGEN 53
raising the temperature of the same mass of water by 1 K. Vaporization can

occur at any temperature, but at the boiling point the tendency to vaporize
becomes so great that all the extra heat energy added to the liquid is used to
convert it into a gas and the temperature remains constant. The boiling
point is a function of the total gas pressure: the higher the pressure, the
higher the boiling point. We have already mentioned the effect of
evaporation and condensation in reducing climatic differences. The thermal
capacity (the amount of heat required to raise the temperature by a given
amount) of large masses of water tends to stabilize temperatures of nearby
land masses by absorbing heat in the summer and releasing it in the winter,
so reducing seasonal temperature differences.
A simple liquid solution contains two substances mixed together
homogeneously in the liquid. One substance, whose physical state as a liquid
is preserved in the solution, is called the solvent; the other substance, which
originally may have been a solid or a liquid or a gas, is called the solute. The
solution consists of the solute particles dispersed amongst, and surrounded
by, the solvent particles (Figure 3.9). The formation of the solution involves
breaking the attractive forces between solute particles so that the solute may
be dispersed in the solvent. For this dispersion to be stable there must be
stronger attractive forces between the solvent and the solute than between
(a)
O o o o X w X X XX x x
O o o X x v X ox X x x °x
o o o o X X
<
X
o o o X X x° X° X X X °
X
X X
o o o o X X
X
xx x ° x x
solid - ordered liquid - less solution - less ordered
structure ordered structure structure, similar to
Key Pure ,iûid
O s o lu te X so lv en t
(b) 8+ H H8+ 5 -0 . 05-
U H -i i- H ,t \ H H /
8 + „ _ 0 © o - H 8+ H 0 H
l l
8+ H H 8+ O O S-
O—
hydrated solute ions showing arrangement of water dipoles around
cations and anions
Figure 3.9 The relationship between solvent and solute in solutions.

54 MAJ O R E L E M E N T S F O U N D IN LI VI N G M A T T E R
solute particles alone or solvent particles alone. When attached to solvent

particles, the solute particles are said to be solvated. If both substances
present are liquids, e.g. water and alcohol, the substance present in excess is
usually called the solvent, but the distinction may not be clear. More
complex solutions can be formed by dissolving more than one substance in
the solvent.
The solvent properties of water are determined by its dipolar nature and
by the presence of hydrogen bonds. The solute particles in an aqueous
solution are said to be hydrated. In the case of ionic substances the dipolar
nature of water makes it particularly suitable as a solvent because the
negative end of the dipole, oxygen, is attracted to the positive ions, and the
positive ends of the dipole, hydrogen, are attracted to the negative ions
(Figure 3.10). The ions at the edges of ionic solids are less strongly held in
the crystal structure as they are not completely surrounded by other ions:
their electrostatic fields will attract water molecules. If enough water
molecules surround the ion they will pull it away from the surface of the
solid, because their combined attractive forces will be greater than the forces
holding the ion in the crystal. The solute ion will become completely
hydrated, moving freely through the solvent and away from the dissolving
solid. The removal of some ions leaves other ions exposed and these are then
hydrated and move away. Eventually either all the solid dissolves or there
are so many hydrated ions in the solution that no more can be accepted and
the solution is said to be saturated. In a saturated solution as many hydrated
ions leave the solid as are returned and a state of dynamic equilibrium exists.
Even when a solid is dissolving, some of the hydrated ions are being
redeposited on the surface, but the rate of removal is more rapid than the
rate of return so that eventually it may all dissolve.
Polar covalent molecules, e.g. ethanol (C2H 5OH), which are similar to
water in that they have a small positive and a small negative charge due to
electronegativity differences between the oxygen and hydrogen of the OH
group, dissolve in water by a similar mechanism. However, the strength of
the solvent-solute interaction is less than with ionic compounds. Non-polar
covalent compounds, e.g. methane (CH4), do not attract water molecules
very strongly and usually the water-water interaction is stronger than the
water-solute interaction, so the non-polar covalent compound does not
dissolve.
When writing the formulae of compounds that are in aqueous solution we
do not normally specify the fact that each solute species is hydrated. If we
want to emphasize this hydration, the symbol 4(acl)’ *s often used - the
formula Na + (aq) Cl- (aq), for example, indicates that the sodium chloride is
dissolved in water and exists as a collection of hydrated sodium ions and
hydrated chloride ions. The number of water molecules directly attached to
HYDROGEN 55
© ©
© ©
© © © 6+
© © © H20 = 6 - 0 =
.H
or
©
© "H
6+
©
©
edge of solid
edge of solid ions have been surrounded by water

molecules and dispersed in the solution
Figure 3.10 The mechanism by which ionic solids dissolve in water.
a given species is determined by the relative size of the water molecules and
the species, its charge and the filling of its electron energy levels. In most
cases there are either four or six water molecules in the hydrated species.
The solubility of most solids increases with a rise in temperature of the
aqueous solution, but the solubility of most gases decreases with a rise in
temperature. This latter effect is of great importance with respect to the
amount of dioxygen dissolved in water. One of the problems with using river
water as a coolant for industrial processes or in electricity power stations is
that the hotter water returned to the river contains less dissolved oxygen and
so is less able to support aquatic life or to oxidize dead organic matter.
Liquid water exists as an equilibrium mixture of undissociated water
molecules, H 20 , hydrogen ions, H + , and hydroxide ions, OH ~ (Eqn 3.15).
H 2O ^ H + + OH (3.15)
The symbol indicates that this is an equilibrium reaction with a constant
interchange between the water molecules and the hydrogen and hydroxide
56 MAJ O R E L E M E N T S F O U N D IN LI V I N G M A T T E R
ions, but there is a fixed relationship between the quantities of species on the
left- and right-hand sides of the equation. For dilute solutions the
equilibrium constant is a function of the molar concentrations of the species
(Eqn 3.16).
equilibrium constant, K = ^ = 1.8 x 1 0 -16 mol dm -3 at 25 °C

[H2Oj
(3.16)
where [ ] indicates the molar concentration of the species inside the square
brackets.
The molar concentration is expressed as the molarity, symbol M, and is
the number of moles of the species dissolved in 1 dm 3 (1 litre) of solution.
One mole contains Avogadro’s number of units of the species. If the species
are atoms, 1 mole contains the relative atomic mass in grammes, e.g. 4 g of
2Ffe; if the species are molecules, 1 mole contains the relative molecular mass
in grammes, e.g. 2 g of H2; if the species are ions, 1 mole contains the relative
ionic mass in grammes, e.g. 17 g of OH~. In many cases, especially in more
concentrated solutions, there are interactions between the solute molecules
so that they are not independent of each other in the solution. Rather than
using the absolute molar concentrations, the properties of the solution are
better described using the activity of the solutes, i.e. the effective con
centrations of the solutes taking the interactions into account. The
equilibrium constant is expressed in the same way as in Equation 3.16, but
the square brackets, [ ], indicate activities rather than molarities.
Undissociated water must be present in great excess because the value of
the equilibrium constant, 1.8 x 10~ 16 mol dm-3, is very small. This means
that any changes in the concentration of the water molecules will be
negligible and the concentration will be essentially constant at
_3/ weight of 1 dm 3 H20 1000
55.56 mol dm —-—;-------- ----- :----------- —
\relative molecular mass, H20 18
Using this value Equation 3.16 becomes
K= ^ , = 1-8 X 1(T16 m oldnT 3 (3.17)

55.56 mol dm -3
Kw = [H+][OH“] = 55.56 x 1.8 x 10"16 mol2 dm “ 6

(3.18)
= 1 x 1(T14 mol2 dm " 6 at 25 °C
The constant, Kw, is called the ionic product of water. In pure water the
concentrations of H + and OH- must be equal, as they can only be formed
by the dissociation of the water (Eqn 3.15). When the concentration of the
two ions is equal, the solution is said to be neutral, and from Equation 3.18
HYDROGEN 57
we see that the concentration of each is 1 x 10 7 mol dm 3 (Eqn 3.19).

[H+] = [OH- ] = 1 x 10- 7 mol dm " 3 at 25 °C (3.19)
To avoid having to keep writing exponential numbers, the hydrogen-ion
concentration, and hence the hydroxide-ion concentration, is conveniently
expressed using the pH scale (Eqn 3.20).
pH = -lo g [H+] (3.20)
A neutral solution, therefore, has a pH of 7. If we also define pOH =
—log [OH- ] and p Kw = -lo g Kw and substitute these forms in Equation
3.18, we obtain
pA:w = pH + p O H = 14 (3.21)
The sum of pH and pOH must always be 14 (at 25 °C) in any aqueous
solution. In a neutral solution pOH = pH = 7 and, in general, pOH =
14 —pH and pH = 14 —pOH. If the hydrogen-ion concentration is greater
than the hydroxide concentration, i.e. if the pH is less than 7, the solution is
said to be acidic. If the hydroxide-ion concentration is greater than the
hydrogen-ion concentration, the pH is greater than 7, the solution is said to
be basic, or alkaline. A broader definition of acids and bases that is not
restricted to aqueous solutions is that an acid is a proton donor and a base is
a proton acceptor. A proton is a hydrogen ion that has not been hydrated.
Returning to aqueous solutions, because almost all acid-base reactions of
environmental interest occur in the presence of water, we find that the
concentration of hydrogen ions does not always equal the concentration of
acid dissolved. In the case of hydrochloric acid, HC1, which is present in the
human stomach at a concentration of about 0.1 M (1 x 10-1 mol dm-3),
the pH of such a molarity is 1, i.e. the hydrochloric acid is completely
dissociated.
HC1 — > H + + Cl- (3.22)
However, ethanoic acid (acetic acid, CH 3COOH), found in vinegar, is
only partially dissociated in water (Eqn 3.23) and only about 1% of the
molecules have liberated hydrogen ions.
CH 3C O O H ^ H+ + CH 3COO“ (3.23)
ethanoic ethanoate ions
acid (acetate ions)
If the concentration of ethanoic acid in water is 0.1 M, the concentration

of H + will be about 1 x 10~ 3 M (0.1 x 1 x 10~2 M) and the pH will be 3.
Acids like ethanoic acid that do not ionize completely in water are called
‘weak’ acids; acids like hydrochloric acid, that do ionize completely, are
called ‘strong’ acids. Bases can also be divided into ‘strong’ bases that ionize
completely, e.g. sodium hydroxide (NaOH, Eqn 3.24), and ‘weak’ bases that
58 MAJOR ELEMENTS l-'OUND IN LIVING MATTER
do not ionize completely, e.g. ammonium hydroxide (NH 4OH, Eqn 3.25).
NaOH —* N a+ + OH“ pH of 0.1 M soln = 13 (3.24)
NH 4OH — > NH+ + OH" pH of 0.1 M soln =11.1 (3.25)

When an acid reacts with a base the products are water and a salt (Eqn
3.26), a compound containing the cation from the base and the anion from
the acid.
H 2SO4 + 2NaOH — ►2H20 + Na 2S 0 4 — >■2Na+ + S O ^ (3.26)
sulfuric sodium sodium sulfate
acid hydroxide (a sait)
With strong acids and bases the resulting solution will be neutral, pH 7,
when equivalent amounts of the two react and when there is no excess of the
acid or base. When weak acids react with strong bases and when strong
acids react with weak bases, the equilibrium point does not occur at pH 7.
The salts that are formed react with water to liberate hydroxide ions, if they
are salts of a weak acid and strong base (Eqn 3.27), or hydrogen ions, if they
are salts of a strong acid and weak base (Eqn 3.28).
NaOOCCH 3 + H20 ^ Na+ 4- CH 3COO~
sodium
ethanoate
+ h 2o ^ N a+ + c h 3c o o h + OH*
undissociated
acid
NH 4CI + h 2o ^ c r + NH+
ammonium
chloride
(3.28)
+ h 2o ^ c r + NH 4OH + h 4
undissociated
base
These reaction types (Eqns 3.27 and 3.28) are often called hydrolysis
because they involve water molecules. Many of the compounds found in
natural systems are made from weak acids or bases.
A number of compounds are insoluble in water but will dissolve in either
an acid or a base. A compound that dissolves in an acid is said to be basic
and a compound that dissolves in a base is said to be acidic. Most metals
have basic oxides, forming alkaline solutions or dissolving in acids, and
most non-metals have acidic oxides, forming acid solutions or dissolving in
bases.
Because the majority of naturally occurring acids and bases are weak,
being only partially ionized in aqueous solutions, the range of pH is
relatively small. The range is also restricted by the action of buffers, which
are weak acids or weak bases in the presence of their salts. The buffer
HYDROGEN 59
solution maintains a reasonably constant pH, even when relatively large

amounts of either acid or base are added. The carbon dioxide-bicarbonate-
carbonate system is a particularly important buffer system regulating the pH
of the oceans and the blood. The mechanism by which this and other buffer
systems operate will be discussed in Chapter 4.
One reason why oxides of sulfur and nitrogen have such a great effect on
the pH of rain is that both sulfuric acid, H 2S 04, and nitric acid, H N 0 3, are
strong acids. Therefore, the concentration of hydrogen ions liberated is
maximized by the complete ionization of the acids.
3.3 Hydroxyl radical formation
In the atmosphere water molecules can be converted to hydroxyl radicals,

OH (Eqns 3.29 and 3.30).
0 3 U-^>B0 2 + O (3.29)
O + H20 — ►20H (3.30)

Although the concentration of hydroxyl radicals rarely exceeds one part in
1012 (a trillion) by volume in the troposphere, they play a key role in many
tropospheric reactions. This is because hydroxyl radicals initiate many of
the oxidation pathways for the chemical species in the troposphere (see
Sections 4.6, 5.2 and 6.2). The increased emissions of methane and other
volatile organic compounds, together with nitrogen oxides and the resulting
ozone, will result in increased consumption and formation of hydroxyl
radicals by reactions such as those illustrated in Equations 3.31-3.38. As a
consequence, in some areas there can be very large reductions in the number
of OH radicals, whereas in other areas there are large increases. Similarly
there can be wide temporal variations at any one place.
OH + CO — > C 0 2 + H (3.31)
H + 0 2 + M —>H 02 + M (3.32)
OH + CH 4 — ►H20 + CH 3 (3.33)
CH 3 + 0 2 + M — > CH 30 2 + M (3.34)
(In Equations 3.32 and 3.34, M is an inert molecule that absorbs energy
released in the reaction.)
CH 30 2 + NO — ►CH30 + N 0 2 (3.35)
CH30 + 0 2 — ►HCHO + H 0 2 (3.36)

formaldehyde
60 M AJ O R E L E M E N T S F O U N D IN L I VI NG M A T T E R
You should note the similarities between reactions 3.31-3.32 and 3.33-
3.34 as well as the fact that the hydroperoxyl radical, H 0 2, is formed at the
end of these sequences of reactions. The H 0 2 radical can react with species
such as nitric oxide, NO (Eqn 3.37), or ozone, 0 3 (Eqn 3.38), to reform
hydroxyl radicals.
H 0 2 + NO — > OH + N 0 2 (3.37)
Compare this reaction to that illustrated by Equation 3.35.
H 0 2 + 0 3 — > OH + 2 0 2 (3.38)
These reactions occur over time scales of seconds so that this rapid recycling
involving the OH and H 0 2 radicals means that they are generally in
equilibrium except when local disturbance occurs due to tropospheric
pollution. It is thought that there has not been a global change in the
average concentration of hydroxyl radicals over the past 20 years.
4 Carbon
Carbon Abundance by weight (the relative abundance is given in

parentheses): Earth, 350 ppm (14); crust, 200 ppm (17); ocean,
inorganic, 28 ppm (10), organic, 2 ppm (15); atmosphere as
C 0 2, 360 ppm (4); as CH4, 1.7 ppm (7). ppm = mg kg-1.
4.1 The carbon cycle
Living organisms are mainly composed of water and various carbon

compounds; therefore the cycling of carbon is of prime importance to the
support of life. We have already seen that the cycling of one element does
not occur in isolation from other elements and some aspects of importance
to the cycling of carbon are dealt with in other chapters.
The carbon cycle is outlined in Figure 4.1. The majority of the carbon is
found in rocks, either as carbonate (CO2-), usually associated with calcium
in limestones (as C aC 03), or as dispersed organic carbon in sedimentary
rocks, particularly shales. The carbonates are described as containing
inorganic carbon, with about three-quarters of the total carbon in the outer
regions of the Earth in these inorganic deposits and one-quarter in dispersed
organic compounds. The combined carbon content of all the other
reservoirs (atmosphere, land biota, soil humus, fossil fuels, marine biota,
dissolved compounds) comes to less than 1 % of the total.
4.2 Aqueous systems
The ocean is a much more complex system than is indicated by the single
reservoir in Figure 4.1. Water is a good absorber of light and there is only
sufficient radiation to support photosynthesis down to about 200 m below
the surface. However, light is not generally the limiting factor for primary
production in the surface layers of the sea. The concentrations of nitrogen,
phosphorus, silicon and some essential trace elements are the major factors
determining marine productivity. The total marine biomass is much smaller
(200 times less) than the terrestrial biomass, reflecting the low productivity
of the majority of surface ocean layers and the great variability from one
area to another. The most fertile areas are very limited, being confined to
narrow bands around a number of continental coasts and the seas near
Antarctica. In each of these regions there are upwelling currents, bringing
higher concentrations of nutrients to the surface. The majority of the
world’s oceans have productivities which are four to ten times lower than
the most fertile areas. The majority of the oceans’ volume is unproductive
because of the lack of light. In addition, there is relatively little vertical
mixing and this prevents the influx of new nutrients into the productive
surface layers.
The primary producers in the oceans are unicellular algae called phyto
plankton, which are capable of photosynthesis. These and the zooplankton
that live on them (Figure 4.2) are capable of only limited locomotion, and
drift with the ocean currents. The zooplankton and phytoplankton provide
food for the organisms called nektons, such as fish and whales, that are
capable of locomotion and for the bottom-dwelling organisms, called
benthos. The average residence time for the carbon in oceanic biota is less
than a month, indicating the rapid turnover that occurs. The gradual
settling out of some of the dead remains of these various organisms leads to
the incorporation of organic compounds in sediments.
(360ppm) (0 .12ppm) (1.7 ppm)

co2 <- CO - — -------CH4
( ) atm ospheric concentration o f compound NB. There is a net increase o f 3.2 xlO kg C a 1 in atm ospheric C 0 2
Figure 4.1 The carbon cycle.

CARBON 63
carnivorous fish
omnivorous fish
excretion
zooplankton and
death
phytoplankton
bacteria and other decomposers release chemicals

for recycling
Figure 4.2 Simplified diagram of an ocean food chain.
The major-carbon reservoir in the oceans is the so-called inorganic

carbon. Carbon dioxide dissolves in water to give a hydrated molecule,
C 0 2(aq) which then forms an equilibrium mixture containing bicarbonate
(hydrogen carbonate, HCO^) and carbonate (CO2-) ions. At pHs lower
than those found in sea water, carbonic acid (H 2C 0 3) will also be present.
CO 2 (gas) CO 2(aq) (4.1)
h 2o + CO 2(aq) h 2c o 3 (4.2)
h 2c o 3 ^ h + + h c o ; (4.3)
HCOJ ^ H+ + C O ^ (4.4)
Most oceanic waters have a pH in the range 8-8.3, as they contain more
hydroxide ions than hydrogen ions due to reactions 4.5 and 4.6, and the
carbonate-bicarbonate mixture contains about 13% carbonate.
hco; co 2 (aq) OH (4.5)
CO2- + H20 ^ H C 0 3“ + OH“ (4.6)

When carbon dioxide dissolves in sea water the overall reaction can be
summarized by Equation 4.7.
C 0 2 (aq) + H 2O + CO2- ^ 2H C 03“ (4.7)
The concentration of the various components varies with depth. In the

surface layers where photosynthesis is active and C 0 2 is being consumed,
64 MAJ OR EL E M E N T S F O U N D IN LI VI NG MATTER
the reaction (Eqn 4.7) moves to the left. Equilibrium reactions have a
constant relationship between the concentration of reactants on the left-
hand side of the equation and the concentration of the products on the
right-hand side of the equation. The equilibrium constant, K Qqm, for reaction
4.7 is:
[HC03-]2
eqm [co2(aq)][h2o] [CO2-] (4-*j
Keqm [C02(aq)] [H20] [CO2"] = [HCOj]2 (4.9)

If the concentration of dissolved carbon dioxide, [C02(aq)], is reduced, the
concentration of bicarbonate ion, [HCO^], must also be reduced. Removing
carbon dioxide causes some of the bicarbonate to be converted to C 0 2, H 20
and CO2-, until the concentration products are again the same on both sides
of Equation 4.9, i.e. reaction 4.7 moves to the left.
In deeper water there is a net production of carbon dioxide due to
respiration and decay processes which oxidize the organic compounds, so
outweighing photosynthesis. Under these conditions reaction 4.7 moves to
the right as the extra carbon dioxide is partially converted to bicarbonate
and an equilibrium is again attained.
These changes in concentration of C 0 2, HCO^ and CO2- affect the
solubility of calcium carbonate, C aC 03. The surface waters contain higher
concentrations of carbonate as reaction 4.7 moves to the left, the solubility
product, K sp, of calcium carbonate is exceeded (Eqns 4.10 and 4.11) and any
calcium carbonate present will not dissolve.
C aC 0 3 (solid) T ^ a(aq) + CO 3 (4-10)
Ksp = [Ca2+] [CO2-] = 4.47 x 10" 8 mol dm ~3 (4.11)

As the depth increases, the concentration of carbonate ion decreases and
calcium carbonate becomes soluble. Shells will, therefore, start to dissolve.
The presence of the various inorganic carbon species plays a particularly
important part in controlling the pH of natural waters.
Buffer solutions and alkalinity
The ocean is described as being ‘buffered’ because relatively large quantities

of acid or base can be added to sea water without causing much change in
the pH. Many freshwater lakes and rivers are not buffered and their pHs
change rapidly with the addition of acid or base. Even the sea is not able to
act as a buffer indefinitely and eventually there will be a marked change in
pH when the buffering capacity is exhausted. The buffer system in the ocean
is quite complex.
CARBON 65
Added acids cause the equilibrium points of reactions 4.1-4.4 to move to

the left, and added bases move the equilibria in reactions 4.5 and 4.6 to the
left; in each case the number of free hydrogen or hydroxide ions is reduced.
Sea water also contains phosphates, silicates and other species, especially
borates (Eqn 4.12), which act as buffers.
H 3BO3 - H + + H 2B 0J ^ H+ + HBO2- ^ H+ + BO3- (4.12)
Because of the large number of equilibrium reactions to be considered,
calculating the buffering capacity of sea water is very difficult. This difficulty
also applies to other natural waters. A practical solution to the problem has
been found. The capacity of the natural water to neutralize acid is called the
alkalinity. The alkalinity is determined by titration of the water with a
strong acid (Figure 4.3). By actually determining the alkalinity curve using a
pH meter and the addition of the strong acid, the effects of all the species in
the water can be taken into account. The carbonate buffer system is the
major factor controlling the ability of most natural water systems to
withstand a large change in pH when acid is added. The longer the section
CD (Figure 4.3), the more stable the water will be. The two sharp increases
in slope correspond to the reactions 4.4 (BC , Figure 4.3) and 4.3 ( DE , Figure
4.3). For most natural water systems these changes occur at pH 8-8.5 and
pH 4-5, respectively.
Fish and many other organisms are unable to survive large drops in pH.
The salmonids (e.g. salmon and trout) are particularly susceptible, and fish
kills can occur at pHs below 4.5-5. The greater the alkalinity of the water,
i.e. the larger the amount of acid required to reach section D E (Figure 4.3),
the less likely are harmful effects due to pH changes. One of the reasons for
the variability in the effects of acid rain is due to the varying alkalinity of
lakes and rivers. Scandinavian freshwater systems tend to have low
alkalinities because the underlying rocks do not provide many carbonate or
other buffering species. Therefore, small additional quantities of acid cause
large pH changes. Similarly, industrial acidic effluents pumped into a high-
alkalinity river may cause little upset whereas in a low-alkalinity river the
same effluent could be devastating.
4.3 Photosynthesis and the formation of carbon compounds
We have already briefly discussed photosynthesis as a source of dioxygen

and as a means of storing solar energy as chemical energy (Chapter 2). The
detailed mechanism of the process is very complex and has not yet been fully
unravelled. However, many of the changes taking place are now known.
66 MAJ OR E L E M E N T S F OU N D IN LI VI NG MAT TER
The light is absorbed by a number of pigment molecules, the most

abundant of which are chlorophyll a and chlorophyll b. In the higher plants
the pigments are concentrated in the green-tissue cells. Chlorophyll
molecules contain a magnesium ion surrounded by a porphyrin-ring
structure (Figure 4.4). The porphyrin-ring structure is found in a number of
biologically important molecules, such as haemoglobin, vitamin B 12 and the
cytochromes. All the porphyrins have four nitrogen-containing pyrrole rings
but with a variety of side chains. The difference between chlorophyll a and
chlorophyll b is due to different groups in position X (Figure 4.4). The
presence of the alternating single and double bonds, called a conjugated
double bond system, allows the electrons in these bonds to be relatively
easily raised in energy. There are two pigment systems in the green cells and
each is responsible for absorbing particular parts of the light spectrum.
One system, containing chlorophyll a, absorbs red light (A ~ 650 nm,
energy ~ 185 kJ m o P 1) to produce excited molecules containing electrons in
higher energy states. These electrons are transferred to form a compound
such as NADPH.
ATP is the contraction for adenosine-5'-triphosphate, a molecule used in
biological systems to provide the energy required to drive reactions needing
an energy input. It is a very important molecule, being the major energy
carrier in metabolic processes. The ATP transfers a phosphate group, PO 4- ,
to one of the organic reactants (Eqn 4.13), which is then able to react in the
Key
AB the carbonate CO 3 ~, buffer zone
CD the hydrogen carbonate or bicarbonate, HCOa, buffer zone
EF evolution of carbon dioxide, C 0 2, from acid solution
Figure 4.3 An idealized diagram of the alkalinity curve obtained when changes in pH are
plotted against the volume of acid added to an aqueous carbonate solution.
CARBON 67
desired manner (Eqn 4.14). The addition of phosphate is called a

phosphorylation reaction.
R O H + A T P — > ROPO 3 + ADP (4.13)
organic phosphorylated adenosine-5'-diphosphate
molecule intermediate
ROPO 3 “ ROX + P 0 3“ (4.14)

reaction organic product phosphate
ATP can be regenerated from ADP by the addition of a phosphate group.

As the system is more or less cyclic (Figure 4.5), ATP acts as an efficient
energy-transfer agent. The energy may come directly from photosynthesis or
from the chemical energy in compounds such as carbohydrates and fats that
are broken down as required to regenerate ATP.
NADPH is reduced nicotinamide adenine dinucleotide phosphate and
acts as a carrier of protons and electrons (Eqn 4.15).
NADPH + oxidized compound — ►NADP+ + reduced products (4.15)
The NADPH can be regenerated from NADP + , nicotinamide adenine
dinucleotide phosphate (Eqn 4.16).
NADP+ + H + + 2e“ — > NADPH (4.16)
During photosynthesis the protons and electrons are provided by water
with the release of dioxygen (Eqn 4.17).
2H20 — ►0 2 + 4H+ + 4e“ (4.17)
The incorporation and reduction of carbon dioxide to form the various
organic products of photosynthesis involves a complex series of cyclic
reactions (Figure 4.5). One molecule of carbon dioxide is added to an
activated organic molecule. The product is then progressively reduced by
NADPH, and rearranged, under the influence of enzymes, until the final
compound, whether a carbohydrate, lipid or protein, is produced. When an
energetically unfavourable reaction has to occur, the driving force is
provided by ATP injecting energy by means of a phosphorylation reaction.
The enzymes provide conditions that favour very specific changes, whether
additions, rearrangements or decompositions. They increase the rate of the
reaction, but are not consumed in the reaction, and are therefore catalysts.
The consequences of photosynthesis are that the photoautotrophs are net
absorbers of carbon dioxide, water and sunlight, and net producers of
organic molecules and dioxygen. The photoautotrophs use some of the
organic compounds as sources of energy for many of the reactions carried
out in their cells. Energy stored as chemical compounds can be transported
and released as required, so increasing the efficiency of the organism because
sunlight is not available during the night, all cells need not be exposed to
68 M AJ O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
(a) Various representations of the structure of pyrrole
» "''C —C H
// w
N N
I I
H H H
(b) Porphyrin: general structure, (c)

with different molecules having
different substituents in CH -i
positions 1-8 V
Figure 4.4 Structures of (a) pyrrole, (b) a porphyrin ring and (c) chlorophyll.
sunlight, and there may be temporary shortfalls in the availability of carbon

dioxide and water. The energy-releasing process (Eqn 4.18) is called aerobic
respiration and may be thought of as the reverse of photosynthesis.
(CTÔ)^ + nOi — » nCC>2 + HH2O + energy (4.18)
The respiration process, like photosynthesis, occurs by a complex series of
reactions involving many steps and the use of enzymes. The energy released
by a reaction like the oxidation of glucose (Eqn 4.19) is not given out all at
once, but rather as smaller packets mainly to regenerate ATP and, therefore,
drive the desired reaction steps in the life processes of the organism.
C6H12O6 + 6O2 — > 6H2O + 6CO2 + energy (419)
Heat is also produced and this may help the metabolic processes, as at
higher temperatures the rate of chemical reactions can be increased quite
significantly. For many reactions involving organic compounds, a 10 K
increase in temperature will double the rate of reaction. These higher rates
of reaction will allow more energy to be produced in a shorter time, thus
enabling many more energy-consuming reactions to take place without
CARBON 69
sunlight
CO2 energy transfer
Figure 4.5 Diagrammatic representation of the use of ATP and NADPH in a photosynthetic
reaction sequence.
running short of energy. By proper use of the heat-transfer properties of

aqueous solutions, the organism can control the environment of its cells and
maintain them at a higher temperature than the external surroundings. This
control produces a more stable internal environment that can be optimized
to suit the needs of the organism. The life-forms that have taken greatest
advantage of the flexibility allowed by utilizing chemical compounds and
respiration as energy sources are the heterotrophs. The photoautotrophs
convert the solar energy into ‘high energy’ chemical compounds. The excess
compounds which they do not use for their own metabolic processes can be
consumed by heterotrophs. The result has been the development of food
chains such as in Figure 4.2, in which the primary producers utilize solar
energy directly and the various consumers depend upon either the producers
or other consumers for their energy intake. The actual carrying out of the
photosynthesis process uses up a lot of the energy extracted from the Sun by
the plants, etc. The consumers do not carry this energy burden and can use
the energy in the already synthesized molecules for their own growth,
biosynthetic needs and the other metabolic processes that control their
internal environment and permit muscular activity.
Carbohydrates and lipids
The two major groups of energy-storing chemicals produced by photo

synthesis are carbohydrates and lipids. One important source of biologically
available energy is provided by the breakdown of monosaccharides such as
glucose (Eqn 4.19). In the presence of dioxygen, the complete decomposition
of the glucose to carbon dioxide and water can be achieved with the release
of the maximum amount of energy (2880 kJ m o P 1) accumulated during
photosynthesis. The majority of this energy is transferred inside the
organism by the 38 molecules of ATP that are synthesized during this
aerobic respiration. The first steps in the oxidation of glucose lead to the
formation of pyruvic acid (CH 3COCOOH) and enough energy to generate
two ATP molecules. Up to this stage the presence of dioxygen is not
required and the reaction steps are common to both aerobic respiration
(oxygen dependent) and anaerobic respiration or fermentation (oxygen
independent). Aerobic respiration leads to carbon dioxide and water
production, but with anaerobic respiration there is no suitable electron
acceptor and all the carbon atoms in the pyruvic acid cannot be converted
into carbon dioxide. Organisms such as yeast produce ethanol (ethyl
alcohol, C 2H 5OH) and carbon dioxide in the best known of the fermen
tation processes. The souring of milk is another fermentation process in
which lactic acid (CH 3CH(OH)COOH) is formed. Those organisms that
obtain their energy by the fermentation pathway are at a great disadvantage
compared to those using aerobic respiration because of the relatively small
amount of energy released during fermentation. With glucose, fermentation
releases 220 kJ m o P 1, whereas aerobic respiration releases 2880 kJ m o P 1.
Glycogen is the polysaccharide that is used as a nutritional reserve by
animals. The equivalent compound in plants is starch, which is stored either
in the roots of tubers, like potatoes, or in seeds, as with wheat, rice and
maize. The other major polysaccharide is cellulose, which contains 30% -
90% of all the carbon in vegetation and provides the main supporting
structure as wood or fibre. Whereas glycogen and starch can be used as food
by humans, cellulose cannot. The polysaccharides must first be broken
down into monosaccharides in order that their energy may be released.
Humans, and many other animals, do not have the necessary cellulase
enzymes, which break up cellulose, in their digestive tracts. Cellulose con
sists of glucose units joined together by /^-linkages (Figure 4.6), whereas
glycogen and starch have their glucose units joined together by a-linkages.
This very small change is enough to give the radical difference in digestibility
and indicates the importance of stereochemical factors in determining
reaction pathways.
The four covalent bonds around a carbon atom are directed tetrahedrally
in space (Figure 4.7) so that they are as far from each other as possible and
all of the bond angles are 109.5°. One result of these directional
CARBON 71
characteristics is that when four different groups are attached to a carbon

atom there are two possible compounds that have identical constitutional
formulae, but different spatial arrangements. These two spatial arrange
ments, called configurations, are mirror images of each other and they are
an example of stereoisomerism. As can be seen from Figure 4.7, but
probably better with three-dimensional models, the two configurations are
not superimposable, no matter how they are rotated. The type of stereo
isomerism shown by these molecules with no plane of symmetry is called
optical isomerism, because the two isomers rotate plane polarized light in
opposite directions. Many organic compounds, such as carbohydrates, have
at least one asymmetric carbon atom, with four different groups attached to
it. The different configurations can influence whether the stereoisomers
react, particularly if enzymes are required to promote the reaction.
Enzymes are proteins that have the ability to speed up organic reactions
without being ‘used up’ themselves. As well as the proteins, the enzyme
molecule usually contains other chemical species, including metals. Both the
protein and the other species must be present for the enzyme to be active;
neither alone is sufficient. Enzymes have different degrees of specificity.
Many will only catalyse one particular reaction of one particular compound.
Others will catalyse reactions of a certain bond type, e.g. a double bond, no
matter what other groups are present. The remaining enzymes lie between
these two extremes.
The enzymes have ‘active sites’ at which the reaction occurs. The
remainder of the enzyme molecule helps to keep the molecule stable and to
provide the correct configuration (spatial arrangement of groups) at the
active site. The enzyme will increase the rate at which the reaction will reach
equilibrium, but it will not change the equilibrium position; it speeds up the
reaction, but does not increase the theoretical yield. The molecule that is to
undergo the reaction is called the substrate: this becomes attached to the
enzyme at the active site (Figure 4.8). The relative shapes of the substrate
and the active site decide the degree of specificity of the enzyme. In some
cases the stereochemical fit has to be much closer than in others. The bound
substrate is now held in such a way that the atoms that are to take part in
the reaction are in a favoured position for interaction with the incoming
reacting species (Figure 4.8b).
A reaction is favoured if the total energy in the chemical products is lower
than the total energy in the reactants (Figure 4.9). For many reactions,
bonds have to be broken before reactions can proceed; the initial
overcoming of these bonding forces requires an input of energy called the
activation energy. The activation energy acts as a barrier to the completion
of the reaction: there must be this energy input before there is the energy
output from the formation of the final product (Figure 4.9b). The larger the
activation energy the more difficult it will be for the reaction to proceed.
Enzymes provide an alternative pathway comprising several steps, each of
72 MAJ OR EL E M E N T S F OU N D IN LIVING MAT TER
(a) An alpha, a , linkage - oxygen A ‘opposite’ oxygen B
® OR
(b) A beta, p, linkage - oxygen A ‘adjacent to’ oxygen B
Figure 4.6 Alpha- and beta-linkages in polysaccharides.
which has a relatively small activation energy; molecules following this

pathway can react more rapidly. In many cases there is no suitable enzyme
and the activation energy is too great for the reaction to proceed. The
breakdown of the polysaccharides in animals’ digestive tracts depends upon
the presence of the enzymes required to reduce the effects of the activation
energy barriers. If the correct enzymes (e.g. cellulase for cellulose) are not
present, no breakdown occurs.
D
D B
IV
the arrangements II, III| and IV are simple
rotations of the same configuration:
none of them is identical to the
configuration in I
Figure 4.7 Stereoisomerism exhibited by a carbon atom tetrahedrally attached to four different
groups.
CARBON 73
Plants use starch as their main energy-storage compound, but animals use
fats. The triglyceride fats contain more material capable of being oxidized
than do carbohydrates of the same weight. The maximum energy that an
organism can obtain from a fat is about twice as much as from carbo
hydrate, on a weight-for-weight basis. Fats, therefore, are more concen
trated energy-storage compounds than carbohydrates. Carbohydrates can
be converted to fats, and when the intake of food is greater than immediate
needs, large quantities of fat can be deposited around the body. Other
properties of fats that make them particularly suitable as storage
compounds are that they are insoluble in water and that the presence of
large quantities does not upset the ionic balance in the aqueous solutions of
the body.
0 2 0 *0 substrate molecule
active site
ENZYME MOLECULE
intermediate
O
bond broken and new

compounds formed
Figure 4.8 A representation o f how an enzyme can influence a reaction mechanism.

4.4 Energy
The use of various fuels and their conversion into different energy forms
(thermal, electrical, chemical, mechanical, etc.) has to be considered with
respect to the ‘usefulness’ of these energy forms and the laws of thermo
dynamics that control the operation of energy systems. The laws of
thermodynamics only deal exactly with systems in equilibrium. If applied to
non-equilibrium systems, approximations must be made, but these are often
relatively unimportant. Statements of the various laws and paraphrases of
these are given in Table 4.1.
Energy is generally defined as the ‘capacity to do work’, and the laws of
thermodynamics indicate how much useful energy (work) we can obtain
from a system. With every energy conversion (e.g. chemical to thermal,
mechanical to electrical) there is a net loss of energy from the system. There
can never be a 100%-efficient conversion of energy. This loss in ‘capacity to
do work’ shows up as an increase in entropy (symbol S). Entropy can be
thought of as the tendency for a system to achieve equilibrium, i.e. its most
probable state of energy distribution. This implies that the system will
become disordered, because an ordered arrangement has a lower probability
than a disordered arrangement provided that there is free movement from
(a) The initial, /, and final, F, (b) Because chemical bonds may need to
energy states for an be broken before the reaction can
energetically favourable proceed, an intermediate excited (higher-
reaction energy) state, H ,, occurs - the energy
required to reach this intermediate state
is called the activation energy, A ,
H\
A, \
(c) The presence of an enzyme can introduce the possibility of a number of

enzyme-plus-substrate intermediate stages (E i, E 2), which lead to a series of
small activation energies (A 2, A 3, A 4)9 each less than A ^
H 3
H2
\ Eld
2 \ / Ik \
(
a4 '
1r
Figure 4.9 The effect of enzymes on the activation energy of a reaction.

CARBON 75
one arrangement to another. Consider the example of three coins that have
been spun (Figure 4.10a). There is one chance that they will land all heads
and one chance that they will be all tails, i.e. two chances of these completely
ordered arrangements. There are six chances that some other arrangement
will occur. Similarly, the spinning of four coins (Figure 4.10b) could give
two arrangements with the highest possible order (all heads, or all tails) and
14 other arrangements showing various degrees of lower order. In general,
the total number of arrangements is 2n, where n is the number of coins
(Figure 4.10). However, once formed, the ordered arrangement of all four
coins being heads or tails will remain until they are spun again. The ground
or table prevents the coins from continuing to spin and eventually reaching
their thermodynamically most probable equilibrium state. Similarly,
ordered systems are common throughout the Universe, preserved in their
ordered arrangement until the restraining or binding forces that hold them
together are broken.
Chemical reactions and phase changes (solid ^ liquid ^ gas) involve heat
changes. If the change occurs under conditions of constant pressure, the
heat absorbed or evolved is called the enthalpy change, A H . The Greek
capital letter delta, A, is commonly used as the symbol for ‘change in the
value of. For a reaction in which heat is evolved (given out), an exothermic
reaction, the value of A H is negative: heat is being lost from the reaction
system. When heat is absorbed (taken in), an endothermic reaction, the value
of A H is positive: heat is being gained by the reaction system. Similarly, if
the entropy of a system decreases, i.e. if the system becomes more ‘ordered’
(e.g. if gas condenses to liquid), the value of A S is negative. When the
entropy of a system increases, i.e. if it becomes more ‘disordered’, the value
of A S is positive.
Table 4.1 The laws o f thermodynamics paraphrased (after Walters, G .A . and E.M . Werweka
1974. Contempory chemistry. Columbus OH: Charles E. Merrill). The so-called paraphrases are
expressions o f how the operation o f the laws o f thermodynamics limits the extraction o f usable
energy from a system
Law Statement Paraphrase
Zeroth There exists a phenom enon called Life is a game

temperature (there are rules)
First Energy is neither created nor destroyed Y ou cannot win; the best
in a process but merely transformed you can do is break even
from one form to another
Second The entropy o f a system and its You can only break even
surroundings increases for any if you live forever
spontaneous process
Third A bsolute zero o f temperature is Y ou cannot live forever
approachable, but unattainable
76 MA J O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
The ability of a reaction to do work is indicated by the free-energy change,

AG, that occurs. The relationship between free-energy change, AG, enthalpy
change, A H, entropy change, A S , and absolute temperature, T , is given by
Equation 4.20.
AG = A H — T A S at a constant temperature and pressure (4.20)
The more negative the free-energy change, the more energy the system can
supply, the more work it can do and the more stable the final products will
be. Stability is high if a lot of energy has to be added to the system to reverse
the reaction.
Fossil fuels combine with dioxygen, when burnt, to produce products that
are thermodynamically more stable than the fuel. The free-energy change
for combustion is negative. The chemical energy is released as heat.
However, for work to be carried out, the thermal energy must be converted
to mechanical energy. The efficiency of this process depends upon the
temperature difference between the heat source before the conversion has
taken place and the temperature after the energy has been extracted (Eqn
4.21).
Carnot efficiency = efficiency of energy conversion
_ T(in) - T(out) (4 -21)
T (m)
where is the absolute temperature before the energy is extracted and

T(out) is the absolute temperature after the energy is extracted.
(a) Three coins H H H,

HHT, HTH. THH,
HTT, THT, TTH
T TT
Total number of arrangements = 2 3 = 8 , with 2 out of 8 having the highest

degree of order (i.e. all heads or all tails)
(b) Four coins HHHH

HHHT, HHTH, HTHH, THHH
HHTT, HTHT, THHT
TTHH, THTH, HTTH
HTTT, THTT, TTHT, TTTH
TTTT
Total number of arrangements = 2 4 = 16, with 2 out of 16 having the highest

degree of order
Figure 4.10 The possible arrangements that may result from spinning (a) three and (b) four
coins.
CARBON 77
For instance, in an oil-fired power station the hot gases entering the boiler
to produce the steam which drives the turbines may heat the steam to 650 K
and the water may leave the condenser at 300 K. The efficiency of energy
conversion would be about 54%:
The efficiency could be increased by raising the input temperature or by

lowering the output temperature. The input temperature is limited by (a) the
temperature of combustion of the fuel, (b) the design of the furnace/boiler
system, and (c) the ability of the construction materials to withstand high
temperatures without deterioration. The lower limit is determined by the
temperature of the cooling water in the condensers and the ambient air
temperature. Modern fossil-fuelled power stations are operating reasonably
closely to their Carnot efficiencies for the steam cycle, but much higher
overall efficiencies could be obtained if the steam cycle could be taken up to
the temperature of the combustion gases, i.e. 1000 °C or 1300 K.
1300 - 300
Carnot efficiency x 100 = 77%
1300
When geothermal energy is substituted for fossil fuel the input temperatures
of the steam from the geothermal field are about 200-250 °C, say 500 K. The
Carnot efficiency is then 40%. The lower the difference between possible
input and output temperature, the lower the efficiency of the system in terms
of the useful work that can be extracted. Any energy source (e.g. fossil fuels
and electricity) that provide high temperatures is considered to be a ‘high
grade’ energy source, whereas sources (e.g. solar water heaters and geo
thermal energy) that can only produce low temperatures are considered to
be ‘low grade’ energy sources.
Solar radiation consists of two components. One component is the direct
radiation received when the Sun is visible. This direct radiation can
be focused so that the energy is concentrated and high temperatures may be
achieved. This is potentially a ‘high grade’ energy source as it can be
converted to other energy forms relatively efficiently. The second com
ponent is the diffuse radiation that is received even when the Sun is obscured
by clouds. The diffuse radiation cannot be focused and only provides
thermal energy proportional to its natural intensity. It is a ‘low grade’
energy source. However, photosynthetic organisms can utilize some of the
diffuse radiation and produce chemicals in which the energy has been
concentrated. The fossilized remains of these chemicals are the source of the
coal, oil and natural gas that we now use as ‘high grade’ energy sources.
4.5 Geochemical accumulation of solar energy
The process of photosynthesis provides plants and ultimately animals with

energy by converting solar energy into chemical energy. Any organic
remains of dead plants and animals that have been buried in sediments can
be thought of as containing trapped solar energy. The majority of these
sedimentary organic compounds are dispersed in the rocks at an average
concentration of 0.5%, but there are distinct localized deposits (coal, oil and
natural gas) where the concentration of organic compounds may be over
90%. These deposits of fossil fuels, that are so crucial to the continuation of
technologically advanced societies, make up only 0 . 1 % of the total
sedimentary organics.
The sites of deposition for the precursors of oil and natural gas were
marine, whereas coal, and the associated methane, originate from terrestrial
plants. There are still a lot of unknown details about how the deposits were
formed. The general stages in the production of fossil fuels were (1)
deposition of large quantities of organic matter and of a relatively small
quantity of inorganic sediments; (2 ) anaerobic conditions which prevented
oxidation of the organics to carbon dioxide; (3) increasing depth of burial
leading to increases in temperature and pressure. In the case of coal,
deposition occurred in swampy sites with the organic matter periodically
being covered by inorganic sediments, probably brought in by flooding of
the area. As the deposit became more deeply buried, the temperature and
pressure rose, bringing about changes: peat — » lignite — > brown coal — »
bituminous coal — > anthracite. During this process the volume of the
deposit decreased and there was ( 1) a loss of hydrogen, nitrogen and oxygen,
leading to an increased percentage of carbon; (2 ) a loss of recognizable plant
remains; (3) an increase in hardness; (4) a reduction in volatile matter; and
(5) an increase in degree of aromatization. Aromatization is the formation of
six-membered rings of carbon atoms with what were once thought to be
alternating single and double bonds (Figure 4.11). In fact, the bonding
electrons were shared evenly between the carbon atoms. This spreading of
electrons is called delocalization and gives a more stable structure than that
given by localized double bonds. The fusing together of the rings reduces the
proportion of hydrogen to very small amounts. Coals are classified by their
rank, which indicates how far the change from lignite (low rank) to
anthracite (high rank) has proceeded. The same rank of coal can be
produced either by a long time at a low temperature or by a shorter period
at a higher temperature. Therefore, coals were not produced in only one
geological period, although in the UK most coals come from the
Carboniferous period.
The reactions bringing about the formation of oil and natural gas are less
well known than those bringing about the formation of coal. Oil is mainly
composed of linear aliphatic hydrocarbons (few aromatics) usually
CARBON 79
containing less than 24 carbon atoms and with 50% having less than 13
carbons. Oil is fluid at the temperatures of formation and extraction.
Natural gas is composed of methane, CH4, the simplest of the hydrocarbons
and the most stable at higher temperatures. It is thought that the majority of
the oil and natural gas that has been formed has seeped away and been lost
from sediments. The deposits we now exploit, and those we hope to find in
the future, result from the oil or natural gas or both having been trapped in
a porous rock with an impervious bed above (Figure 4.12).
The burning of all fossil fuels to release energy produces carbon dioxide,
water and nitrogen oxides, together with sulfur dioxide in the case of coal
and most oil (Eqn 4.22).
CH 4 or CzHyS + 0 2 + N 2 — > H20 + C 0 2 + NOx + S 0 2 (4.22)
natural gas coal and oil air
The problems associated with the acidic sulfur and nitrogen oxides are
discussed in later chapters. The amount of carbon dioxide released by
combustion of fossil fuels has risen from 0.34 x 109 tonnes (99% from solid
fuels) in 1860 to 9.2 x 109 tonnes (55% solid fuel, 33% oil, 9% natural gas)
in 1960 and 19.5 x 109 tonnes (41% solid fuel, 41% oil, 15% natural gas) in
1986, an average rate of increase of about 3% per year. One of the
consequences has been that atmospheric carbon dioxide levels have risen
from about 290 ppm in 1860 to 354 ppm in 1990. Carbon dioxide is not toxic
at these concentrations and increased amounts in the atmosphere may
increase rates of photosynthesis and growth for some plants.
4.6 Greenhouse effect
The heat balance of the Earth will be affected by increased amounts of

atmospheric carbon dioxide because the molecules absorb longer wave
length, IR electromagnetic radiation, while being transparent to shorter
wavelength, visible and UV radiation (Figure 4.13). When the Earth
reradiates the solar energy that has fallen on its surface the radiation is in
the IR portion of the spectrum. The lower the temperature of the radiation
the longer the wavelength of the maximum energy output. This means that
the solar radiation is only partially absorbed by carbon dioxide on the ‘way
in’ (Figure 4.14), but a much higher proportion is absorbed on the ‘way out’
and trapped in the atmosphere. As the concentration of carbon dioxide rises
the amount of radiation trapped will increase and the temperature of the
atmosphere will rise. This has been called the greenhouse effect because the
trapping principle is similar to that operating in a greenhouse, where the
glass reduces the loss of IR radiation. It is now thought that the carbon
dioxide concentration will reach twice its pre-industrial level in 70-100 years
time.
80 MAJ OR EL EMEN TS F OU ND IN LIVING MATTER
(a) Different representations for the aromatic structure of benzene

H
FL r /H
cj: c
H H
(i) (ii) (iii)
H
(b) The aromatization process found in the formation of coal

H H
H H
H H
H
before aromatization, after aromatization,
18 C and 18 H 13 C and 9 H
Figure 4.11 Aromatic structures, (a) Different representations for the aromatic structure of
benzene, (b) The aromatization process found in the formation of coal.
Whilst some aspects of the greenhouse effect are known with a high
degree of certainty, there is much that is speculative. Trying to piece
together the likely effects and predict what the consequences will be provides
a good illustration of the complexity of environmental systems.
Facts
Gaseous molecules in the atmosphere, such as H 20 , C 0 2, CH4, N 20 , 0 3 and
CFCs, each absorb characteristic parts of the IR spectrum (e.g. Figure 4.13,
the absorption spectrum of carbon dioxide). The amount of IR absorbed
varies from compound to compound and is proportional to the number of
molecules of that compound in the atmosphere. The amount of solar
CARBON 81
oil and/or natural gas

trapped in dome structure
Figure 4.12 The trapping of oil and/or natural gas in sdimentary rocks.
radiation entering the Earth’s atmosphere is balanced by the amount leaving

(Figure 4.14). If there is an increase in IR-absorbing molecules in the
atmosphere, the temperature rises until the radiation emitted again balances
the radiation being absorbed. A new steady-state is reached. If there was no
water vapour or carbon dioxide in the atmosphere the temperature at the
Earth’s surface would be about 254 K (-1 9 °C) and life would not exist.
The atmospheric concentrations of C 0 2, CH4, N 20 , 0 3 and CFCs are all
increasing (Table 4.2). The concentration of water vapour is so variable
(0%-5%) that it is not possible to know whether there is an overall increase
or not. It should be noted that water vapour is responsible for more IR
radiation absorption than any other atmospheric component. However, it is
usually considered that its effect is approximately constant and that changes
are driven by other factors. Carbon dioxide and water vapour absorb IR
with wavelengths shorter than 8000 nm and longer than 12000 nm. This
leaves a ‘window’ of unabsorbed IR that could escape from the Earth’s
atmosphere. The recently introduced CFCs and HCFCs are absorbing
radiation in the 8000-12000 nm band. They are, therefore, capable of
blocking this ‘window’ as are ozone, methane and dinitrogen oxide. A
doubling of carbon dioxide concentration is calculated to increase IR
absorption by 4 watts per square metre (4 W m-2) of the Earth’s surface.
This extra heat should cause some more water vapour to enter the
atmosphere and this would absorb another 2 W m~2. These increases are
relatively small when compared to the present total of 240 W m ~ 2 of solar
radiation that is being absorbed. About 100 W m ~2 of this total is due to
water vapour and 50 W m -2 to carbon dioxide. Doubling the carbon
dioxide concentration has such a small effect because a high proportion of
82 MAJOR E L EMENTS FOU ND IN LIVING MAT TER
Wavelength (nm)
Figure 4.13 The infrared absorption spectrum o f carbon dioxide.
the relevant IR outside the 8000-12000 nm ‘window’ has already been

absorbed by the carbon dioxide and water already present in the
atmosphere.
Extrapolation and hypothesis

It is possible to extrapolate recent changes in gas concentrations into the
future. The validity of the extrapolation will depend upon (a) the precision
and accuracy of the measurements made in the past, and (b) the
continuation of the processes that produced past increases. If past
radiation
ultraviolet visible infrared
Figure 4.14 The absorption of electromagnetic radiation by molecules in the Earth’s

atmosphere. The higher the concentration of water (H20 ) and carbon dioxide (C 0 2), the
greater the proportion o f infrared absorbed and then re-emitted to Earth rather than to space
until a new equilibrium is reached.
CARBON 83
measurements are incorrect (as appears to have been the case for N 20 ,
where values were overestimated due to problems with the analytical
method), then future projections will also be incorrect. Assumptions about
future production and emissions are particularly difficult to make. Whilst
the world’s population is projected to increase by about 100 million people
per year, it is not clear how this will affect greenhouse gas emissions. If living
standards rise, the use of fossil fuels and the output of carbon dioxide will
rise faster than present trends. Similarly, emissions of methane (from paddy
fields and from ruminants) and dinitrogen oxide (from fertilizer
applications) are dependent upon agricultural productivity. Ozone increases
in the troposphere will be affected by the rate of urbanization and increases
in motor vehicle usage. CFC production has started to decline, but the
known substitutes are also greenhouse gases and the future rate of release of
CFCs that are at present trapped in insulating foams and in refrigerators is
unknown. To make matters worse, the quantities of materials being
transferred between the major sources and sinks are often uncertain. For
instance, in the carbon dioxide cycle there appears to be about 1.5-4 x 109
tonnes of carbon dioxide unaccounted for. This represents up to 15% of the
extra carbon dioxide that human activities are thought to be releasing to the
atmosphere (Table 4.2). The extra carbon dioxide that human activities are
adding to the atmosphere is only 3%-4% of the natural cycle, so some small
discrepancy in the cycle is not surprising.
Table 4.2 Changes in concentration of some greenhouse gases and their average atmospheric
lifetimes
Atmospheric concentration Annual rate Atmospheric

of increase lifetime
Gas Pre-1800 1990 (%) (years)
(ppmv) (ppmv)
Carbon dioxide 280 353 0.5 150
Methane 0.8 1.7 1 10
(ppbv) (ppbv)
Carbon 40 60 0.2 days
monoxide
Dinitrogen 288 310 0.25 150
oxide
(pptv)* (pptv)
Nitrogen oxides 40 250 0.3 days
(as nitrogen dioxide)
Non-methane 100-500 900 ? days
hydrocarbons
CFC-11 0 280 4 65
CFC-12 0 484 4 130
Other Cl 0 -1 0 0 0 1-5 1-400
compounds
*Parts per trillion (1 x 10 12) by volume.

The greenhouse gases show a direct effect due to the IR-absorbing

properties of the molecules involved. In addition, there can be indirect
effects related to the chemical reactions that the gases undergo in the
atmosphere. For example, methane shows a direct effect as the methane
molecules in the troposphere absorb IR radiation. Methane is mainly
removed from the atmosphere by a series of reactions initiated by the
hydroxyl free radicals (Eqn 4.23) that produce carbon dioxide and water,
which are greenhouse gases in their own right.
CH 4 + HO* — ►CH; + H20 (4.23)
CH 3 series of reactions — > C 0 2 + H20 (4.24)

Thus, even when destroyed, the methane leaves behind an ‘indirect’ effect of
radiation absorption by water and carbon dioxide. Hydroxyl radicals are
also involved in the removal of carbon monoxide from the troposphere (Eqn
4.25).
CO + HO* + 0 2 — > C 0 2 + HOO* (4.25)
hydroperoxyl
radical
If the quantities of carbon monoxide and methane are both increasing, there
will be competition for the available hydroxyl radicals. Unless there are also
new sources of hydroxyl radicals the average lifetimes of these gases will be
extended and they will exert their greenhouse effects for a longer period of
time.
The hydroxyl radical is involved in the removal mechanisms of the majority
of gaseous pollutants. There is great concern that the lack of sufficient
hydroxyl radicals will increasingly hinder the ability of the atmosphere to
cope with the ever larger quantities of potentially polluting emissions that are
entering it. However, some polluting emissions actually produce hydroxyl
radicals and so help slightly to alleviate the damage. Tropospheric ozone is a
prime example of a hydroxyl radical producer (Eqns 4.26 and 4.27).
0 3 + hv — > 0 2 + O (4.26)
H 20 + O — ►2HO* (4.27)
Increased emissions of methane mean that a greater quantity of methane
enters the stratosphere and forms hydrogen chloride, HC1, by reacting with
chlorine atoms. This reaction breaks the ozone destruction cycle that
involves chlorine (see Chapter 2) and helps to preserve the ozone layer.
Variations in the ozone concentration at different altitudes have different
effects on temperature changes at the Earth’s surface. Ozone in the upper
stratosphere absorbs UV and IR radiation from the Sun and prevents it
reaching the Earth’s surface. This warms the stratosphere and cools the
CARBON 85
troposphere. The ozone in the troposphere absorbs solar UV and IR

radiation, together with some of the IR emitted from the Earth. This warms
the troposphere. The relatively high concentration of ozone at the base of
the stratosphere tends to have a proportionately greater absorbing effect on
radiation leaving the Earth than on radiation arriving from the Sun. This
would imply that the destruction of ozone in the ozone layer would reduce
the greenhouse effect.
Any gaseous emission that breaks down to yield a greenhouse gas (e.g.
methane, carbon monoxide), or interferes with hydroxyl free radical con
centrations (e.g. methane, carbon monoxide, nitrogen oxides, HCFCs), or
affects ozone concentrations in the troposphere (e.g. methane, carbon
monoxide, nitrogen oxides), or ozone concentrations in the stratosphere
(e.g. carbon dioxide, methane, nitrogen oxides, CFCs, HCFCs) will have an
indirect effect on the amount of radiation that is absorbed or emitted by the
Earth and its atmosphere.
It is possible to attempt to estimate the relative impact that different
compounds will have on the absorption of IR radiation. This relative scale
of global warming potentials has each gas compared to carbon dioxide
(Table 4.3). The comparison can be on a basis of one molecule to one
molecule or on a mass-for-mass basis. The relationship between these two
values is determined by the relative molecular masses, e.g. if the per
molecule warming potential ratio for C 0 2:CH4 is 1:27, then the per unit
mass ratio will be 1:74 because the respective molecular masses are 44 and
12. The factors that need to be taken into account include:
(a) the IR absorption properties of each gas, including the effects of
overlapping absorption bands;
(b) the atmospheric lifetime of each gas; and
(c) the indirect effects of each gas, as outlined above.
The models usually assume that a small quantity, say 1 kg, of each gas is
released into the troposphere. The scaling up of these results to estimate the
effects of total present releases, or past or future releases, can then be carried
out (Table 4.3). The values are integrated over the required time period to
indicate the cumulative effect over that period. Whilst the general trends may
be shown, the models are so dependent upon the assumptions being made
that they cannot be relied upon for detailed predictions. Table 4.3 indicates
that methane is very important immediately after its release, but its short
atmospheric lifetime means that its relative importance as a greenhouse gas
rapidly declines. It should be noted that, because all of the gases released in
one time period are then being removed from the atmosphere, the radiative
effect of the gases released in 1990 will be more than halved in 2090.
Hypotheses concerning the climate changes that may arise from increases
in greenhouse gases are dependent upon these uncertain extrapolations
being introduced into climate models. A general circulation model (GCM) is
86 MAJ O R E L E M E N T S F O U N D IN L I V I NG M A T T E R
used to look at possible future global climate trends. This model involves
calculating values for various parameters at specific grid points above the
Earth’s surface. The individual results for each grid point are then combined
to give an integrated picture showing changes with time of features such as
temperature, rainfall, etc. The GCM is extremely complicated and requires
vast amounts of computing power to recalculate the values for each grid
point. However, the model can be no better than the assumptions and data
that are used in its production. A number of the key features of a GCM are
the following.
(a) It has a low resolution (grid points have horizontal spacings of at least
100 km, with spacings of 200-300 km more usual, and vertical spacings
of 1 or 2 km).
(b) Radiation effects can be described by exact equations, but, to reduce
computing demands, approximations are used.
(c) Convection effects in the atmosphere are one of the main ways heat is
transferred. There is a lack of detailed knowledge on the operation of
these effects and higher resolution models are needed to realistically
incorporate the flows of energy.
(d) Clouds can either increase absorption of solar radiation because of the
water vapour they contain or reflect the solar radiation back into space.
Which of these effects would be dominant if cloud cover increased is
uncertain.
(e) The interactions between the oceans and the atmosphere with respect to
heat transfer, rate of warming and carbon dioxide absorption are un
certain. The importance of oceanic eddy currents in controlling climate
conditions is recognized (the climate of the UK and Ireland is modified
by the Gulf Stream eddy current system). The resolution of the model is,
again, not high enough to allow realistic incorporation of the effects.
(f) There is a lack of knowledge on how land plants will affect the
absorption or release of carbon dioxide and also whether methane that
is at present trapped in the tundra will be released in large quantities if
temperatures rise.
(g) If temperatures increase there should be an increase in both evaporation
and precipitation of water. If the precipitation occurs over the Antarctic
there will be a net removal of water from the oceans to the land because
the temperature there will still be low enough for snow to form. How
much this will compensate for the expansion of the water in the oceans
as the temperature increases, and for the extra flow of water into the
oceans as lower latitude/altitude glaciers melt, can be only crudely
estimated.
(h) There are a number of feedback effects which can increase the rate at
which greenhouse gases build up in the atmosphere. Examples include
(i) the extra water vapour produced if temperatures rise; (ii) the release
CARBON 87
Table 4.3 Estimates of global warming potentials, over the next 100 years, of greenhouse gases
released from anthropogenic sources in 1990
Proportional contribution to
global warming potential (%)
1990 annual ------------------------------------------
emissions Time horizon (years)
Source Gas (Tg) (20) (100)
Fossil-fuel Carbon dioxide 19 500 26 44

combustion
Deforestation 6500 8 14
Total C 0 2 26000 34 58
Agriculture, Methane 365 39 23
natural gas
Motor vehicles Carbon monoxide 450 4 3
Combustion Nitrogen oxides 37 8 3
Transportation (as nitrogen dioxide) 19 4 2
Agriculture mainly Dinitrogen oxide 2.8 1 1
various sources Non-methane 90 3 1
hydrocarbons
Refrigerators CFC-11 0.29 1 2
Air-conditioners CFC-12 0.42 3 6
Foams, solvents, Other Cl 1.1 2 2
aerosols compounds
of methane that is at present frozen in the soils of the tundra; (iii) the
reduced solubility of carbon dioxide in sea water at higher temperatures;
and (iv) increased microbial activity in soils breaking down organic
matter more rapidly, in what are now temperate climates, to release
more carbon dioxide. The concern is that once a global warming event
is initiated the rate of change could be self-accelerating.
The results from the various models indicate a variety of temperature
rises, rainfall changes, etc. Although these models tend to show the same
general trends they are not precise enough to allow detailed planning
decisions to be made. In 1997, the ‘best’ estimates were that a doubling of
the pre-industrial carbon dioxide concentration from 280 to 560 ppmv (in
2060) would give a global average temperature increase of 1.6 K and a 3%
increase in precipitation. Larger temperature changes would be found closer
to the poles and smaller changes would be shown in equatorial regions. It is
probable that the higher mean temperatures would be achieved by greater
temperature increases in winter than summer. As for rises in sea-level,
figures up to about 40 cm are thought to be most probable.
The movement of warmer climate zones nearer the poles would also move
the regions where particular crops grow in a similar manner. For instance,
the major grain-growing areas would be shifted northwards in North
America and Europe. However, the more northern soils are generally less
fertile and thinner. This would suggest that yields would be decreased. Some
88 MAJ O R E L E M E N T S F O U N D IN L I VI NG M A T T E R
plants increase their yields in the presence of extra carbon dioxide provided
there is sufficient water and nutrients. Most of the main crop plants are
described as C 3 plants (an early metabolic product of carbon dioxide
fixation is 3-phosphoglyceric acid containing three carbon atoms) and these
might give increased yields. This group includes wheat, rice, potatoes, barley
and cassava, which between them make up over 50% of global crop
production. Another group of plants form oxaloacetic acid, a four carbon
molecule, when they fix carbon dioxide. They do not react so positively to
increased concentrations of carbon dioxide. They belong to the C4 group
and examples include maize, cane sugar and sorghum, which have about a
20% share in world food crop production. Most trees are C 3 plants, but
again increased stress due to climatic changes may more than wipe out any
extra growth resulting from higher carbon dioxide levels.
Some regions will gain in food productivity, others will lose. It seems
likely that the climatic changes will not appreciably reduce the productive
capacity of the Earth, but they could well disrupt the present imperfect
economic and social balance of wealthy and poor nations.
If all the presently estimated reserves of fossil fuels were burnt, the
maximum concentration of carbon dioxide in the atmosphere might reach
2000 ppm in 200-300 years, giving a temperature rise approaching 6 °C. Of
the global coal reserves, about 94% are located in six countries, namely the
(former) USSR (45%), the USA (25%), China (14%), Australia (2.5%),
Germany (2.5%) and the UK (1.6%). Coal is just as geographically
restricted in occurrence as oil and natural gas, but the reserves are about ten
times greater. The actual rate of release of carbon dioxide will be largely
decided by the policies of these six countries.
The mean temperature (15 °C) now being experienced in the northern
hemisphere is higher than the norm (13 °C) over the past 1 million years.
During the past 3000 years the mean temperature has usually remained
within 1 °C of the present, with warmer centuries occurring about as
frequently as cooler ones. The last warming period terminated in 1940, and
up to the late 1960s the mean temperature was dropping. This has been
followed by erratic behaviour with wider than normal variations making the
identification of a definite trend up or down difficult to detect. The rate and
magnitude of the carbon dioxide warming that could occur over the next
century could be greater than any that have occurred before. The
greenhouse effect is a very complicated phenomenon which has highlighted
how little is known about the working of biogeochemical cycles and the
consequences of their perturbation by human activities. It is unfortunate
that arguments about the validity of hypothetical climatic changes and their
consequences have obscured the important factor that present trends of
resource exploitation are not sustainable. Modification to present fossil-fuel
demands is required whether climate or sea-level forecasts are correct or not.
5 Nitrogen
Nitrogen Abundance by weight (the relative abundance is given in

parentheses): crust, 20 ppm (31); ocean, dissolved N2, 15.5 ppm
(11), soluble compounds, 0.7 ppm (17); atmosphere, 75.53%
( 1). ppm = mg kg~'.
Nitrogen, in the form of dinitrogen, N 2, makes up 78% by volume (76% by

weight) of the Earth’s atmosphere. Unlike dioxygen, 0 2, the other major
component of the atmosphere, dinitrogen has a low chemical reactivity and
is not directly available to the majority of living organisms. One con
sequence of this is that lack of available nitrogen is often a major factor
limiting plant growth, and the application of nitrogenous fertilizers
produces greatly increased crop yields.
The dinitrogen molecule has three covalent bonds joining the two atoms
together, N=N . Before a compound can be formed, these bonds must be
broken. This process requires 950 kJ mol-1 to destroy all three bonds.
Despite this very large energy input, a number of microorganisms have been
able to develop systems capable of overcoming this energy barrier. As a
result, nitrogen cycles in nature at a rate sufficient to allow plants to grow
wherever there are adequate water supplies, unless some other exceptional
condition prevents growth. The diagrammatic representations of the nitro
gen cycle (Figures 5.1 and 5.2) show that there are a number of chemically
different, mobile, nitrogen-containing species. The quantitative aspects of
many of the transformations in the cycle are not well known and the figures
given for the fluxes are often no better than educated guesses.
The relative thermodynamic stability of the various nitrogen species can
be determined, and this is shown on the scale headed ‘Free energy of
formation’ in Figure 5.1.
The nitrogen cycle is dominated by reactions involving biological
material. All the reactions in the series
N2 — ► N H 3 — > N 0 2 — > NO^ — > amino acids — > proteins
dinitrogen ammonia nitrite nitrate
and the reverse reactions back to N 2 can be carried out by microorganisms.

Natural inorganic reaction mechanisms do not produce ammonia from
dinitrogen; however, high temperatures (caused by lightning in natural
90 MAJ O R E L E M E N T S F O U N D IN LI VI NG MAT T E R
Oxidation Free energy

state of
formation,
AG
+1
less sta b le
+2 --
+4 4- t
p o sitiv e
0— 0
-3 —
neg a tiv e
+3 —
m ore stab le
+5 —
-3 —
Reactions
1 fixation 4 am m o n ifica tio n
2 nitrification 5 d entrification
3 a ssim ila tio n by plants 6 n itr a te -c o n ta in in g p recip ita tio n , o fte n as

nitric acid in acid rain
m icroorgan ism s play a part in rea ctio n s 1, 2 , 4 and 5
Figure 5.1 Chemical species found in the nitrogen cycle, illustrating changes in oxidative state
and relative stability.
systems, furnaces and automobile engines in industrial systems) can cause

N 2 and 0 2 to combine to form nitrogen oxides. These oxides are gradually
removed from the atmosphere as nitrates. This extra supply of nitrate
supplements the nitrate produced by microorganisms.
NITROGEN 91
NH3/NH4+- n 2o / n o / n o 2
2 . 3.8 x 109 13
30 1300
140/ r / * \ 50 /fT
£ dissolved N 3 x iqsJ S s S
5 compounds
‘1..»
io f -ft ;
SEDIMENT
x 109 kg Na-1
x 109 kg N reservoirs fluxes
Figure 5.2 The nitrogen cycle, illustrating some of the quantitative aspects of the movement of
nitrogen between land, sea and atmosphere.
In 1910-14, Haber and Bosch developed a method for producing

ammonia from atmospheric N 2 which has led to the growth of a large-scale
nitrogen fertilizer industry. The output of nitrogen fertilizers, about
80 x 106 t a _1, is approaching the estimated fixation of nitrogen by micro
organisms, about 140 x 106 tonnes a-1. The fact that the increase in world
food supplies has, overall, kept pace with the increase in population has
largely been due to increased use of nitrogen fertilizers.
5.1 Natural transformation processes in the nitrogen cycle
The biologically mediated transformation of dinitrogen into proteins

provides organisms with molecules capable of undertaking a wide variety of
functions, in tissue structure, enzymes, hormones, etc. The transformation
also releases energy (free energies of formation become more negative) that
can be utilized by the organism. However, the biogeochemical cycling of
nitrogen involves the breakdown of the proteins and the subsequent reversal
of the reaction sequence to replace the dinitrogen originally used. Why
should microorganisms apparently use up energy converting the more stable
compounds into less stable ones? In practice, of course, a similar problem
92 MAJ OR EL E M E N T S F O U N D IN LI VI NG MAT TER
must occur in all geochemical cycles. If more stable species are produced in
one-half of the cycle, the continuation and completion of the cycle demands
the subsequent production of less stable species and, consequently, the
energy released in one half of the cycle must be balanced by the absorption
of energy in the other half. Examination of the nitrogen cycle (Figure 5.1)
shows that the movement of the nitrogen involves (a) changes in oxidation
state, (b) changes in energy and (c) reactions with other elements
(particularly oxygen, hydrogen and carbon). Closer investigation of these
factors should help us to understand why the cycle keeps turning.
The major biological electron-releasing process is the oxidation of
carbohydrate to form carbon dioxide (Eqn 5.1).
CH20 + H20 — 4 C 0 2 + 4H+ + 4e” AG, - ^ k J m o r V (5.1)

The fixation of nitrogen requires a source of electrons to bring about the
reduction of N(0) to N (—3) (Eqn 5.2).
N 2 + 8 H+ + 6 e~— > 2 NH 4 AG, + 2 7 k J m o r 1e“ (5.2)

This half-reaction tells us that 27 kJ of energy is absorbed for each mole of
electrons being taken up by the nitrogen, i.e. the half-reaction will not be
favoured in energy terms, unless it can be combined with another half
reaction that will give the complete reaction a negative free-energy change.
Combining Equations 5.1 and 5.2 gives Equation 5.3.
CH20 + H20 + N 2 + 8 H+ + 6 e~ — > C 0 2 + 4H+ + 4e“ + 2NH+
AG, (—47 + 27) kJ mol-1 e“
(5.1, 5.2)
3CH20 + 3H20 + 2N 2 + 4H+ — > 3C 0 2 + 4N H t

. (5.3)
AG, —120kJ mol- N 2
Because this reaction (Eqn 5.3) releases energy, it is thermodynamically

favourable and the microorganisms can derive energy from it. It should be
noted in particular that the energy released when the carbohydrate is
oxidized more than outweighs the energy required to produce ammonium
ions when hydrogen ions, H +, are the source of hydrogen. By linking the
nitrogen cycle to the carbon cycle, the microorganisms are able to carry out
energetically unfavourable half-reactions through the indirect use of solar
energy to power the conversion. The apparent paradox of ‘impossible’
energy changes in the constant revolution of the geochemical cycles is
removed as soon as we realize that cycles are interlinked, so that energy is
transferred from one cycle to another, and that in addition energy is being
constantly added to the terrestrial system, particularly from the Sun.
NITROGEN 93
Although Equation 5.3 expresses the overall process involved in the

fixation of N2, the detailed mechanism is still not completely understood,
despite the large amount of research being carried out on the problem. If
natural nitrogen fixation could be controlled, so that it replaced the use of
industrial nitrogen fertilizers, there would be great savings in energy both in
the manufacture and transport of the fertilizer. At the same time there
should be less waste, as biological production should match biological
requirements. The natural fixation of nitrogen is carried out by
microorganisms, which may be free living or symbiotic, but all of which
contain the enzyme nitrogenase. Symbiotic organisms can only survive if
they live in association with other organisms. The root nodules of legumes
(e.g. peas) contain nitrogen-fixing bacteria, and there are also nitrogen-
fixing blue-green algae that are symbiotic with fungi in lichens or with some
ferns.
The free-living nitrogen fixers may be either bacteria, some of which live
in oxygen-rich (aerobic or oxygenic) conditions, whereas others live in
oxygen-deficient (anaerobic or anoxic) conditions, or may be blue-green
algae. Nitrogenase is very sensitive to 0 2 and those cells that respire
aerobically have had to develop various mechanisms to prevent oxidative
damage.
The enzyme nitrogenase consists of two large proteins. One of these
contains two atoms of molybdenum, 24-32 atoms of iron, 24-30 labile
sulfur atoms and has a relative molecular mass of about 2 2 0 0 0 0 , whereas
the other protein contains only four atoms of iron, no molybdenum, four
labile sulfurs and has a relative molecular mass of about 68 000. The two
atoms of molybdenum are essential to the activity of nitrogenase and no
fixation will occur if they are absent. The precise mechanism of the reaction
is not known, although it has been assumed that N 2 is bound to the
molybdenum and reduced at this site by a process such as the following:
EMo E M o -N = N -H
nitrogenase e
NH
By a process of this type, the organism, instead of taking a single leap over
the activation-energy barrier (the energy required to separate the triple
bonded nitrogen molecule into two reactive nitrogen atoms), climbs over the
94 MAJ O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
barrier in a number of smaller steps. The energy for the process is

transferred to the enzyme via magnesium adenosine triphosphate (MgATP),
which is hydrolysed to the diphosphate and free phosphate (Eqn 5.4).
MgATP ^ MgADP + PO^ + energy (5.4)
The transfer of electrons is favoured by the ability of both iron and
molybdenum to exist in two relatively easily interchangeable oxidation
states:
Fe2+ ^ Fe3+ + e“ Mo4+ ^ Mo5+ + e~
Both the energy and the electrons come ultimately from the oxidation of
carbohydrate. This one step in the nitrogen cycle requires the coming together
of the nitrogen, carbon, oxygen, hydrogen, sulfur, phosphorus, magnesium,
iron and molybdenum cycles, and the essential requirement for the very small
quantities of molybdenum highlights the fact that the need for certain critical
elements may be out of all proportion to the quantities involved.
The total amount of nitrogen fixed by microorganisms is difficult to
estimate precisely, but is thought to be of the order of 50 x 106—150 x 106
t a-1. The free-living nitrogen fixers excrete about 80% of their assimilated
nitrogen in a plant-available form to produce 1-5 kg N ha -1 compared to up
to 100-300 kg N ha -1 from leguminous symbiotic fixers. The nitrogen yield
varies widely with conditions, being greatest where photosynthesis occurs
most readily. It has been estimated that 12% of plant photosynthesis goes to
support nitrogen fixation, as three molecules of 0 2 are required to oxidize
enough glucose to provide the energy to reduce one molecule of N 2.
Other steps in the microorganism-controlled portions of the nitrogen
cycle include nitrification, ammonification and denitrification.
Nitrification
This conversion of ammonium ions to nitrate (Eqns 5.5 and 5.6) is essential
for the growth of the majority of plants, as they are able to absorb nitrate
but not ammonia or ammonium.
4NH+ + 6 0 2 —■>4 N 0 2 + 8 H + + 4H20 (5.5)
4N 0 2 + 2 0 2 — > 4 NO 3- (5.6)
Unfortunately, nitrate is very soluble in water and easily leached from soils.
Therefore, a build-up of a nitrate reserve in the soil is not possible.
NITROGEN 95
Ammonification
When plants and animals decay, the more complex molecules are utilized by
various organisms and eventually converted into simpler molecules or ions.
The nitrogen-containing compounds eventually form ammonia or
ammonium ions. For example:
(NH2)2CO + H 20 —■» 2NH 3 + C 0 2 (5.7)
urea
Denitrification
The regeneration of dinitrogen from nitrate occurs under both aerobic and
anaerobic conditions in the soil and oceans. Under anaerobic conditions,
organisms can use nitrate to replace dioxygen as an electron acceptor and as
their source of respiratory energy (Eqn 5.8).
5CH20 + 4 N 0 3~ + 4H+ — ►2N 2 + 5C 0 2 + 7H20 (5.8)
The reduction of nitrate does not always form dinitrogen. Appreciable
quantities of nitrous oxide (dinitrogen oxide), N 20 , may also be produced.
As gaseous N 20 is relatively inert in the troposphere, it is only slowly
removed and is the second most abundant nitrogen species (0.3 ppm) in the
atmosphere. The concentration of N 20 in the atmosphere is growing at the
rate of 0.3% per year.
5.2 Nitrogen oxides in the atmosphere
As well as the biologically mediated reactions, there are a number of other

reactions. Probably the most important of these occur in the atmosphere
and involve the cycling of various oxides of nitrogen. This part of the
nitrogen cycle has been the subject of some concern due to the production of
increasing quantities of nitrogen oxides by humans.
In addition to the nitrous oxide (N 20 ) added to the atmosphere by
denitrification reactions, nitric oxide (NO) and nitrogen dioxide (N 0 2) are
produced at high temperatures (Eqns 5.9 and 5.10) in areas where there are a
lot of thunderstorms this may be a significant input source of oxides of
nitrogen.
N2 + 0 2 —» 2NO (5.9)
nitric oxide
N2 + 2 0 2 — > 2N 0 2 (5.10)
nitrogen dioxide
The N20 gradually passes from the lower atmosphere into the
stratosphere where it is rapidly converted into dinitrogen (95%) and nitric
oxide (5%). Solar radiation with a wavelength below 250 nm (UV radiation)
96 MAJ OR E L E M E N T S F O U N D IN LI VI NG MAT TER
has enough energy to break up the N 20 molecules (Eqn 5.11 and 5.12). The
photolysis of N20 can only occur at heights above 20 km because the short-
wavelength radiation is absorbed by molecules such as N 20 and 0 3 and,
therefore, removed as it passes through the upper atmosphere.
N20 NO + N (5.11)
N20 N2 + 0 (5.12)
Further nitric oxide can be formed by the reaction of nitrous oxide with
excited (high-energy) oxygen atoms (Eqn 5.13) which are also produced by
short-wavelength radiation.
N 20 + 0 — > 2NO (5.13)
As discussed in Chapter 2, the nitric oxide is able to catalyse the
decomposition of ozone which could allow more harmful UV radiation to
reach the surface of the Earth.
Some of the nitric oxide, NO, reacts with either atomic oxygen or ozone
to form nitrogen dioxide, N 0 2, which then combines with water to give
nitric acid, H N 0 3 (Eqn 5.14).
NO N 02 ^ H N 03 (5.14)
or O 3
The nitric acid is then rained or washed out, either as the free acid or
combined with ammonia as ammonium nitrate, NH 4NO 3. A number of
other reaction pathways involving the oxidation and removal of the
nitrogen oxides occur, especially in the lower atmosphere. This is still an
area of great uncertainty, mainly because the concentrations of the
molecules involved are so low that it is very difficult to trace their fates.
The burning of fossil fuels in furnaces and automobile engines raises the
gas temperature sufficiently to allow dinitrogen and dioxygen to combine. In
general, the higher the combustion temperature, the greater the quantity of
nitrogen oxide. In global terms, anthropogenic emissions from these sources
are only about 8 % of naturally produced nitrogen oxides. However, in
urban areas the relative levels can be elevated several hundred times under
certain climatic conditions so that whereas the global concentration NOx is
3 x 10~ 3 ppm, the concentration in some inner cities is 1-2 ppm. When
associated with high hydrocarbon levels and sunlight, these high local
concentrations of nitrogen oxides lead to the development of photochemical
smogs (Figure 5.3). Photochemical smogs contain a wide variety of organic
compounds - such as peroxides (oxidants), aldehydes and ketones (form
aerosols), and organo-nitrates (lachrymators) - that are harmful in various
degrees.
NITROGEN 97
(a) Early morning (b) Later morning

sunlight
(ultraviolet radiation)
WARMER AIR
COOLER AIR N
2NO + 0 2 —> N O 2 (brown)/
vehicle . N 0 2 + 0 2 -> NO + 0 3
exhausts v 2' n I build-up of (CH->)„ and
VCO
inversion prevents dispersion of oxidation of NO gives brown colour

emissions to haze - build-up of ozone
(c) Late morning, afternoon (d) Night

sunlight
(ultraviolet radiation)
dark
dispersal
(C H 2)„ + (N O , O 3, N 0 2, (speed depends upon
H 20 ) form peroxides, whether inversion
carbonyl compounds, breaks down)
organo-nitrates, etc.
further absorption of solar energy without sunlight (and less traffic)

produces eye irritants and various no further build-up - therefore
other harmful compounds partial or complete dispersal is
possible
Figure 5.3 Conditions for smog formation.
It is ironic that the reduction in smoke-based smogs in the UK brought

about by the Clean Air Acts (see Chapter 6 ) has provided conditions that
favour the formation of photochemical smogs. The formation of photo
chemical smogs is dependent upon there being high enough concentrations
of nitrogen oxides and volatile organic compounds, especially hydro
carbons, together with sufficient sunlight, particularly UV-A. The smoky
atmosphere earlier this century reduced the amount of sunlight so that the
photochemical reaction sequence was rarely initiated.
Solar radiation provides the energy to break some of the bonds in
nitrogen oxides and volatile hydrocarbons. One important sequence of
reactions (Eqns 5.17-5.21) is started by the formation of atomic oxygen
from nitrogen dioxide (Eqn 5.15).

N 0 2 + h v { \ < 420 nm) — ►NO + O (5.15)
The reactive atomic oxygen can then produce the following:

(a) ozone by reacting with dioxygen (Eqn 5.16);
(b) organic free radicals, that are also very reactive, by reacting with
hydrocarbons (Eqn 5.17). It should be noted that about 60% of non
methane volatile organic compounds are from natural sources (trees
etc.), with 16% from wood combustion (fuelwood, deforestation) and
savanna burning, 7% from gasoline use and 5% from the organic
chemicals industry;
(c) hydroxyl free radicals by reacting with water vapour (Eqn 5.18).
Hydroxyl free radicals are key reactants in many tropospheric reactions.
They are particularly important in controlling the removal of methane
and hence the rate at which the concentration of this greenhouse gas
increases (Chapter 4).
0 2 + 0 + M —+ O 3 + M (5.16)
(M is an energy absorbing molecule, e.g. N 2)

RH + O —> R* + variety of products (5-17)
hydrocarbon organic
free radical
H20 + O — ►2HO* (5.18)

hydroxyl
free radical
The early stages of photochemical smog formation are mainly

dependent upon reactions between hydroxyl radicals and hydrocarbons.
HO* + RH — > R* + H20 (5.19)
R* + 0 2 — > ROO* (5.20)

organic peroxyl
free radical
ROO* + N O — > RO* + N 02 (5.21)

organic alkoxyl
free radical
These reactions do not occur immediately and their occurrence depends

upon there being high enough concentrations of the various reactants.
As has already been indicated, the subsequent reaction sequence is very
complicated but ozone and the products illustrated in Figure 5.3 are
typically produced.
NITROGEN 99
If atmospheric conditions tend to be stagnant because of temperature

inversions, as is the case in Los Angeles and Mexico City, photochemical
smog develops in situ. However, as the concentrations of nitrogen oxides
and hydrocarbons become generally higher, the presence of elevated levels
of tropospheric ozone and the other products of these photochemically
induced reactions is also becoming more widespread. The slow rates of
reaction mean that the pollutants may appear many miles from the areas
where the reactants were released into the atmosphere. For instance, the
Grand Canyon in the USA is now being affected by photochemical smog
whose source of nitrogen oxides is mainly in Las Vegas. Some of the
hydrocarbons are of natural occurrence. Similarly, high concentrations of
ozone in rural areas of southern England have been related to polluted air
moving north from France and reacting in sunny weather to form ozone.
There are high levels of ozone (90-130 ppbv) appearing over the Atlantic
and Pacific Oceans hundreds of miles from land, but associated with large-
scale forest burning. The fires release hydrocarbons and nitrogen oxides that
react to form ozone.
The increase in the formation of photochemical smogs has followed the
increase in use of motor vehicles. These release both nitrogen oxides and
hydrocarbons into the atmosphere. Attempts to reduce the photochemically
induced pollution have concentrated on altering the exhaust emissions of the
vehicles. One method is to fit catalytic convertors to the exhaust system.
When the exhaust gases pass through the catalytic convertor system the
nitrogen oxides are reduced to dinitrogen (Eqn 5.22) and then the
hydrocarbons and any remaining carbon monoxide are oxidized to carbon
dioxide and water (Eqns 5.23 and 5.24).
2 NO + 2CO — > N 2 + C 0 2 (5.22)
2CO + 0 2 — ►2C 0 2 (5.23)
RH -f x 0 2 — >yC 0 2 + zH20 (5.24)

A mixture of metals, including the rare metals platinum and palladium, and
metal oxides, such as chromium oxide, can be used in the catalysts. The
catalytic action is destroyed if the petrol contains lead and this has been the
driving force behind the move to unleaded petrol. The catalyst system is
most effective when it is hot. This means that on short journeys the expected
90% reduction in nitrogen oxide and hydrocarbon emissions will not occur.
The fuel efficiency of cars fitted with catalytic convertors is reduced by about
3%—10%. Therefore, the reduction in photochemical pollutants by this
method will increase emissions of carbon dioxide. It appears that the long
term solution to the problems caused by motor vehicles will only be
achievable by either changing the propulsion unit or by reducing the number
100 MA J O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
of motor vehicles. There are increasing quantities of platinum, palladium,

rhodium and chromium compounds being found in roadside dust and in
road runoff. These metals form compounds that can be toxic.
About the same quantity of nitrogen oxides are produced from large
stationary sources (power stations and industrial furnaces) as from motor
vehicles. Whilst their tall stacks tend to lead to wider dispersal and a lower
involvement in photochemical smog formation, they have raised the general
background concentration of nitrogen oxides. Methods of control of emis
sions involve a change of burner design, which has already been introduced
in a number of power stations, and there is the possibility of treating the flue
gases to remove nitrogen oxides if this was required.
There is increasing evidence that in the UK the various emissions from
motor vehicles and their photochemically formed products are causing
urban health problems, especially respiratory illnesses. Ozone is extremely
harmful to plants and it has been suggested that much of the damage that
was blamed on ‘acid rain’ (see Chapter 6 ) could have been induced by ozone
rather than sulfur dioxide, sulfuric acid or nitric acid. Ozone produces
organic free radicals by reacting with the hydrocarbons released naturally by
the plants and it is these free radicals that appear to interfere with the
normal biochemistry of the plant. However, as nitrogen oxides are also
present in the ozone-polluted air, it could well be that these, and the
associated nitric acid (Eqn 5.14), are responsible for much of the damage.
Nitric oxide is now recognized as playing an important part in human
metabolic processes being involved in the control of muscle relaxation, in
the way macrophages operate in the immune system and in the transmission
of nerve impulses in the brain.
5.3 Nitrogen fertilizers
There has been a massive increase in the industrial fixation of atmospheric

nitrogen over the past 40 years to keep pace with the 20-fold increase in
nitrogen fertilizer usage in the UK.
Dinitrogen and dihydrogen combine in the presence of an iron catalyst to
produce an equilibrium mixture of reactants and ammonia (Eqn 5.25). The
ammonia is removed by condensing it to a liquid and the unused N 2 and H 2
are recycled. Although the conversion rate in any one pass of gases over the
catalysts may only be 10 %, constant recycling of the reactants means that
eventually very high percentage conversions are achieved.
Fe catalyst
40 0 -5 4 0 °C
N 2 (g)+ 3 H 2(g) - 2NH 3 (g) (5.25)
[g) [g) 8 0 -3 5 0 atm
Methane, CH4, is still used as the source of hydrogen in most countries,

NITROGEN 101
even after the rises in the price of natural gas. The methane is mixed with
steam and passed over a nickel catalyst to give an equilibrium mixture
displaced well to the right of Equation 5.26.
Ni catalyst
CH4(g) + H 20 (g) 750_ ^ 5oc CO(g) + 3H2(g) (5.26)
35 atm
It is becoming increasingly more economic to produce ammonia near to the

sources of cheap natural gas (such as the Middle East) and then ship it to the
user country, rather than to ship the natural gas and produce ammonia near
the point of use. Present-day nitrogen fixation plants produce about 1000
tonnes of N H 3 per day and operate at about 80% of the maximum energy
efficiency. The use of coal as a feedstock to replace natural gas would
increase the energy usage of the plant by 50% and the building costs of the
plant would also be about 50% greater.
Nitric acid (H N 03) is manufactured from ammonia (Eqns 5.27, 5.28 and
5.29) and then combined with more ammonia to form ammonium nitrate
(NH 4N 0 3), a popular solid fertilizer. (It is also used in explosives.)
Pt—Rh catalyst
4NH 3 + 5 0 2 ^ 4NO + 6H20 (5.27)
2NO + 0 2 ^ 2N 0 2 (5.28)
3N 0 2 + H20 ^ 2H N 0 3 + NO (5.29)
These reactions are all thermodynamically favourable, but all have kinetic
problems that still have to be overcome. The platinum-rhodium catalyst
(Eqn 5.27) is only efficient under optimum conditions and various side
reactions occur. No catalysts have yet been found for the conversion of
nitric oxide, NO, to nitric acid. As a result, very large reaction towers are
required and, as these are not 100 % efficient, nitric acid plants are
recognizable by the brown-yellow fumes of the mixture of nitrogen dioxide
(N 0 2) and dinitrogen tetroxide (N 20 4) that they emit. (N 0 2 and N 20 4 exist
in equilibrium with each other, with a higher proportion of N 0 2, which is
brown, at higher temperatures.)
Over the years there has been an increase in the use of compounds
containing higher concentrations of nitrogen, together with higher
concentrations of nitrogen in the applied fertilizers. Compounds used
include ammonium sulfate ((NH 4)2 S 04), which has 21% N; ammonium
nitrate (NH 4N 0 3), which has 33.5% N; urea ((NH 2)2CO), which has 45%
N; and liquid ammonia (NH3), which has 82% N. Environmental and
economic costs make the correct pattern of application to maximize the
nutrients’ efficient uptake essential. Increasing the amount of nitrogen
applied to a crop gives large increases in yield up to an optimum, but at

higher levels the yield may be reduced.
5.4 Nitrate in water supplies
The ploughing up of grassland to grow arable crops and the increasing

amounts of nitrogen-based fertilizers that have been used in many countries
have led to much higher concentrations of nitrate being found in both
ground and surface waters. This nitrate can encourage algal blooms to
develop (see Chapter 7) in watercourses. There has been a lot of concern
about increased nitrate levels in drinking water. The EC and WHO
standards have been set at 50 mg N 0 3~ dm” 1, but 50-100 mg dm -3 may be
'acceptable’, although the WHO standard states, Tf the nitrate content is
within the acceptable range and the water is otherwise chemically and
bacteriologically satisfactory, it may not give rise to trouble, but physicians
in the area should be warned of the possibility of infantile methaemo-
globinaemia occurring.’ It is this risk to children below the age of 6 months
that appears to be the major health problem caused by elevated nitrate levels
in drinking water. However, there have been no cases in the UK since 1972.
The majority of cases in other countries, such as the 1300 in Hungary
between 1976 and 1982, have been associated with well water and symptoms
of microorganism-induced stomach infections. A further potential hazard
may be the formation of carcinogenic nitrosamines in the human digestive
system by the conversion of nitrate to nitrite and subsequent reaction with
amino acids. There is no clear evidence that there is any increase in stomach
cancer in populations living in areas where nitrate levels are in the 50-100
mg dm -3 range.
Methaemoglobinaemia is the name given to the effects of a reduction in
the ability of the haemoglobin in red blood cells to carry oxygen. Normal
haemoglobin contains iron(II), Fe 2 + , which binds reversibly to 0 2. Nitrite
converts the iron(II) to iron(III), Fe 3 + , which does not bind to 0 2; oxygen
can no longer be carried by red blood cells containing these oxidized groups.
The haemoglobin in new-born children has a slightly different structure to
the haemoglobin of an adult. This foetal haemoglobin (about 60% of total
haemoglobin at birth) is more susceptible to oxidation. In the first few
months after birth the proportion of foetal haemoglobin declines, as does
the susceptibility to methaemoglobinaemia. In addition, the conditions in
the gastrointestinal tracts of very young children are more favourable to
nitrate-reducing bacteria than the conditions in the digestive tracts of older
humans. Therefore more of the ingested nitrate is reduced to nitrite, which
then reacts with the haemoglobin. Cattle also have digestive systems capable
of supporting nitrate-reducing bacteria and they too can suffer from
methaemoglobinaemia if nitrate levels are high in the water they drink.
NITROGEN 103
5.5 Balanced diets and food production
Although proteins, carbohydrates and fats are the major dietary

requirements for humans, many other compounds are needed to give a
healthy body. What constitutes a complete balanced diet is not precisely
known, but the major features of such a diet are recognized. The WHO has
produced recommended daily allowances (RDAs) for energy, protein,
vitamins and minerals for reasonably healthy individuals. The RDAs vary
with age and sex, but, because of natural individual variations and the
inadequacy of the data on which the balances are based, the recommended
intakes may be insufficient for some people and over-generous for others.
Nitrogen is only taken up by plants in certain forms, mainly nitrate, and
then used to produce proteins. Animals cannot produce proteins from
simple ions, but must ingest proteins and use these as a source of amino
acids to synthesize the proteins they require. Therefore, proteins are an
essential requirement of any animal’s diet. Some animals obtain the required
proteins from plants (herbivores), others feed off other animals (carnivores).
Humans belong to the group that utilizes both plants and animals
(omnivores). Proteins are not required as a major energy source for human
beings as we get energy from carbohydrates and fats.
Not only must the diet contain enough protein - about 0.8 g protein per
kg body weight - but these proteins must be of the correct type. Humans are
unable to synthesize nine essential amino acids (Table 5.1) and these must be
supplied in the proteins eaten. Different foods contain different quantities of
the essential amino acids. Some protein sources, e.g. eggs, fish, meat, are
described as ‘high quality’ because they contain high quantities of all the
essential amino acids, whereas most vegetable protein is ‘low quality’
because it is deficient in one or more of the essential amino acids (Table 5.1).
The deficiency of just one amino acid reduces the degree of utilization of all
the rest, because the proteins that are synthesized from them contain fixed
proportions of each amino acid. For instance, an adult requires 1 part of
phenylalanine to 0.73 parts of lysine. In rice, there are only 0.42 parts of
lysine to 1 part of phenylalanine. As there is not sufficient lysine to allow full
utilization of the phenylalanine, rice is relatively deficient in lysine.
Vegetarian diets must contain complementary protein sources. For example,
by combining legumes (e.g. beans and peas) that are higher in lysine and
lower in methionine, with cereals (e.g. wheat, rice and maize) that are lower
in lysine and higher in methionine, a balanced protein diet can be achieved.
In developing countries, the majority of the population relies on a few
crops for its staple diet. Amino-acid deficiencies may be widespread if the
correct balance of cereals, legumes and vegetables is not achieved.
Worldwide, the increases in population have been balanced by increases in
food production so that the average energy intake has remained steady. The
increased production has been achieved by a particularly large increase in
Table 5.1 The amounts of essential amino acids in some foods (mg amino acid per 10 g food)
Cows’ Hens’
Name Abbreviation Beans Maize Rice milk Beef eggs
Isoleucine lie 37 30 36 47 53 54
Leucine Leu 74 116 79 95 82 86
Lysine Lys 94 30 42 78 87 70
Methionine and Met + Cys 47 43 40 33 38 57
cystine
Phenylalanine and Phe + Tyr 68 84 99 102 75 93
tyrosine
Threonine Thr 56 40 33 44 43 47
Tryptophan Trp 12 8 14 14 12 17
Valine Val 39 51 57 64 55 66
cereal yields and resulting diets have become less varied. This dependency on
a few species is highlighted by the fact that five crops (wheat, rice, maize,
potato and barley) appear to contribute a greater tonnage to world food
stocks than all other food crops added together. Although a worldwide
balance is being achieved, there is insufficient transfer from overproducing
to underproducing areas. Malnutrition and famine will remain major
problems until problems of transport and wastage are overcome.
The use of animal protein to give better balanced diets in the developing
countries suffers from a number of problems:
(a) although many animals will eat cellulose-based plant material, which
humans cannot digest, there are few parts of the world where this can be
grown in large enough quantities on land that could not be used for
growing directly usable food crops;
(b) animal products deteriorate very rapidly and their effective utilization
depends upon preservation methods that are often energy expensive and
demand relatively high technology;
(c) many countries have religious and cultural restrictions that prevent
either the killing or consumption of animals;
(d) the conversion of vegetable protein to animal protein is a very inefficient
process, ranging from about 4% efficiency in beef production to about
2 0 % efficiency in poultry production.
It would seem that amino-acid deficiencies will be best overcome by

varied vegetable-protein-based diets, and, towards this end, changes in the
genetic stock of non-cereal crops to increase yield and reduce disease
susceptibility are being actively researched.
Smaller quantities of vitamins and mineral elements are required in
addition to the major components of the diet, carbohydrates, fats and
proteins, which provide energy and build up or renew body tissue. The
mineral elements include all the elements apart from carbon, hydrogen,
NITROGEN 105
oxygen and nitrogen that are essential for the correct functioning of the
body. The functions include formation of the skeleton, maintenance of the
electrolytic balance in body fluids, electrochemical stimulus of nerves and
muscle, activation and structure of enzymes, and oxygen transport. Details
of the function of individual elements will be discussed in the relevant
chapters. Vitamins are organic compounds of varying degrees of complexity
whose RDAs vary from 60 mg for vitamin C to 6 fig for vitamin B12.
Vitamins were named before their chemical constitutions were known;
letters were used to distinguish the various extracts that were found to be
essential for life (Latin vita = life). As extraction and separation techniques
improved, some of the vitamin extracts were found to contain a number of
active ingredients which were distinguished by the use of added numbers,
e.g. Bi, B2. When the chemical structures had been determined, trivial names
were given (Table 5.2). Apart from vitamin D, which can be synthesized in
the skin when it is exposed to sunlight (and, therefore, may not strictly be a
vitamin), the vitamins must be eaten as part of the diet. The vitamins may be
classified as water soluble or fat soluble. The water-soluble vitamins are
easily eliminated from the body, in the urine, and removed from foodstuffs,
if cooked in water. They must be present in the daily diet if deficiencies are
to be avoided. The fat-soluble vitamins are more stable, being less easily
destroyed by heat; any vitamins in excess of daily requirements are stored in
the liver. This storage process means that there is not the same requirement
for regular daily supplies. However, these vitamins are also quite toxic,
unlike the water-soluble ones, and excessive intakes, particularly of vitamins
A and D, can lead to undesirable effects.
Table 5.2 Vitamins, their recommended daily allowances (RDAs) and possible effects of
deficiency in human diets
RDA
Vitamin Male Female Deficiency effects
W ater-soluble
B group
Thiamine (Bj) 1-1.5 mg 0.7-1.1 mg Beriberi
Riboflavin (B2) 1-7 mg 1.3-1.8 mg Cracked skin, eye lesions
Niacin 18 mg 15-21 mg Pellagra
Pyridoxine (B6) 2 mg 2 mg Anaemia, dermatitis
Cyanocobalamin (B12) 0.003 mg Pernicious anaemia
Pantothenic acid 10 ng Neuromotor (rare)
Folic acid c. 0.4 ng Anaemia
Biotin 0.3 ng Dermatitis
Ascorbic acid (C) 30 mg 30-60 mg Scurvy
Fat-soluble
Retinol (A) 0.75 mg 0.75-1.2 mg Eye disease, skin lesions
Cholecalciferol (D) 2.5 ng 2.5-10 ng Rickets
Tocopherols (E) 15 mg N ot known
Phylloquinone (K) 0.03 mg Internal haemorrhages
6 Sulfur
Sulfur Abundance by weight (the relative abundance is given in

parentheses): Earth, 1.8%—2.9% (5 or 7); crust, 260 ppm (16);
ocean, 905 ppm (6 ); atmosphere, 0.6 ppb (15). ppm = mg kg-1;
ppb = Mg kg-1.
6.1 The sulfur cycle
The range of sulfur concentrations given for the Earth indicates the
uncertainty of our knowledge of the inner mantle and core where most of
the sulfur is concentrated.
The cycling of sulfur at the Earth’s surface has been greatly increased
since the start of the Industrial Revolution by the demand for fuel, metals
and fertilizers. Despite the great deal of study the sulfur cycle has received in
the past few years, there is still some uncertainty about many of the fluxes
(Figure 6.1). In the case of anthropogenic emissions to the atmosphere,
knowledge of the extraction and usage of fossil fuels and sulfide ores gives a
good indication of gaseous sulfur oxide outputs. It is noticeable that the
majority of the anthropogenic effects lead to an increase in oxidation state
for the sulfur (Figure 6.2), whereas the biologically mediated natural cycle of
sulfur has a large component in which the oxidation state is reduced. The
cycles of sulfur and nitrogen have a number of similarities which will be
discussed in the following section, but one important difference is that the
major reservoir for nitrogen is the atmosphere, whereas the major available
reservoir for sulfur is the crust, with only a small, but potentially damaging,
proportion in the atmosphere.
Microorganisms and the sulfur cycle

There is a strong analogy between sulfur and nitrogen in the way that
microorganisms influence their biogeochemical cycling. Each element tends
to be present in living organisms in its most reduced form, i.e. nitrogen (—3)
as amino groups, —NH 2, and sulfur (—2 ) as hydrosulfide groups, —SH.
Sulfur is an important secondary constituent of amino acids and proteins.
The ability of this sulfur to form sulfur-sulfur bonds allows cross-linking in
proteins by so-called disulfide linkages (Figure 6.3). There can be both
SULFUR 107
ATMOSPHERE \7]
Figure 6.1 Some quantitative aspects of the sulfur cycle.
intermolecular bonding linking together adjacent proteins and so developing

large-scale structures (e.g. hair and nails) and intramolecular bonding,
giving specific spatial characteristics to the protein (e.g. enzymes). When
organic sulfur compounds are decomposed by bacteria, the initial excreted
sulfur product is often hydrogen sulfide, H2S (Eqn 6.1), in the same way that
organic nitrogen compounds yield the hydrogen-containing products
ammonia, N H 3, or ammonium ions, NH4.
R _ SH bacteria H z S + R H ^
organic organic
hydrosulfide com pound
Many marine phytoplankton produce compounds that break down to

produce dimethyl sulfide, (CH 3)2S. Dimethyl sulfide is a major biogenically
produced sulfur compound, releasing about 20-40 TgS a -1 from the oceans.
Dihydrogen sulfide, H 2S, is more important in terrestrial and salt-marsh
environments. Dimethyl sulfide, like dihydrogen sulfide, is rapidly oxidized
to form sulfur dioxide and, ultimately, sulfate (Eqn 6.2). Carbonyl sulfide,
OCS (structurally similar to carbon dioxide, C 0 2 or OCO), is the most
abundant sulfur species in the atmosphere (approximately 0.5 ppbv).
Though it is produced in much lower quantities than sulfur dioxide and
dimethyl sulfide, OCS has a relatively long residence time (3.5-7 a). This
gives atmospheric loadings of 5 TgS as OCS, 1.5 TgS as sulfate aerosol and
0.5 TgS as S 0 2. Carbonyl sulfide is mainly produced from biogenic
108 MAJOR E L E M E N T S F O U N D IN LI VI N G MA T T E R
A tm o sp h e r ic L ith osp heric O xid ation Free
MO microorganisms can bring about these reactions

* marine phytoplankton often release dimethyl sulfide, (CH3)2S
Figure 6.2 Chemical species found in the sulfur cycle, illustrating changes in oxidation state
and relative stability.
organosulfur compounds (containing -SH groups) in the oceans and by

photooxidation of carbon disulfide, CS2 (concentration in atmosphere
0.001-0.006 ppbv, rapid turnover, produced from organosulfur compounds
and industrial sources); together with a variable amount coming from
biomass combustion. The major sinks for OCS are plants, via the
photosynthesis mechanism, and adsorption in soils and wetlands, with the
remaining 15-20% reacting with hydroxyl radicals, OH, to form sulfates.
The formation of this sulfate has been suggested as being the main non-
volcanic source of sulfate aerosols in the stratosphere. This possibility has
increased interest in the cycling of OCS and the part it might play in the
chemistry of ozone destruction (Chapter 2) and in the absorption of infrared
radiation (Chapter 4). There is no indication that there has been a change in
the global mean concentration of OCS in the past 20 years.
SULFUR 109
(a) The formation of a disulfide linkage by the combination of two cysteine

groups on adjacent segments of protein chains - the reaction occurs under
reducing conditions
O H O O H
II II 1
- u -
-C — N- - N- - C- N—
U
1
1
I 1 1
H CH2 H H ch2 H
11
SH s
1
1
SH s
1
I 1
o ch2 O O ch2 O
II 1
— N-pC — C — N-pC — C— C— N
1 1
I I I i ! 1 1
HI H H I H H h
cysteine group
(b) Inter-molecular bonding joining (c) Intra-molecular bonding

two protein molecules together holding a protein chain in
a particular shape
Figure 6.3 The formation of sulfur-sulfur bonds (disulfide linkages) in proteins.
Some microorganisms in muds produce elemental sulfur, a yellow solid,

which is comparable with the production of dinitrogen gas from nitrogen
compounds.
The oxidation of the reduced forms of sulfur by dioxygen (Eqn 6.2) may
occur either through the action of microorganisms in the soil, the sediment
and the water column, or without biological control, particularly in the
atmosphere.
1 10 MA J O R E L E M E N T S F O U N D IN L I V I N G M A T T E R
S02 SO 3 — ►SOj- (6 .2 )
sulfur sulfur sulfate
sulfide may not be dioxide trioxide
formed)
The half-reaction for the reduction of sulfate (Eqn 6.3) is energetically

unfavourable.
S O ^ + 9H+ + 8 e“ — ►HS + 4HzO AG, +21.4 kJ mol“ 1 e" (6.3)

To carry out this half-reaction the microorganism combines it with a half
reaction such as the oxidation of carbohydrate that will give an overall
negative free-energy change, leading to sulfate reduction (Eqn 6.4).
SO^ + H + + 2CH20 — > HS + 2 H 20 + 2C 0 2

AG, -25.6 k J m o r 1 e~ (6.4)
The sulfate is acting as an electron acceptor and the oxidation of the
carbohydrate is able to proceed. The energy released to the organism is only
about one-fifth of that which is obtainable when dioxygen acts as the
electron acceptor in aerobic respiration (Eqn 6.5). Nitrate can also act as an
electron acceptor (Eqn 6 .6 ). This reaction releases three times as much
energy as the reduction of sulfate (Eqn 6.4), but sulfate reduction does
produce slightly more energy than is obtained by the methane-producing
fermentation reaction (Eqn 6.7).
CH20 + 0 2 — > C 0 2 + H20 AG, —125.5 kJ mol -1 e~ (6.5)
2CH20 + N O j + 2H+ — > 2C 0 2 + H20 + NH+ AG, -82.2 k J m o r 'e "

(6 .6 )
2CH20 — >■CH 4 + C 0 2 AG, -23.5 kJm ol -1 e~ (6.7)

The consequences of this order of energy production are that if all four
mechanisms are possible, then organisms that gain their energy by aerobic
respiration will be favoured (Figure 6.4). The greater quantity of energy that
the aerobic respirators obtain from a given carbohydrate source will allow
them to develop at the expense of microorganisms depending upon less
efficient energy-releasing processes. When the dioxygen supply becomes
depleted and the conditions become anaerobic, the nitrate reducers will be
most favoured. The nitrate concentration is much lower than the sulfate
concentration under marine conditions and the nitrate is soon depleted,
allowing the sulfate-reducing microorganisms to become dominant. The
formation of hydrogen sulfide (H 2S) is a characteristic feature of anaerobic
SULFUR 111
(a) Marine conditions (b) Fresh-water conditions
for marine and freshwater systems, the surface waters are generally aerobic
with a plentiful supply of dioxygen, but at depth or in the sediments conditions
become anaerobic
(c)Soils
o2------ »co2
N 05----------- > n h ;
fermentation-----------
anaerobic conditions result when the soil is saturated with water or an

impermeable layer forms preventing access by dioxygen - fermentation
reactions are particularly common in buried refuse tips
Figure 6.4 Electron acceptors found under different natural environmental conditions.
marine sediments due to the high levels of sulfate, as compared with nitrate,
in sea water. In soils, where nitrate levels are often higher than sulfate levels,
ammonia is produced under anaerobic conditions. When sulfate
concentrations are very low, methane bacteria become the dominant form.
Examples include (a) fresh waters, in which sulfate is naturally at a low level;
(b) marine muds, in which the sulfate has already been converted to sulfide;
and (c) sewage sludge, in which both nitrate and sulfate are at low levels. In
oceanic surface waters dimethyl sulfide is formed much more commonly
than H2S because of the presence of the compound dimethyl sulfono-
propionate produced by some species of phytoplankton. Dihydrogen sulfide
112 MAJOR E L E M E N T S F O U N D IN LI VI N G MA T TE R
is associated more with anaerobic sediments that are found in swamps and
on sea-floors.
The hydrogen sulfide that is produced may be released as a gas to the
atmosphere, where it is oxidized (Eqn 6.2) (as is dimethyl sulfide), or it may
react with metal ions in the sediments or water column to form insoluble
sulfides. The later transition metals and those metals which come after the
transition metals in the periodic table are especially likely to form insoluble
sulfides. Iron, because it is present in relatively large quantities, forms the
major sulfide mineral reservoir as troilite, FeS (Eqn 6 .8 ), and as iron pyrites,
FeS2 (Eqn 6.9)
2Fe(OH ) 3 +3H 2S — ►2FeS +S + 6H20 (6 .8 )
iron (III) troilite
hydroxide
FeS + S — ►FeS2 (6.9)

pyrites
The black colour of many sediments is partially due to the presence of

iron sulfides as well as organic matter. The association of sulfide minerals,
particularly iron pyrites, with rich organic marine sedimentary deposits such
as black shales and coal can lead to acidity when these deposits are exposed
to the Earth’s atmosphere. Such exposure can be due to uplift and
weathering or mining. Oxidation of the sulfides leads to the formation of
sulfuric acid (Eqn 6.10).
2FeS2 +2H 20 + 7 0 2 — » 2FeS0 4 + 2H 2 S 0 4 (6.10)
pyrites iron (II) sulfuric
sulfate acid
This redox reaction can occur rapidly in the presence of water and dioxygen,
especially when microorganisms are involved. The acid produced may be
neutralized as it passes through rocks and soil in the ground water especially
if it is formed slowly by natural weathering processes. Because of the greater
solubility of many metals in acid solutions, extensive leaching occurs. Many
black shales contain high concentrations of potentially toxic elements and
the increased mobilization of these metals in the acidic waters may cause
elevated levels to appear in plants and aquatic biota. The problem becomes
much more serious in metalliferous mine-waste dumps that can have some
toxic metals present in parts per hundred, rather than the parts per million
of normal rocks and soils. The mining of metal sulfide ores and coal leads to
the exposure of large quantities of sulfides and hence to the production of
much larger quantities of acid in localized areas than does the weathering of
shales. The resultant large addition of acid, sometimes enriched in toxic
metals, can lead to major pollution problems in the areas surrounding the
mining operation.
SULFUR 113
6.2 The sulfur dioxide problem
Sulfur dioxide (S02) is introduced into the atmosphere by both natural and
human activities. The amount of sulfur dioxide produced by anthropogenic
sources in the mid 1990s was estimated to be 190 Mtonnes compared to 76
Mtonnes from natural sources; but in the northern hemisphere,
anthropogenic sulfur dioxide totalled 170 Mtonnes whereas natural sources
totalled only 40 Mtonnes. This difference between northern and southern
hemispheres reflects the higher proportions of land mass and so-called
developed countries which use large quantities of fossil fuels.
The sulfur dioxide in the atmosphere is oxidized by a wide variety of
mechanisms that include gas-gas interactions called homogeneous oxidation
(as there are no phase differences; Eqn 6.11) and reactions occurring in
solution, with or without the presence of catalysing agents (called
heterogeneous oxidation if there are phase differences between reactants; Eqn
6.12a and b). Manganese appears to be the most effective catalyst.
HO* + so2 — ►HSO* hso; HSO* + n o 2 ^ 2 h 2 s o 4 + h n o 3

(6. 11)
S 0 2(aq) H- O 3 (aq) --- ►SO3 (aq) + 0 2 (g) --- ►H 2 S 0 4 (6.12a)
alternatively
S 0 2(aq) + H 20 2(aq)^ S 0 3(aq) + H 20 —+ H 2S 0 4 (6 . 12 b)
Reaction sequence 6.11 involves a number of free radicals (HO*, HSO*,

HSO*, HSO*) all of which are reactive species containing a single unpaired
electron, indicated by the dot in the symbol. Free radicals can be formed in
the atmosphere by a large number of reactions, usually involving photolysis,
in which a covalent bond is split by the absorption of solar radiation. The
UV part of the solar spectrum is the portion normally involved (Eqn 6.13).
03 0 2 + O* ^ 2HO* (6.13)
ozone wavelength excited hydroxyl
310 nm oxygen free
atom radical
Depending upon the amount of moisture in the atmosphere, 20-80% of

the sulfur dioxide emitted into the air is oxidized to sulfate whilst the
remainder is removed by dry deposition (Figure 6.5). Sulfate has a relatively
small depositional velocity and most of it is removed by wet deposition
(Figure 6.5). The sulfur dioxide and sulfate mixture has an average lifetime
of 2-6 days in the atmosphere during which time it may travel up to 4000
km from its source. Dry deposition, despite its name, involves sorption of the
sulfur compounds mainly on moist surfaces such as vegetation, wet
114 MAJ O R E L E M E N T S F O U N D IN LI V IN G M A T T E R
Figure 6.5 Mechanisms by which sulfur dioxide and its oxidation products are removed.
buildings, soil and water bodies. Wet deposition involves removal by rain or
snow and is also called ‘precipitation scavenging’. Material entering clouds
is rained out, whereas material below clouds is washed out. Most sulfur
oxides entering a rain belt will be removed within 2 0 0 km.
The actual mechanism of dispersion of sulfur dioxide from point sources
such as power stations or smelters is very complicated, being dependent
upon climatic conditions, topography, chimney height and design. In
general the higher the chimney the more widely will the sulfur dioxide be
dispersed, but lack of atmospheric turbulence can lead to a concentrated
plume travelling hundreds of kilometres before dispersing. Very low
chimneys, as on houses, are especially ineffective in dispersing sulfur
compounds. In the UK, the average concentration of sulfur dioxide in the
atmosphere is about 33 /xg m-3, of which about 90% is from anthropogenic
sources. However, this average value hides wide variations between different
areas of the country and between different periods. The range of daily
average readings is typically 50 times greater than the annual range. Five-
minute averages and 1-h averages may be ten times and five times greater
than the daily average, respectively. The short-term variations are mainly
due to changes in the meteorological conditions. The spatial distribution of
SULFUR 115
sulfur dioxide concentrations closely follows the spatial distribution of low

and medium-height chimneys. The highest sulfur dioxide concentrations are
in the larger towns and the much lower levels in rural areas may be only
10%-20% of the central urban values. The average urban values for the UK
were 188 jig S 0 2 m ~ 3 in 1958, 144 ^g S 0 2 m -3 in 1970 and 73 jig S0 2 m 3 in
1977. This reduction illustrates very clearly the success of the enforcement of
the Clean Air Acts (1956 and 1968) and the conversion of houses to the
convenient heat sources of natural gas and electricity. In the same period,
the emission of S 0 2 from tall chimneys, largely associated with electricity
power stations, has increased from 1.4 to 3 Mtonnes, but the emissions from
low chimneys have decreased from 1.7 to 0.6 Mtonnes.
The extent of acidic rainfall appears to be growing because the use of
taller chimneys causes wider dispersion of the sulfur and nitrogen oxides.
Localized very high levels have been reduced, but delocalized higher levels
have been increased. Rain normally has a pH of 5.6, when in equilibrium
with the carbon dioxide in the atmosphere. If the pH drops below 5.6, the
rain is described as being acidic. The sensitivity of an ecosystem to acid rain
depends upon the quantity of acid deposited, upon the ability of the rock,
soil and water systems to neutralize the acid and upon the resistance of the
living organisms to any consequent changes.
Rocks may be classified into four types based on their ability to neutralize
acids (Table 6.1). The essential features to note are that the rocks that are
most resistant to normal chemical weathering also have the lowest ability to
neutralize acids and that the greater the proportion of calcium and
magnesium carbonates in the rocks, the greater the neutralizing effect. Soil
composition is partially a function of the underlying rocks, but the degree of
weathering and the amount of organic matter can greatly modify the soil’s
properties.
Cation-exchange capacity has been used to define the sensitivity of soils to
acid precipitation (Table 6.2). Clay minerals and organic matter contain
sites at which hydrogen ions can be attached to the solid and at which metal
ions can be released into the solution (Eqn 6.14). This cation exchange
lowers the concentration of hydrogen ions in the soil water.
(Clay/organic matter) —M* + H+ —> (clay/organic matter) — H+ + M+
free bound
hydrogen hydrogen
ion ion
(6.14)
The cation-exchange capacity of the soil is limited and the presence of free
carbonate minerals is of overwhelming importance. Other exchange
reactions are also possible (Chapter 12).
The major factor controlling the ability of natural water systems to
absorb acid inputs without major changes in pH is the alkalinity (Chapter
4). The lower the alkalinity, the greater the sensitivity to acid rainfall. It is
116 MAJOR EL EM EN T S F O U N D IN LIVING MAT TER
Table 6.1 Classification of rock formations according to their ability to neutralize acid
(reprinted with permission from Glass, N.R. et al. 1982. Effects of acid precipitation. Environ.
Sci. Technol. 16, 162A-8A. Copyright© 1982 American Chemical Society)
Type number Description and examples
I Low or no buffering capacity, overlying waters very sensitive to acidification

e.g. granite, syenite, granite gneisses, quartz sandstones or equivalents
II Medium to low buffering capacity, acidification restricted to first- and
second-order streams and small lakes, e.g. sandstones, shales,
conglomerates, high-grade metamorphic rocks, intermediate igneous rocks,
calcsilicate gneisses
III High to medium buffering capacity, no acidification except in cases of
overland runoff in areas of frozen ground e.g. slightly calcareous, low-grade
metamorphic rocks, intermediate to basic, ultrabasic and glassy volcanic
rocks
IV ‘Infinite’ buffering capacity, no acid precipitation of any kind, e.g. highly
fossiliferous sediments or metamorphic equivalents, limestones, dolomites
clear that the most sensitive members of the three systems (rock, soil and
water) will usually occur in the same area (a) because slow-weathering rocks
form thin soils containing few clay minerals and the nutrient content is
generally low; (b) because the poor soils support less vegetation, which
means in turn that the soils have low organic matter contents; and (c)
because as the runoff water has picked up little calcium and magnesium
carbonate from the soils, the streams, rivers and lakes all have low
alkalinities.
The effects of acid rain may be directly related to the acidity of the
rainfall, as seen in the dissolution of limestone statues, buildings and rock
outcrops. In other cases, the effects may be indirect, as when the acid causes
the release of aluminium in soils which then reaches levels at which it is toxic
to trees. There are also possible beneficial effects to be taken in to account,
Table 6.2 Soil sensitivity to acid precipitation, based on the chemical characteristics of the top
25 cm of soil (reprinted with permission from Glass, N.R. et al. 1982. Effects of acid
precipitation. Environ. Sci. Technol. 16, 162A-8A. Copyright © 1982 American Chemical
Society)
Cation-exchange
capacity Other relevant
Sensitivity (meq* per lOOg) conditions
Non-sensitive (a) Any value Free carbonates present, or

subject to frequent flooding
(b) >15.4 None
Slightly sensitive Values from 6.2 to 15.4 Free carbonate absent; not
Sensitive <6.2 Free carbonate absent; not
*Milli-equivalent - see page 175.

SULFUR 117
such as the increase in levels of available sulfur and nitrogen which may
reduce or remove deficiencies in these nutrients. Distinguishing the indirect
effects in complex ecosystems is extremely difficult, particularly as the effects
may only become apparent after several years. For instance, there was no
change in the composition of water collected 20 cm below the surface of a
soil in a forest until 2 years after the start of the addition of simulated acid
rain, pH 4. The concentration of hydrogen, sulfate, calcium and magnesium
ions then all rose together.
The concept of the critical load has been widely used to identify areas at
risk or already suffering damage. The critical load can be defined as that
quantity of a substance that can be applied to an environment without
producing significant harmful effects on specified indicator organisms. In
theory, for example, it is possible to calculate the amount of sulfur- or
nitrogen-based acid deposition falling on a given area and determine
whether the ecosystem will be harmed. In practice this requires the
identification of sensitive species and determining what changes will be
deemed to be significant, i.e. reduced growth of roots rather than mortality.
Clearly the critical load should be greater for a calcareous soil than for a
peaty soil, but quantifying the load is not easy. A large number of critical
load maps have been produced for various areas of Europe and these have
proven useful in driving through internationally agreed targets for emission
reductions. Despite the reductions, it has been estimated that critical loads
are still exceeded in half of Europe, with fish deaths continuing to occur in
southern Scandinavia.
The effects of acid rain and of sulfur dioxide emissions are very varied and
a number of them are briefly discussed below.
Human health. Levels of S 0 2 above 500 fig m ~ 3 (24 h average) affect asthma
and bronchitis sufferers if levels of smoke are about 250 fig m~3. Increases in
sudden deaths and hospital admissions are noted at about 750 jig m ~ 3 for
both S 0 2 and smoke. The infamous London fog of 5-8 December 1952 led
to 4000 deaths with S 0 2 and smoke levels of about 4000 /ig m -3. The
relative importance of sulfur dioxide appears to be much less than that of
smoke, but each enhances the effect of the other. The identification of the
causes of particular effects on health is usually a very long, time-consuming
and expensive enterprise because of the lack of suitable data bases. In the
case of S 0 2 and smoke measurements, should one compare average values
for 5 min, 1 h, 24 h, 1 week, 1 month or 1 year periods? Where should the
sampling stations be situated relative to the population being studied? It
seems that for many health effects it is the incidence of occasional high levels
of smoke and S 0 2 that is important rather than the long-term average.
In 1961, before the 1956 Clean Air Act had become effective, smoke and
sulfur dioxide levels were about 300 fig m -3 in the city of Sheffield. These
values are about four times higher than the current (1997) EC recommended
limits. By 1983 there had been a 90% reduction in the smoke and sulfur
dioxide concentrations. Deaths in the city from bronchitis had fallen by
about 70%, matching similar reductions in the rest of the UK. Whilst
improved medical treatment and changes in smoking habits have played a
part in this reduction in respiratory illness, air-quality improvement has also
been a major causal factor. The reduction in smoke and sulfur dioxide
concentrations was brought about by both fuel substitution (gas and
electricity for coal) and changes in technology (larger electricity generation
units and taller flue stacks).
The increased acidity of water, leading to increased levels of dissolved
metals, is causing concern in those communities which depend on well
water. In large-scale public-supply systems, slaked lime (Ca(OH)2) is added
to the water to raise the pH above 7. This prevents the solution effects on
lead and copper pipes that may be found in soft-water areas even without
the input of acid rain. Any previously dissolved metals will be precipitated
from solution by this treatment. It is more difficult to control the pH in
isolated, intermittent water supplies from wells.
Vegetation. Sulfur is an essential nutrient and up to 70 kg ha -1 may be

needed for optimum growth with intensive agriculture. Forest trees require
much smaller quantities of sulfur, being mainly composed of cellulose, and
there are few areas where sulfur has been reported as a limiting factor for
tree growth. In the UK, soils receive 15-100 kg ha -1 a ' 1 from rain and this
is usually sufficient for most crops. In others parts of the world (e.g.
Australia, New Zealand, and East and Central Africa) sulfur deficiencies
occur and these have become more apparent as sulfur-containing fertilizers
- such as ammonium sulfate ((NH 4)2S 0 4) and superphosphate (Ca(H 2P 0 4)2
+ C aS04) - have been replaced by more concentrated, sulfur-free sources of
nitrogen and phosphorus.
Direct damage by acid rain or atmospheric sulfur dioxide is largely
associated with foliar injury affecting transpiration, photosynthesis, leaf
protective coatings and the leaching of ions from leaves. In the case of
agricultural crops there is no clear pattern of decreased yields at the levels of
S 0 2 found in rural areas.
Forests are much more sensitive to damage, mainly because they grow on
poorer soils and are in a precarious equilibrium with their environment. As
well as direct damage to leaves, the increased rates of removal of essential
metals such as magnesium and potassium from the soils, and the
mobilization of potentially toxic metals such as aluminium, lead, zinc and
copper, all produce stress, possibly leading to death (Chapter 10).
Fish. Eggs and fry are especially sensitive and population depletion is most
often caused by failure of these juvenile stages to develop rather than by
actual fish kills. Incidences of fish kills are usually associated with dramatic
SULFUR 119
sudden increases in acid input, in many cases due to the melting of snow.
During the winter the acidic components are trapped in the snow. When the
temperature rises in the spring, the contaminated snow melts first and
releases the acids in a short concentrated burst that can lower the pH by 1-
1.5 units to a value of about 4.5. This melting effect is an example of the
depression of freezing point of a solvent due to the presence of dissolved
species. With the reduction in pH, fish suffer from excessive loss of sodium
from the gills. The levels of sodium in the blood may be reduced by a half in
2 days, thus upsetting the equilibria in the fish’s body fluids. The presence of
calcium in the water inhibits this loss of sodium. Different fish species show
different sensitivities, with minnows being especially sensitive and eels and
pike most resistant to increased acidity. Tolerant species and individuals
have been identified, but whether they would grow fast enough to be
suitable for restocking commercial fisheries is not known.
As in soils, the presence of acid water produces increased levels of
potentially toxic metals in rivers and lakes. Metals at these elevated levels
may be taken up by fish and in some cases may play a part in reducing the
fish population.
Other aquatic flora and fauna. Molluscs and crustacea rarely survive below
pH 6 , being more sensitive than fish. In general, species diversity is very
much reduced with increased acidity, although some species survive even
though fish are absent. Organic decay is much slower in acid lakes and
benthic Sphagnum species (moss) may cover lake bottoms when calcium is
low and light transmission is high.
Buildings and metals. Building stone containing calcium or magnesium

carbonates is readily attacked by acid rain with the formation of a soluble
sulfate (Eqn 6.15).
CaC03(s) + H2S 04(aq) --- > Ca(aq) + S^ 4 (aq) + H20(j) + C 0 2(g) (6.15)
The building stone may be a limestone or marble (both C aC 03) or it may be

a sandstone in which the quartz grains are held together by a coating of
calcium carbonate or iron oxide. The iron oxides will also dissolve in acid
water (Eqn 6.16).
Fe20 3(s) + 3H 2S 04(aq) > 2Fe(aq) + 3S04(aq) + 3H 20^) (6.16)
Sulfur dioxide reacts more slowly under dry conditions but overall the
effects are the same.
120 M A J O R E L E M E N T S F O U N D IN L I VI N G M A T T E R
The presence of atmospheric sulfur dioxide, nitrogen oxides and acid rain
have all increased the rates of corrosion of metallic structures, such as
bridges, and motor vehicles. It is difficult to quantify these effects as there
are also other factors such as sea spray and road de-icers which are probably
more important causes of accelerated corrosion.
Remedial measures for the sulfur dioxide problem

The major source of the sulfur dioxide responsible for the increase in acid
rainfall is the combustion of fossil fuels. The sulfur content of various fuels
are: coal (0.1 %—6 %), fuel oil (0.75%-3%), petroleum (0.04%) and diesel oil
(0 .2 2 %), with natural gas being essentially sulfur free as delivered to the
consumer. About 61% of the S 0 2 comes from the burning of coal, 25%
from oil products, 10% from the smelting of copper sulfide ores and 1.5%
from lead and zinc sulfide smelting. The control of sulfur emissions can be
achieved by a number of means.
Flue-gas desulfurization. The sulfur compounds are removed from the

emitted process gases. This should be easier for the smelting industries where
the concentration of sulfur oxides in the gases can be relatively high (5% -
15%) and direct conversion to sulfuric acid is possible. If the sulfuric acid is
not saleable, conversion to elemental sulfur reduces storage problems and
allows easier transport to other markets. In fossil-fuel combustion, the
concentration of sulfur compounds is usually less than 0.3%. These dilute
gases can be scrubbed with alkaline solutions or suspensions of various
compounds (Eqns 6.17-6.21).
CaC 0 3+ S02 ^ C aS 0 3 + C 0 2 (6.17)

impure
CaO + S 0 2 ^ C aS0 3 sludge (6.18)
dumped
2CaS0 3 + 0 2 + 4H20 — > 2CaS0 4 • 2H20 , (6.19)
MgO + S 0 2 —* M gS0 3 ^ MgO + S02 —♦ H 2S 0 4 (6.20)

reused concentrated
N a 2S 0 3 + H20 + SOz — ♦ 2N aH S0 3 ^ Na 2 S 0 3 + H 20 + S02

reused concentrated
— > H 2SO 4
(6.21)
The products may then be dumped, sold or the absorbent regenerated and
the sulfur compounds dumped or sold. The market for saleable sulfur
compounds, such as sulfuric acid, gypsum (CaS0 4 -2H20 for plaster board)
SULFUR 121
and ammonium sulfate, is limited. They are all low-cost items and cannot
support the high transport costs incurred in delivering them over large
distances. In the UK, about 750000 tonnes of sulfur are imported annually
compared to an output from electricity power stations of about 1.3 x 106
tonnes S a-1. More sulfur could be produced than is used, thus reducing the
price of the sold sulfur compounds. Desulfurization methods that yield
throw-away products are much cheaper to operate but produce large
quantities of waste that has to be disposed of. A typical British 2000 MW
power station would yield about 1 Mtonnes of wet sludge or 210000 tonnes
98% H 2S 0 4 a -1 or 67 000 tonnes S a -1 if the desulfurization efficiency was
about 90%. The dewatering of the dumped sludge can lead to water-
pollution problems and large areas of land are required for storage, e.g.
about 1 km x 100 m if the sludge was 10 m deep, for the 10 year output of a
2000 MW power station.
The Drax power station is the largest coal-fired power station in Europe
with a gross capacity of 3960 MW. It has been refitted with a flue-gas
desulfurization system that will produce about 1 Mtonnes per year of
gypsum. The limestone-gypsum process that is being installed is based on
reactions 6.17-6.19. The gypsum is separated from the sludge for sale or for
dumping, depending on demand. The sulfur dioxide emissions from the flue
stacks should be reduced by about 90% from 350-400 to 35-40 ktonnes a-1,
provided that there are no breakdowns in the flue-gas desulfurization
system. About 11 Mtonnes of coal are burned each year at Drax and this
yields 2 Mtonnes of ash for disposal. The flue-gas desulfurization system will
produce an extra 70 000 tonnes of waste sludge (65% solids) and 1 Mtonnes
of treatment water each year that will also have to be disposed of. The
process will require about 0.7 Mtonnes a -1 of limestone to be mined and
then transported 70-100 km to Drax. It is clear from these figures that the
local environmental impact of this development will be considerable.
Fuel desulfurization. About half the sulfur in coal is present as pyrites, FeS2,
and approximately 80% of this could be removed by grinding up the coal
and using a variety of separation techniques. The removal of the organically
bound sulfur is much more difficult and requires the conversion of the coal
into new liquid or gaseous fuels. Oil can be desulfurized at the oil refinery by
the extension of techniques that are used at present for the partial removal
of sulfur. In each case the cost of the desulfurization process is high.
Fuel substitution. This includes the use of lower-sulfide fuels such as natural
gas (favoured solution in the UK), or the substitution of a 1% S coal for a
3% S coal, the replacing of fossil fuel-fired power stations by nuclear-power
stations (favoured solution in France and a number of other countries) and
122 MAJOR E L EM EN T S F O U N D IN LI VIN G M AT TER
the introduction of so-called ‘alternative energy’ sources, e.g. solar energy,

wind, waves, hydropower, geothermal energy (although the last is often
associated with sulfurous emissions such as H 2S).
Treatment o f affected areas. The liming of land and the addition of

limestone to rivers and lakes has been tried. Because of the low economic
value of the crops, the large areas to be covered and the need for constant
renewal of the applications, these methods do not appear to be feasible
except for localized areas of possibly high-yielding agricultural land.
As all remedial methods involve increased costs to producers of sulfur

dioxide, there is great reluctance by them to reduce the emissions effectively.
7 Phosphorus
Phosphorus Abundance by weight (the relative abundance is given in

parentheses): Earth, 0.2% (10); crust, 1050 ppm (11); ocean, 88
ppb (19). ppm = mg kg-1; ppb = /ng k g "1.
The solubility and volatility of naturally occurring phosphorus compounds

is low, so the geochemical fluxes of the element are mainly dependent upon
suspended-solid transfer by rivers to the ocean and upon dust transfer in the
atmosphere. Estimates of the various fluxes of phosphorus (Figure 7.1)
reflect this low mobility. Many of the values are not very well known
because of the heterogeneous nature of particulate matter and the difficulty
of adequately sampling the flows. In almost all cases the phosphorus is
present as the orthophosphate group, P 0 4“ , bound to a cation in insoluble
inorganic compounds or as a component of organic molecules. Typical
inorganic compounds are the apatites (Cai0(PO4)6(F, OH)2), calcium
phosphate (Ca 3(P 04)2), aluminium phosphate (A1P04) and iron(III)
phosphate (FeP04). Phosphorus is an essential constituent of the energy
transferring molecules ATP, ADP and AMP, and of the genetic and
information-carrying molecules DNA and RNA. This means that
phosphorus is an essential element for all living organisms and it is often a
limiting factor in the fertility of soils and aquatic ecosystems. The low
solubility of the inorganic compounds limits its availability as a nutrient.
The actual composition of the phosphate minerals is more complex than
the formulae given, with a high degree of isomorphous substitution between
* 2 j ^ j I o I
the major cations Ca , Al , Fe and Fe , and the inclusion of relatively
large quantities of trace elements (Table 7.1).
The majority of phosphorus added as a fertilizer is rapidly immobilized by
inorganic compound formation, and it has been suggested that soluble
phosphorus rarely migrates more than 2 or 3 cm from a fertilizer granule.
The concentration of phosphorus in lake and river waters is low (60 ppb)
and most of the phosphorus transported to the oceans is in particulates and
suspended sediments. Of the 20 x 109 k g P a _1, about 9 x 109 kg P a ^ 1 are
believed to be due to increased erosion caused by deforestation and
extensive agricultural activities. Unlike nitrogen, increased concentrations
of dissolved phosphorus in water bodies is not always due to excess fertilizer
in land runoff. However, there is increasing evidence that the diffuse input
124 MAJOR E L E M EN T S F O U N D IN LI VING MAT TER
DUST PARTICLES IN ATMOSPHERE
x 109 kg Pa 1
x 109 kg P -> fluxes
( ) concentrations
Figure 7.1 The phosphorus cycle.
from soils saturated in phosphate fertilizers is becoming a more important

source of potentially available phosphorus. The major causes of increased
dissolved-phosphorus loadings are sewage disposal and the soluble
polyphosphates used in detergents. The concentration of soluble phosphate
in sewage effluent has been decreased from 40% to 15% in the UK because
of changes in detergent formulation and improved sewage treatment.
Although the phosphate group (PO4 ) and its related anionic forms
(HPO 4- and H 2PO 4 ) generally have low solubilities, polyphosphates such
as the triphosphate ion (P3Ojq ) have greater solubilities over a wide range of
conditions. The polyphosphates are mainly added to organic detergents to
bind the Ca2+ and Mg2+ ions as soluble polyphosphate complexes. This
action prevents the formation of insoluble carbonates, with a rise in
temperature or pH of the water. The latter is important because organic
detergents work more efficiently under alkaline conditions. The poly
phosphates also act as buffers, helping to stabilize the pH by reacting with
acidic components encountered during the washing process. A number of
different substitutes for polyphosphates have been suggested, but all have
proved to have drawbacks. The substitutes may be less suitable in
detergents, e.g. sodium carbonate is too alkaline, or more undesirable
environmentally, e.g. sodium nitrilotriacetate (NTA), N(CH 3COONa)3.
PHOSPHORUS 125
Table 7.1 Trace-element concentrations in phosphate rock compared with their concen
trations in normal soil (both in mg kg-1)
As Cd Cr Hg Pb U
Phosphate rock 190 100 1600 1000 100 1300

Soil 20 0.4 50 0.25 25 1
NTA forms soluble complexes with cadmium and mercury, and produces
nitrate on aerobic breakdown; bacterial action on NTA and its breakdown
products can form carcinogenic nitrosamine compounds.
Only 20%-30% of the soluble phosphates are removed in secondary
sewage treatment (Chapter 15), but 90% can be removed during tertiary
treatment when the addition of lime together with iron and aluminium
compounds causes precipitation of the respective metal phosphates.
Residual soluble phosphates in bodies of water encourage growth of
photosynthetic algae, especially in lakes. The phosphorus concentration in
the water decreases as phosphorus is accumulated by the biota and
subsequently enters the sediment as the biota die and sink to the bottom of
the water body. Either the phosphates are remobilized into the water
column as the organic compounds decay, or they are immobilized by
"5 I ry I o i i
inorganic compound formation with Al , Ca , Fe and Fe .
The photosynthetic algal population in water bodies is limited by the need
for adequate nutrients and light. In lakes, nitrate and phosphate levels are
often low and one or other of these may limit the growth of the algae and of
the food chain that depends upon these primary producers. If we consider
nitrogen and phosphorus only, one phosphorus atom is needed by algae for
every 1 2 -2 0 nitrogen atoms to form the various nitrogen- and phosphorus-
containing molecules in their cells. If the N:P ratio in water was 30:1, say, all
the phosphorus would be consumed before all the nitrogen (Figure 7.2a),
whereas if the N:P ratio was only 6:1, the more rapid removal of the
nitrogen would limit biotic growth (Figure 7.2b). However, many studies
have shown that if there is adequate phosphorus, nitrogen fixing blue-green
algae develop to increase the N:P ratio effectively and allow further growth.
The addition of soluble phosphate allows a large mass of algae to develop,
cutting down the light transmission in the water. When the algae die, the
dissolved oxygen is removed as the organisms decay. Because the rate of
multiplication of the algae is very rapid the term algal bloom is applied and
there is a rapid change in appearance of the water to a cloudy, greenish
soup.
Lakes are especially susceptible to algal blooms as the build-up of
nutrients occurs more readily than in the flowing-water conditions of
streams and rivers.
Key
■---- nitrogen ------------ phosphorus - biomass
(b)
c 6
£ o
i 5
c 4
<
D
g
O 3
o2
CL
z 1
Time
Figure 7.2 The relationship between the development of biomass and the relative
concentrations of nitrogen and phosphorus.
Eutrophication is the term given to the enrichment of a body of water with

nutrients. There has been an increase in recent years in the rate of
eutrophication of lakes and rivers due to the release of (a) nitrates from
excess fertilizers and sewage effluent; and (b) phosphates from sewage
effluent. Algal blooms in estuaries and coastal waters have also become
increasingly common for the same reasons. In sea water, nitrate rather than
phosphate is usually the limiting nutrient, the reverse of the freshwater
situation.
(a) Biolimiting elements (b) Bio-unlimiting elements
in zone A there is active removal no net removal by

by living organisms organisms in zone A
Figure 7.3 The change in concentration with depth in the ocean for (a) biolimiting elements,
and (b) bio-unlimiting elements.
PHOSPHORUS 127
Nitrogen and phosphorus are described as being biolimiting elements,

which means that the concentration of these elements limits biological
growth. The variation in concentration of the biolimiting elements with
depth in the ocean is characteristic (Figure 7.3a). At the surface, where
photosynthesis is at a maximum, the concentration of the biolimiting ele
ments (nitrogen, phosphorus and silicon) is very low. With increasing depth,
photosynthesis and elemental uptake decreases and the concentration of the
elements in the sea water increases. The bio-unlimiting elements, such as
sodium, potassium, magnesium, sulfur and chlorine, show no measurable
depletion in surface waters (Figure 7.3b).
Part Three Major elements in the Earth’s crust
The crust is the outermost solid layer of the Earth and contains about 0.4%
of the mass. It is much richer in silicon and oxygen (Table P l.l) than the
Earth as a whole. The crust is very heterogeneous, being made up of a large
number of very different rock types. A rock type is defined by the minerals it
contains and the supposed conditions under which it formed. A mineral is a
naturally formed inorganic compound whose composition may be quite
complex. Many minerals have a fixed crystal lattice, but the atoms, ions or
molecular species occupying the lattice positions may differ by greater or
lesser amounts from one crystal to the next.
The conditions of formation of rocks can be inferred from the following
features:
(a) the minerals present. Each mineral is formed under a characteristic
range of temperature and pressure;
(b) the texture of the rock. This is determined by the sizes, shapes and inter
relationships of the minerals in the rock; and
(c) the large-scale morphological features. For example, one rock may in
trude into another, indicating that it was once molten; or a rock may show
ripple marks, indicating that it was deposited as a sediment under water.
The many different rock types are grouped together under three headings
depending on how they were formed:
(a) igneous rocks have been formed by the cooling down of a molten mass;
(b) sedimentary rocks have been formed by the accumulation and
compaction of minerals and rock fragments at temperatures close to
those normal for the Earth’s surface; and
(c) metamorphic rocks have been formed by the action of increased pressure
or temperature or both on igneous or sedimentary rocks.
It has been estimated that the crust contains about 65% igneous rocks,
8% sedimentary rocks and 27% metamorphic rocks. Most of the sedi
mentary and metamorphic rocks are found in the continental crust and, in
fact, about 80% of the surface is composed of sedimentary rocks.
Igneous rocks are thought to form from molten materials, called magma,
derived from either the upper mantle at mid-ocean ridges and rifts, where
crustal plates are moving apart, or by the remelting of mainly crystalline
130 M A J O R E L E M E N T S F O U N D I N TH E E A R T H ’S C R U S T
rocks in subduction zones where plates are converging (Figure P3.1). As the
molten material cools, those minerals that are stable at high temperatures
will crystallize out. This changes the composition of the remaining magma.
Further cooling produces new minerals until all the magma has solidified
(Figure P3.2). Which specific minerals form is determined by the com
position of the magma at the site of crystallization. Silicon and oxygen being
the two most common elements, the major minerals are silicates containing
[Si04] units linked together by the most common cations - aluminium,
calcium, iron, magnesium, potassium and sodium. The higher-temperature
minerals are enriched in iron, magnesium and calcium, whereas the lower-
temperature minerals contain more sodium and potassium.
Silicates can be thought of as salts of an acidic oxide, Si0 2 (which forms
silicic acid, H 4Si04), and of basic oxides (e.g. Na 20 , K 20 , CaO and MgO;
Eqn P3.1).
2MgO + Si0 2 —♦ Mg 2 Si0 4 (P3.1)
The apparent proportion of Si0 2 in the rock is used to subdivide the igneous
rocks into acidic (Si0 2 > 6 6 %), intermediate (53%-66% Si02), basic (45% -
52% Si02) and ultrabasic (<45% Si02) rocks. These subdivisions have
nothing to do with the liberation of hydrogen ions and do not imply a
specific pH for a particular rock type. In general, only acidic rocks actually
contain free Si0 2 as quartz. In all other cases the Si0 2 is bound up in the
silicates.
(a) Two tectonic plates moving apart (b) Two tectonic plates converging
- leading to upflow of molten - one passes under the other,
rock from mantle forming a subduction zone where
crustal rocks are remelted
plate D
<-------
♦ ♦ ♦ ♦ magma formed by remelting o f crustal rocks
Figure P3.1 The introduction of magma into crustal regions as a result o f plate movements.
M A J O R E L E M E N T S IN THE E A R T H ’S C R U S T 131
Melt (magma)
decreasing tem perature o f crystallization
------------------------------------------------------------------------------►
p ro p o rtio n o f S i0 2 an d H20 in m elt increases
[S1 O 4 ]
A)
K
Na
Ca
Mg
Fe
pyroxene biotite mica quartz

olivine amphibole muscovite mica trace-
element
minerals
Silicate [S i0 4] single single double sheets three-dimensional

structures units chains chains
Three- plagioclase feldspar

dimensional * ►
calcium-rich sodium-rich
orthoclase feldspar
potassium-rich
basic rocks acidic rocks

e.g. gabbro basalt e.g. granite
<-----------------------------------------------------------------------------------------------------------
increasing ease o f weathering
Figure P3.2 The crystallization sequence as magma cools to form a series of igneous rocks.
The two most commonly occurring igneous rock types are those that are
basaltic in composition and associated with the oceanic crust, and those that
are granitic in composition and typical of the continental crust.
The minor elements, present as less than 1% of total mass, follow two
different pathways during the solidification of a magma. As the major
elements are removed by crystallization, the relative concentration of the
minor elements increases in the remaining magma. If the concentration of
the minor elements becomes great enough, they will form the minerals of
which they are major components. This will be particularly important for
elements forming minerals with low solubilities. The last remnants of the
132 M A J O R E L E M E N T S F O U N D IN THE E A R T H ’S C R U S T
magma are especially rich sources of minerals of the less common elements,
and their crystallization often provides deposits of minerals concentrated
enough to be worth mining.
The second pathway followed by minor elements is to become
incorporated in the crystal structures of the major minerals. This process is
called isomorphous substitution and involves one element occupying a
position in the crystal lattice normally occupied by another element. The
olivine group of minerals shows isomorphous substitution between the
major cations Fe2+ and Mg2+ to give a series of compounds ranging from
fayalite (FeSi04) to forsterite (MgSi04). The formula is often written
‘(FeMg)Si04’ to indicate the possible substitution. In addition, replacement
of Mg2+ (ionic radius 72 pm) and Fe2+ (ionic radius 75 pm) by ions such as
Ni2+ (68 pm), Cu2+ (73 pm) and Cr3+ (73 pm) may occur so that olivines
can contain parts per million (mg kg-1) or parts per thousand (g kg-1) of
these elements.
The crystal lattice will remain stable if ions of similar size substitute for
each other. The greater the similarity in size, the greater the possibility of
substitution. The crystal contains atoms held together either by the transfer
of electrons to form ions or by the sharing of electrons to form covalent
bonds and molecular species. The substitution of one element for another
will occur most readily if this causes minimum disruption to the electron
distribution. Fe2+ and Mg2+ have similar sizes and the same charge, so they
often interchange; but Fe3+ (ionic radius 55 pm), because of its different
charge and radius, does not normally substitute for Mg2 + . When there is a
difference in oxidation state between substituting atoms, e.g. Ca2+ (100 pm)
and N a + (102 pm) in plagioclase feldspars, the electrical neutrality of the
crystal is maintained (a) by substitution of a second element of different and
compensating oxidation state somewhere else in the mineral, e.g. NaAlSi30 8
becomes CaAl2Si20 8, where Al3+ (39 pm) replaces Si4+ (26 pm); (b) by
addition of extra ions into a suitably sized hole in the structure; and (c) by
removal of a balancing species to leave a hole in the structure. Although the
general principles guiding substitution in minerals are known, the detailed
factors at work in a complex magma or solution are still being disentangled
and vary from system to system. The results of these substitution pos
sibilities are that most minerals contain trace amounts (less than 0 .0 1 %) of
elements that are not normally given in the formula for the mineral. These
small amounts can be important sources of elements whose properties may
lead to either enhanced or depressed growth of organisms.
Igneous rocks are unstable under the low pressure and temperature
conditions of the upper surface of the crust and they break down in the
process called weathering (Chapter 8 ). The fragments are often deposited
under the sea in flat beds that on burial become compressed and cemented
together to form detrital sedimentary rocks. These rocks are classified on the
basis of particle size and this also correlates to some extent with mineral
M A J O R E L E M E N T S IN THE E A R T H ’S C R U S T 133
composition. There are also chemical sediments that are formed by

precipitation from solution, usually in the ocean. The limestones (C aC 03)
and dolomites (CaM g(C03)2) are the most abundant examples, with
evaporites (largely NaCl, CaS0 4 and CaS0 4 -2H20 ) formed by the
evaporation of sea water being the next most common examples.
Contact metamorphic rocks are formed by the alteration of rocks near to
igneous intrusions by the action of heat and some pressure. Regional
metamorphic rocks are produced by heat and pressure, usually due to deep
burial or deformation during mountain uplift periods when great stress is
applied to the rocks causing new minerals to be formed. If the effects
become extreme, the rocks become molten and the difference between
metamorphic and igneous rocks is lost.
Although the majority of the crust is composed of silicate minerals, it is
often relatively rare minerals that have been concentrated by one of the
rock-forming processes that are exploited as sources of raw materials.
Examples include sulfide minerals of lead and zinc from the latter stages of
magmatic crystallization; bauxite deposits of aluminium from weathering of
igneous rocks and lithium phosphate in evaporite deposits. The un
controlled exploitation of these limited resources will lead to world
shortages unless we stop redispersing over the face of the Earth these
elements that natural processes have taken so long to concentrate. The
second law of thermodynamics indicates that disorder will arise from order
but there seems to be little to gain from hastening the change!
8 Silicon
Silicon Abundance by weight (the relative abundance is given in

parentheses): Earth, 14.3% (3); crust, 29.5% (2); ocean, 2.9
ppm (14). ppm = mg kg-1.
8.1 Silicate minerals
The majority of the Earth’s crust is composed of silicate minerals, and these
minerals have been classified on the basis of how the [Si04] units are
arranged (Figure P3.2). The individual [Si04] unit (Figure 8.1) can be
considered to consist of four closely packed oxide ions, O2- with a silicon
ion, Si4 + , occupying the tetrahedral hole between them. In practice the
Si-O bonds have a large degree of covalent character. The Si4 +- 0 2~ bond
has been estimated to be 52% covalent. The Si-O bond (bond energy:
372 kJ m o P 1) is over twice as strong as the Si-Si bond (bond energy:
180 kJ mol-1); therefore, the Si-O arrangement is the preferred structure
wherever, as in the Earth’s crust, there is sufficient oxygen present to allow
its formation. Each oxygen can form bonds with two atoms of silicon, and
so adjacent [Si04] units can be joined together by the sharing of oxygen
atoms to give chains, sheets or three-dimensional networks.
The various minerals are characterized by the structural arrangement of
[Si04] units and the major cations present, but in most silicate minerals there
tends to be widespread substitution of one element by another of similar
size. If all four oxygens of one [Si04] unit are shared with other [Si04] units,
the overall formula becomes Si0 2 and the product, quartz, is a giant
molecule. When aluminium, Al3 + , replaces some of the silicon, Si4+, the
structure requires further cations - such as calcium, Ca 2 + , potassium, K + ,
or sodium, N a + - to regain electrical neutrality. Such minerals are called
aluminosilicates. Examples are the plagioclase feldspar group, (Ca, Na) (Al,
Si) AlSi2Os, and potash or orthoclase feldspar, KAlSi3Og.
The structural features of the silicate minerals (Figure P3.2) are often
reflected in their bulk properties. Mica, for instance, separates into thin
sheets due to cleavage parallel to the structural layers which are only weakly
held together; and blue asbestos, one of the amphiboles, is fibrous due to
cleavage parallel to the chains of silicate units.
SILICON 135
Key
oxygen £ silicon
(a) An expanded view (b) The tetrahedron (c) A top view of an

of the [S i0 4] formed by joining [S i0 4] tetrahedron
tetrahedron the oxygen atoms - the Si is below the
centre point
Figure 8.1 The tetrahedral [Si04] unit found in silicate minerals.
8.2 Weathering
The solid rocks that compose the bulk of the crust do not remain compact,
coherent masses when exposed to the atmosphere. In many areas they are
covered by a soft particulate layer called soil. Even where the solid rocks
appear uncovered by soil or other fragmented material, close examination
reveals that the surface layers have a slightly different appearance and
composition from those of inner regions. Also, over a period of time, the
outer layers are being removed. This disintegration of solid rocks is part of
the weathering process in which the rocks and minerals are altered until they
are chemically and physically in equilibrium with their surroundings.
It is convenient when looking at the mechanism of weathering to divide
the process into two mechanisms that operate together and reinforce each
other’s actions:
(a) physical, or mechanical, weathering, in which the rock and subsequent
fragments are broken into smaller particles and transported from one
locality to another, lower site; and
(b) chemical weathering, in which the chemical composition of the rocks
and fragments is changed to produce more stable compounds or species.
The mechanical breakdown into smaller particles produces a larger
surface area over which chemical reactions can occur and the changes in
chemical composition tend to weaken the structures so that they are easier
to break up.
For the environmental chemist, one of the most important features of
weathering is that it mobilizes many chemical substances. It is this mobility
aspect that we shall concentrate on. In general, the lower the solubility of a
136 M AJ O R E L E M E N T S F O U N D I N TH E E A R T H ’S C R U S T
compound the smaller will be the interaction between that compound and a
live organism. Therefore, processes like weathering that affect the solubility
of elements are of prime importance in controlling the viability of
organisms. There is a wide variety of often quite complex reactions occur
ring during weathering and in this book we shall only illustrate some of
the general principles by considering aspects of the weathering of igneous
rocks.
The composition of the parent rock and the weathering conditions
together control the proportion of soluble and insoluble products formed
during weathering. The majority of the minerals in igneous rocks were
formed at high temperatures and usually high pressures. In general, the
higher the apparent temperature of formation of the mineral, the more
rapidly it is likely to weather (Figure P3.2). The more ionic the bond, the
more soluble in water the mineral is likely to be. The Si-O bond has more
covalent character than the metal-oxygen bonds in minerals. It is found that
minerals in isostructural groups with the greatest proportions of [Si04] units
are the most stable, e.g. sodium-rich plagioclases have 61%—69% Si0 2
and are much more stable than the calcium-rich plagioclases with 43% -
51% Si02.
The isomorphous substitution of one element for another in silicate
lattices, which is widespread, can cause either an increase or a decrease in
the stability of the crystal structure. The consequence is that the individual
crystals of a mineral in a rock may weather at very different rates, depending
upon the substituted elements. Also the trace elements released by this
weathering can vary markedly from rock to rock, even though the mineral
composition appears very similar.
Figures 8.2 and 8.3 illustrate the general trends during weathering, and
some of the breakdown products for individual minerals. It should be noted
in particular, that water is a prerequisite for these reactions and in many
arid areas the amount of water is so low that physical weathering is the
dominant mechanism. The reactivity of aqueous solutions is increased by
the presence of hydrogen ions, which aid the dissolution of metallic
elements. The acidity of the water can arise from three major sources:
(a) gases dissolved from the atmosphere. The main example is carbon
dioxide, which gives an equilibrium pH of 5.7, but in some areas of the
world (e.g. northern Europe), the contribution from sulfur dioxide has
become even more important and sometimes the pH has dropped to
about 4;
(b) the oxidation of plant remains (Chapter 4). This can increase the
concentration of carbon dioxide in the soil atmosphere (the gas oc
cupying the space between the soil grains) by a factor of a hundred; and
SILICON 137
□ solids
Figure 8.2 The general processes that occur during the weathering of igneous rocks.
(c) the formation of organic acids during the decay and partial oxidation of
plant remains (Eqn 8.1). This can lead to a pH in the range of 4-5.
organic C + 0 2 — ►RCOOH + ArOH — > RCOO" + H+ + ArCT + H +
carboxylic acid phenols
(8 . 1)
Reaction of the acidic solution with the silicate minerals reduces the
acidity of the aqueous solution (Eqn 8.2), and it may even become neutral or
alkaline.
2H+ , + M 2Si04^ H 2M Si0 4 + (8.2)

acidic solution altered silicate neutral solution
These changes in pH may also change the solubility of the species present
(Figure 8.3). If the pH is between 5 and 9, silicon is more soluble than
aluminium and iron, and will be leached out of a rock or soil to leave behind
a mixture of hydrated aluminium and iron oxides which will form a lateritic
soil (more aluminium oxide) or feralitic soil (more iron oxide). When the pH
is below 5, aluminium becomes more soluble than silicon and will be leached
out. The solubility of iron also increases at low pH, especially if the ground
becomes waterlogged for part of the year and reducing conditions are
produced (Chapter 9). Low pH, as it is usually associated with organic
matter, tends to occur close to the surface of a soil or rock. As the acidic
water percolates through the soil, reacting with the minerals, the pH rises
and the solubility of iron and aluminium is reduced. The aluminium and
iron compounds precipitate out of solution and often form a distinctive
layer, called the B horizon.
138 MAJOR E L E M E N T S F O U N D IN THE EA R T H S CRUST
(a)
Figure 8.3 The chemical weathering of a number of common minerals found initially in
igneous rocks.
The part played by the decay of organic matter in the formation of carbon
dioxide and organic acids in soils has been described. As well as being
responsible for lowering the pH and making the soils more acid, the organic
decomposition processes can affect the progress of weathering in other
ways. One major effect can be to change the redox conditions. Any such
changes bring about changes in the solubility of elements such as iron
(Chapter 9), sulfur (Chapter 6 ) and nitrogen (Chapter 5). Many of the
organic compounds produced during decomposition can act as complexing
agents which may increase or decrease the solubility of an element. Organic
compounds with high relative molecular masses, such as those that make up
peat and the humose layers in soils, are insoluble in water. Therefore,
metals, e.g. lead, forming complexes with these substances are held in
immobile forms in surface layers of soils (Chapter 13). Compounds with
lower relative molecular masses (values less than 1000 ), and which contain
OH or COOH groups, are more likely to form soluble complexes with
SILICON 139
metals and so increase the mobility of the metal. The binding of the organic
compound to the metal ion in the complex prevents the metal ion reacting
with other chemicals. Thus, the chemistry of the complexed ion can be
completely different from the chemistry of the simple ion. For instance,
iron(III), Fe 3 + , will often precipitate from solution (Eqn 8.3) when the pH
rises above 4 (Chapter 9). If oxalic acid, HOOCCOOH, is present an iron-
oxalic-acid complex such as trioxalatoferrate (III), [Fe(OOCCOO)3]3“ , is
formed that is soluble at pHs higher than 4 (Eqn 8.4).
Fe3+ + 3H20 — >Fe(OH ) 3 +3H+ (8.3)
insoluble
Fe3+ + 3HOOCCOOH — ►[Fe(OOCCOO)3] “ 3 + 6 H+ (8.4)

soluble
One of the great difficulties in studying natural solutions is knowing in

what form an element is actually present. Is the copper in the soil-pore water
a simple hydrated ion or is it in a complex with, for example, citric acid, as
[Cu(C6H 40 7)]2-? The interaction of the organic compounds, produced by
microbial action, with the minerals in rocks and soils can prove to be the
dominant factor in determining the rate at which weathering proceeds. This
is because of the way in which chemical properties, and especially solubility,
can be altered. The chemical reactions that occur are often very complicated
and there is little detailed knowledge of the actual changes occurring in
natural systems.
A characteristic feature of soils is the formation of a series of layers of
different composition, called horizons (Figure 8.4), parallel to the daylight
surface. The thickness, composition and appearance of the various horizons
varies widely from place to place, being determined by the interaction of
source material, climate, topography, biological activity and age. The
general pattern found shows movement of material away from the surface.
The movement is initially downwards, but may then become lateral with the
ground-water flow. Intermediate stages result in the accumulation of
particular types of matter in certain horizons (e.g. organic matter in Ao
horizons; iron oxides, clays and co-precipitated trace elements in the B
horizon) or in the removal of materials from certain horizons (e.g. silicon or
aluminium, depending upon pH, from the E horizon).
The general changes occurring in silicate-based rocks during weathering
and soil formation can be summarized as:
(a) breakdown into smaller particles;
(b) formation of new minerals that have a greater proportion of octahedral
structures stable at low temperatures and pressures;
(c) the preferential loss of silicon, found in tetrahedral units, compared to
aluminium and iron, found in octahedral units;
140 MA J O R E L E M E N T S F O U N D IN THE E A R T H ’S C R U S T
Symbol
for horizon
> 35% organic matter

> 20% organic matter, often waterlogged
usually contains well-decomposed organic matter

mixed with the mineral grains (often
dark coloured)
has lost varying amounts of clay, iron and

aluminium (often light coloured)
increased concentrations of clay, iron and

aluminium oxides, humus (often brown
coloured)
unconsolidated bedrock material - little

chemical alteration
bedrock
Figure 8.4 Diagrammatic representation of an idealized soil profile.
(d) increasing numbers of OH- ions, or even H20 groups, compared to 0 2~

ions in the new minerals;
(e) preferential loss of sodium, calcium and magnesium compared to
potassium, aluminium and iron; and
(f) general mobilization of trace elements as the original silicate minerals
disintegrate (although these elements may be trapped again in the new
low-temperature minerals).
Ultimately both the soluble components (2.5 x 109^ x 109 tonnes a-1)
and the particulate residues (6.5 x 109—18 x 109 tonnes a-1) from
weathering will be transferred to the oceans. The most important transfer
agents are the rivers (89%), but glaciers (7%) and ground water (2%) both
provide significant inputs to the ocean. Dust (0.2%-0.5%) blown into the
atmosphere can be of considerable local importance. The rivers have been
estimated to have an average ratio of dissolved:suspended material of 1 :2 .6 ,
but higher transfer rates and ratios (1:4.5) have also been suggested. The
actual ratio of dissolved:suspended load varies greatly from river to river
and even from continent to continent. About 80% of all suspended material
entering the world’s oceans comes from South-East Asia. The distribution
of the dissolved load entering the oceans is much more evenly spread
between the continents, but Australia and Antarctica provide very low
inputs due to their arid and frozen natures, respectively.
9 Iron
Iron Abundance by weight (the relative abundance is given in

parentheses): Earth, 34.8% (1); crust, 5.0% (4); ocean, 3.4 ppb
(28). ppb = ng kg~‘.
Assuming that the core is mainly composed of liquid iron and that the
mantle contains a high proportion of ferromagnesian silicates, both will have
higher concentrations of iron than that in the crust. In addition, the
oxidation state of the iron changes from 0 , the free metal, to 2 (called
iron(II) or ferrous iron) in ferromagnesian minerals, and to 3 (called
iron(III) or ferric iron) in many crustal rocks.
The oxygen-rich atmosphere of the Earth ensures that both iron(0) and
iron(II) are unstable under normal conditions at the Earth’s surface and
both are oxidized to iron(III) (Eqns 9.1 and 9.2) producing the characteristic
red-brown yellow colours of the various forms of iron(III) oxide.
4Fe + 3 0 2 — >4Fe3+ + 6 0 2-(— >Fe 2C>3 ) (9.1)
4Fe2+ + 0 2 — >■4Fe3+ + 2 0 2“ (— ►Fe20 3) (9.2)

The low solubility of iron(III) oxides means that the cycle of iron (Figure
9.1) is dominated by solid-transfer reactions and most of the iron reaching
the oceans is carried by rivers as suspended solids. Of the estimated
1.1 x 1012 kg a -1 iron transported by rivers to the oceans, only 1.4 x 109
kg a -1 is thought to be in solution.
9.1 Iron in natural systems
The lithosphere
The changes in oxidation state of iron in the Earth’s crust are of great
importance in understanding its properties, including mobility. Many of the
factors that are important for iron are also important for other elements
with variable oxidation states - manganese, for instance, is very similar to
iron. The relative stabilities of iron(II) and iron(III) are such that only small
changes in natural environmental conditions can cause either iron(II) to be
r *
i A TM O SPH ER E
I
L.
dust
dust
LA N D
OCEAN
suspended solution F e34
solids (3 ppb)
(99.87%)
--------------------------1
sediments
oxidizing
conditions
iron(III) oxide
reducing
conditions
iron(II) minerals
diagenesis
(low tem perature)
metasomatism
(high tem perature)
Figure 9.1 The iron cycle, illustrating changes in oxidation state.
oxidized to iron(III) or iron(III) to be reduced to iron(ll), with consequent

large changes in solubility. Changes in either pH (i.e. proton activity) or
redox potential, Eh (which is a measure of how oxidizing or reducing a
system is, i.e. it is a measure of electron activity) are effective. The Eh-pH
diagram (for example, see Figure 9.3), also known by engineers as a
Pourbaix diagram, is a useful way of illustrating which forms of an element
may be stable under specific conditions of pH and Eh. The diagram contains
so-called regions of dominance, inside whose boundaries one form is the
most stable under that set of Eh-pH conditions.
When considering natural systems on the surface of the Earth, only a
limited range of pH and Eh need be investigated. Because water is stable on
IRON 143
the Earth’s surface, redox potentials that would cause either the oxidation of
water (Eqn 9.3), i.e. high values of Eh, or reduction of water (Eqn 9.4), i.e.
low values of Eh, must not occur. In practice the natural range of Eh values
is even narrower, being mainly confined to the region between +0.6 V and
—0.8 V, with surface water being in the range + 0.2 V to + 0.5 V (Figure 9.2).
2H20 ^ 0 2 + 4H+ + 4e“ (9.3)
2H20 + 2e" ^ H 2 + 20H~ (9.4)

The normal range of pFt of waters in natural systems is 4-9, being controlled
WATER OXIDIZED
IX
h \ 0 2+ H+
t
oxidizing
n 1 \
K.
r ! » >
M U
X h 2o
1
4
\
_
H 2 + OH
s \
— \ \
WATER REDUCED
reducing
0
1
2 4
1
6
1
8
1 1
10
\
XI
12 14
i
■4----------------- acidic alkaline------------------►
pH
Key
----------------- boundaries within which most normal environmental systems lie
1 rain 2 rivers 3 oceans (surface waters) 4 waterlogged soils
5 reducing marine sediments
6 water affected by sulphide oxidation products
Figure 9.2 The Eh-pH conditions of some natural environments.

by the C 0 2- H C 0 j - C 0 2_ system. Occasionally, low values below pH 4 may

be found, usually due to the oxidation of sulfide minerals, either as a natural
process (often microbially mediated) or as a result of mining which brings
sulfide minerals into contact with the atmosphere. Values higher than pH 9
are associated with alkaline environments, mainly due to the presence of
sodium carbonate in desert regions.
The Nernst equation (Eqn 9.5) provides a more formal definition of redox
potential, Eh:
(9.5)
where Eh is the equilibrium redox potential, in volts, compared to a

standard hydrogen half-cell, which has a value of 0.0 V; F? is the standard
reduction potential at pH = 0, 25 °C, 1 atm and unit activities of solute
ions; R is the gas constant, 8.314 J m o P 1 K P1; T is the absolute temperature,
degrees K; n is the number of electrons transferred; F is the Faraday
constant, 96487 C m o P 1; [oxidized] and [reduced] are the activities of
oxidized and reduced species, respectively.
Although the Eh value is the value compared to the hydrogen electrode, in
the majority of measurements other electrodes are used and a conversion
factor applied.
Hydrogen ions are released when water is oxidized (Eqn 9.3), therefore,
changing the H + activity (or H + concentration) of H20 and 0 2. This
dependence of Eh on pH is shown below when values typical of the
conditions on the Earth’s surface are substituted in Equation 9.6.
(9.6)
As the water can be considered to be pure, its activity is constant with a

value of 1 .
At a temperature of 298.15 K (25 °C), = + 1.23 V. Thus;
8.314 x 298.15
Eh = 1.23 + x 2.303 x log ([0 2][H+]4)
4 x 96487
1.23 + 0.0148 x log[02] + 4 x 0.0148 x log[H+]
= 1.23 + 0.01481og[02] + 0.0591og[H+]

IRON 145
But
log[H+] = -p H
and at the Earth’s surface
[O2] = partial pressure of O2 in the Earth's atmosphere
= 0.21 atmospheres
Therefore
Eh - 1.23 + 0.00148 log (0.21) - 0.059 pH
= 1.23 + 0.01 —0.059 pH
= 1.22-0.059 pH
For iron the simplest approximation to natural conditions is illustrated by

the Fe-H 20 system (Figure 9.3), which indicates the boundaries of the
regions of dominance of the various species at two concentrations of iron.
At the boundary line between two regions of dominance the activities of the
two species are equal, but the activity of a species decreases very rapidly
outside its own region of dominance. The region of iron(III) hydroxide
stability includes much of the Eh-pH range found in natural systems (Figure
9.2). The stability region for metallic iron lies below the water stability
region, indicating that metallic iron is unstable and will tend to convert to
Fe2+ or Fe(OH)3.
Rain water running through a soil containing organic matter could have a
pH of 4.5 and Eh of + 0.5 V (position A in Figure 9.3), and any iron
minerals in the soil will tend to dissolve. As the water flows through the soil,
reaction with other minerals, such as carbonates, in the soil will raise the pH
to a value of 6 , say (position C in Figure 9.3). However, when the pH
approaches 5, the iron will precipitate as iron(III) hydroxide (position B).
Thus, the iron will have been transported from the mineral near the surface
of the soil to the region of higher pH that may be a few millimetres,
centimetres or metres away. If there was a lot of rain and the soil became
waterlogged, the water would occupy all the pores in the soil, displacing the
air and its associated oxygen. Microbial respiration would use up the small
amount of dissolved oxygen in the water and conditions would become
anaerobic. The Eh might drop to —0.1 V (position D). As the water moves
through the soil, the pH would again rise, but now the Fe(OH ) 3 boundary
would not be reached until pH 9 (position E). In waterlogged reducing
conditions, the transport of soluble iron(II) is likely to be more extensive
than in aerobic conditions. In practice, because more Fe2+ will be dissolved,
the iron molarity is likely to increase from about 10“ 7 M (5.6 fig dm~3) to
about 10~ 4 M (5.6 mg dm-3) and the Fe(OH ) 3 boundary will be between pH
7 and 8 (position F). If there was much water movement, this would still
146 MAJOR E L E M E N T S F O U N D IN THE E A R T H ' S C R U S T
acidic pH alkaline
Key
------------ boundaries within which most environm ental system s lie
-------------( F e 2 + ] = 10- 7 M
------------ [F e 2+ ] = 10 -4 M
A ------- F see text
Figure 9.3 The Eh-pH diagram for the iron-water system. (After Garrels, R.M. and L. Christ
1965. Solutions, minerals and equilibria. New York: Harper & Row.)
lead to extensive leaching. The leaching of iron in waterlogged soils is the

characteristic feature of gleying and in acid soils in the formation of podzols
(Figure 9.4).
In natural systems there are many different dissolved species other than
iron, and these can influence the behaviour of iron by reacting with it to
form either relatively insoluble compounds (e.g. sulfide or phosphate) or
stable complexes (e.g. organic acids with iron(III)) that prevent the iron
IRON 147
organic matter
O organic matter (peat)
organic low pH
acids gleyed horizon Fe
F e2+
leaching o f F e2+
+ A l3+ i
water
higher
F e3+ builds up iron pan F e3
PH
clay colloids Fe +oxides + clay form
accumulate an impervious layer
preventing free drainage
(a) Podzol (b) Peaty stagnogley
hotter climate -
surface erosion
removes upper soil layer
slow leaching
water table (wet season)

F e ,+ + A l,+ form
hard impervious layer
mottled F e2+ +
F e 3+
water table (dry season)
saturated soil - F e2+

leached out
(c) Groundwater gley (d) Laterite
Figure 9.4 The formation of podzolic, gleyed and lateritic soils.
being precipitated. Diagrams including all possibilities would be very

complicated, but an approximation to many natural conditions is given by
the Eh-pH diagram for the F e -C 0 2-S -H 20 system (Figure 9.5). The
normal range of conditions found in soils is outlined and it can be seen that
haematite (Fe 20 3), siderite (FeC 03), pyrites (FeS2) and soluble Fe2+ are all
possible phases. In general, the most common iron species are Fe2+ in acidic
148 MAJOR E L E M E N T S F O U N D IN THE E A R T H ’S CR U S T
reducing conditions and haematite in less acidic and in alkaline oxidizing

conditions. Although haematite is the most stable oxide form, goethite
(FeO-OH) and other hydrated oxides are almost as stable and just as
insoluble. The transformation from one of these hydrated solids, which may
be precipitated first, to haematite is very slow. It is often found that
haematite is formed in warm wet regions and goethite elsewhere.
Because the boundary between the Fe2+ and Fe 20 3 domains is just on the
acid, reducing side of normal surface waters, relatively small changes in pH
or Eh can cause either marked dissolution or precipitation of iron. For
K ey
s' N
( ) possible conditions in soils [ F e 2 + ] = 10_f> M
v [C O .M = l M
A, B see text [S 2"] = 10_ 6 M
Figure 9.5 The Eh-pH diagram for the F e-H 20 - C 0 2-S system. (After Garrels, R.M. and L.
Christ 1965. Solutions, minerals and equilibria. New York: Harper & Row.)
IRON 149
example, ground waters tend to be reducing and contain several milli

grammes per cubic decimetre of dissolved Fe2+, but on emerging from a
spring the Eh will rise rapidly as oxygen is dissolved (movement from A to B
in Figure 9.5) and a red-brown precipitate of iron(III) oxide will form. The
first-formed precipitate is usually a gelatinous hydrated iron(III) oxide,
Fe 20 3 ftH20 , that gradually dehydrates on ageing, although formation of
Fe 20 3 may take years. When in the freshly precipitated, highly hydrated
form, the iron(III) is more likely to redissolve than when in the partially or
fully dehydrated form. The surface area of the fresh precipitate is very high
and the stoichiometric charge balance is not very good. As a result many
other ions, particularly other metals, may be sorbed and co-precipitated
(Figure 9.6). The precipitate acts as a scavenger for these metals and tends to
collect in the soil’s B horizon, either because the pH is higher in this horizon
or because it acts as a barrier to the transport of colloidal iron(III) oxide
particles (size less than 1 x 10- 6 m) by ground water.
The most noticeable effects of iron redox reactions in soils are seen in
podzolization, gleying and laterite formation. A podzol is typically formed
in a cool temperate climate in which there is sufficient rainfall to maintain
downward leaching and in which the breakdown of organic matter is slow
(Figure 9.4a). The acid conditions favour the dissolution of Fe2+ and Al3 +
and their transport from the A horizon, together with organic matter, to the
K ey
X" anion, e.g. P O 4-
M e" + cation, e.g. P b : + . Z n : +
Figure 9.6 An illustration of surface processes associated with hydrated iron(III) oxide.
150 MAJ OR E L E M E N T S F O U N D IN THE E A R T H ’S C R U S T
B horizon. Here the higher pH favours precipitation of iron(III) oxide,

together with the accumulation of clay and other colloids. The result is a
grey silica-rich A horizon and a brownish B horizon. If the B horizon is
relatively impervious (perhaps due to clay), the upper portion of the soil will
tend to become waterlogged (Figure 9.4b) and the reducing conditions that
develop (gleying) promote the further leaching of iron. The periodic drying
out of the upper layers favours the formation of an iron pan (a hard
impervious layer of iron(III) oxide) at the top of the B horizon. In soils with
an oscillating water table near the surface, the gleyed regions may be below
the surface (Figure 9.4c). This zone is typically mottled due to the presence
of Fe2+ and Fe 3 + , whereas the permanently saturated zone underneath
contains Fe2+ that is being leached away. In hotter climates the dropping of
the water table may cause most of the iron in this zone to oxidize rapidly to
iron(III) and form an extensive iron pan (Figure 9.4d). This layer also
accumulates aluminium oxides and, as it is impervious, subsequent heavy
rainfall tends to wash off the looser soil above, leaving the hard lateritic
layer exposed.
The biosphere
The concentration of iron in the biosphere is much lower than in the
lithosphere, but iron is essential to the functioning of all organisms and it
has been suggested that iron deficiency is probably the most prevalent
deficiency state affecting human populations. As we have seen already,
although iron is a common constituent of soils, levels in solution are
generally low and it is not very available.
One of the functions of iron is to act as an oxygen carrier in vertebrates.
Oxygen is carried to the cells of the body by haemoglobin molecules
concentrated in the red blood cells of the bloodstream (Figure 9.7). The
presence of haemoglobin (Hb) raises the oxygen carrying capacity of the
blood from about 3 to 200 cm 3 d m '3. The red blood cells, erythrocytes, are
8 /im in diameter and each contains about 280 x 106 molecules of haemo
globin. The cells of the body contain myoglobin, which accepts and stores
the oxygen carried by the haemoglobin. Both haemoglobin and myoglobin
(Figure 9.8) contain iron(II) bound to the four pyrrole nitrogen atoms of
protoporphyrin IX. This arrangement is called the haem group. The iron is
also bound to a nitrogen atom from a histidine group that is part of a
protein chain and called the globin part of the molecule. Haemoglobin
contains four of these units and binds four molecules of 0 2, one to each
iron, whereas myoglobin consists of only one unit and binds only one 0 2
molecule. Myoglobin has a greater affinity for oxygen than has
haemoglobin. The affinity of haemoglobin for 0 2 varies with pH, being
lower at lower pHs (higher carbon dioxide concentrations in the tissues).
IRON 151
( ~ 97% HbQ2)
LUNG
arterial blood
H b02
a H b02
I
■* Hb Hb” Mb° 2
i i lung capillary tissue capillary
venous blood
( ~ 75% H b 0 2) + C 0 2(aq)
Figure 9.7 Diagrammatic representation o f the transport of oxygen from lungs to body cells
by blood.
This helps the transfer of 0 2 to myoglobin, and when the C 0 2 carried by the
blood is released to the lungs, the lower C 0 2 and higher 0 2 concentrations
favour 0 2 pick-up. The globin reduces the ability of H20 and 0 2 molecules
simultaneously to approach the iron(II), which would then be oxidized to
iron(III). The iron(III) complexes, methaemoglobin and metmyoglobin, do
not bind 0 2, which explains the reduced 0 2 transport induced in infants
with methaemoglobinaemia (Chapter 5). The globin is not completely
successful in preventing methaemoglobin production, but an enzyme
reduction mechanism keeps the level to about 1 %.
Carbon monoxide, CO, complexes more strongly than does 0 2 with the
Fe 2 + , forming carboxyhaemoglobin (HbCO; Eqn 9.7).
H b 0 2 + CO ^ HbCO + 0 2 (9.7)
If someone suffering from carbon monoxide poisoning is given pure oxygen
to breathe, the equilibrium reaction 9.7 will be moved to the left and the
conversion of HbCO to H b 0 2 will be promoted. Whether this treatment
proves successful depends upon the extent of oxygen deficiency in the body
before treatment commences.
The iron(II)-iron(III) transition (Eqn 9.8) is made use of by many
molecules involved in electron-transfer reactions, such as the ones we came
across when discussing the role of nitrogenase in the fixation of nitrogen.
152 M A J O R E L E M E N T S F O U N D IN TH E E A R T H ’S C R U S T
Figure 9.8 Structure of oxygenated myoglobin.
Fe2+ ^ Fe3+ + e" (9.8)

Animals, including humans, have only a limited ability to excrete
metabolic iron, so the correct iron balance in the body is mainly achieved by
adjustments to the rate of absorption. Normal adults only absorb about
5%—10% of the iron in a balanced diet, whereas iron-deficient individuals
absorb 15%—20%, or more, of the iron. The iron has generally to be in the
iron(II) state and it tends to be more readily absorbed if already bound to
haem groups. The detailed mechanism of absorption is not understood and
there appear to be many interacting and interfering factors. The majority of
the iron in the body (about 4 g in an adult) is continuously recycled, thus
counterbalancing the relative difficulty of absorption. Iron deficiency arises
either from poor diets (intake less than 1 0 -1 2 mg d-1) or by excessive loss,
usually due to bleeding. The deficiency reduces the level of haemoglobin in
the blood, producing anaemia, which in turn reduces the transport of
oxygen for energy production in the cells, leading to listlessness.
9.2 Iron in industrial systems
Iron is the most commonly used metal, with iron production at about 540
Mtonnes per annum and steel production at 780 Mtonnes per annum. (Steel
production is higher due to the recycling of scrap steel and to the other
metals added to iron to make the steel.)
Iron is produced by the reduction of various ores (haematite, Fe 20 3 ;
goethite, FeOOH; magnetite, Fe 30 4 ; siderite, F eC 03), but iron(III) oxide is
by far the major component. One of the reasons iron has been used by
I RON 153
humans for so long is that this reduction is fairly easily achieved using
carbon (Eqn 9.9) and associated compounds.
2Fe 20 3 4 - 3C — > 4Fe + 3C 0 2 (9.9)
Charcoal was used initially, but nowadays coke is the source of carbon.
The reduction is carried out in a blast furnace which is in essence a large
steel cylinder (perhaps 30-40 m high, 10-17 m diameter) lined with
refractory bricks to withstand the high temperatures. Iron ore, coke and
limestone are added from the top, through a double bell which prevents the
escape of poisonous gases; and hot air, often partially enriched in oxygen
and some hydrocarbon fuel, is blown in from near the bottom.
The initial reactions of coke and hot air (Eqns 9.10 and 9.11) produce
enough heat to support the other reactions in the blast furnace, provided
that the initial air temperature is above 500 K. (Usually it is 1200-1600 K.)
C + 0 2 — >C 0 2 (9.10)
2C + 0 2 — > 2CO (9.11)

The C 0 2 reacts with more coke, producing more carbon monoxide (Eqn
9.12).
C + C 0 2 —* 2CO (9.12)
Any C 0 2 formed by the reduction of iron(II) oxide (Eqn 9.13) is reconverted

to CO above 1200 K (Eqn 9.12).
FeO + CO — ►Fe + C 0 2 (9.13)
At lower temperatures the proportion of C 0 2 in the gas increases until the
gas leaves the blast furnace. The presence of unoxidized CO means that the
gas has about one-tenth of the energy of an equal volume of natural gas, and
this energy is utilized by burning it so that it either pre-heats (via heat
exchangers) the air entering the blast furnace, or drives plant and electrical
generators on the site.
The iron from the blast furnace is called pig iron, and the majority of it is
kept molten and used to make steel. Because of its high carbon content, pig
iron is very brittle; although it can be cast it cannot be rolled or worked
easily.
The slag is a complex mixture of compounds such as calcium alumino-
silicates formed by the reaction of lime, CaO (a basic oxide), with the
various acidic oxides of silicon, aluminium, manganese, phosphorus, etc.
Oxide impurities are concentrated in the slag but any impurities reduced to
the elemental stage (as occurs near the bottom of the furnace) are more
soluble in the molten metal. After tapping it from the furnace the slag is
dumped, with varying amounts being used for bricks, concrete, ballast and
insulation wool.
Steels are alloys of iron, containing quantities of other elements that
modify the properties of iron. The quantities are controlled to produce the
desired material, whether a ductile low-carbon steel (0.2% C), or a stainless
steel (18% Cr, 8 % Ni), or a high-speed cutting steel (18% W, 5% Cr, 0.7%
C). The extremely high variety of steels manufactured is mainly derived
from pig iron by a process that involves the removal of impurities in the pig
iron by oxidation and then adding alloying elements as required.
The majority of this so-called primary steel is now made using the oxygen
furnace in which high-pressure oxygen is blown into a mixture of scrap and
molten pig iron for about 15 min, to produce about 300 tonnes of steel in
30— 40 min. As in the blast furnace, the impurities are removed in a slag
formed with added lime. The oxidation of the impurities is highly
exothermic and the scrap is added to absorb the excess heat. Because of its
rapid turn-round time and more efficient use of energy, the oxygen furnace
has replaced the open-hearth furnace that was the preferred method until
about 20 years ago. The oxygen furnace produces large quantities of fine red
dust, Fe 20 3, and efficient fume- and dust-extraction systems have had to be
developed to reduce this pollution problem.
Electric-arc furnaces are used to produce secondary steel, i.e. steel made
from steel scrap as opposed to pig iron. They produce 25-125 tonnes of steel
in 2-4 h and are used to make high-grade special steels that justify the high
cost of electricity and pollution-control equipment. These costs have to be
incorporated into the selling price. Because electric-arc furnaces use scrap,
their total energy costs are lower than for other processes (Table 9.1).
The iron and steel industry is ranked as the second most polluting
industry in the UK - coke production is the first - and the cost of adequate
pollution-control measures is high because of the large quantities of
Table 9.1 Energy needed to produce 1 tonne o f steel
Blast furnace
Electric-arc
furnace Oxygen furnace Open-hearth furnace
(100% scrap) (30% scrap) (40% scrap)
Total energy input

(MJ/tonne steel) 13 000 22000 25 000
% Energy efficiency* 55 35 30
, „ . theoretical energy to convert ore to steel

Energy efficiency = -------------- ---------- :----------------------- :------- ,
actual quantity ol energy used
IRON 155
materials handled. In a new steelworks these costs are likely to be a quarter

or a third of the total capital costs. As the steel-making process is no more
efficient after the installation of the control equipment, this added
expenditure, plus the running costs, makes steel production more expensive
in countries with strict pollution-abatement policies.
9.3 Corrosion
The Eh-pH diagram for Fe-H 20 (Figure 9.3) indicates that iron is unstable
under the conditions existing on the Earth’s surface. This instability is
exhibited by the formation of rust (a hydrated iron(III) oxide of variable
composition), which is the best-known example of corrosion - the
deterioration of a substance by environmental constituents. The costs of
corrosion are enormous, having been estimated as costing the UK 3.5% of
its gross national product.
The corrosion process involves the transfer of electrons as the corroding
metal is oxidized (Eqn 9.14). This means that for corrosion to occur there
must be an electron acceptor (usually oxygen), but it need not be present at
the site of corrosion if the electrons can be transferred to it at some other
site:
M ^ M 2+ + 2e“ 0 2“ ^ MO (9.14)
The presence of water often enhances the rate and extent of corrosion:
(a) it can provide electron acceptors in either acid (Eqn 9.15) or alkaline
solutions (Eqn 9.16):
M ^ M 2+ + 2e~ ^ H2 (9.15)
2M— >2M2+ + 4e~ ° 2±HJ2° 4o h (9.16)

(b) it can provide an electron-transfer medium, particularly if it contains
dissolved ions (as do sea water, or water plus road de-icers);
(c) it can remove reaction products that could inhibit further reaction by
building up a protective coating, especially if it contains dissolved ions
that can form soluble complexes with the metal ions, e.g. [FeCl4]~;
(d) it can modify the structure of the reaction products so that they provide
less inhibition to corrosion - e.g. rust is hydrated iron(III) oxide,
Fe20 3 nH20 , whose volume is much greater than that of metallic iron.
Rust forms a loose, porous coating, whereas in the absence of water
Fe 20 3 will form a coherent, non-porous protective layer because its
volume and crystal structure are much closer to that of metallic iron.
The surprising feature about corrosion is not that it occurs, but that in
many cases the extent is much less than we might expect from diagrams such
as Figure 9.3 and from a knowledge of the free energies of formation, AG/,
of the oxides (Table 9.2). The oxides all appear to be very much more stable
than the metals, yet nickel and chromium are added to iron to form stainless
(non-corroding) steel, and aluminium is widely used as an untreated
construction material. In each case the oxide has a crystal structure closely
related to that of the metal. A thin, non-porous coating of oxide rapidly
forms on the metal’s surface preventing further contact between unreacted
metal and oxygen, or other electron acceptor, and further corrosion is
prevented. Prevention of contact between reactants is one way of stopping
corrosion; the second method is to provide excess electrons to react with the
electron acceptor in place of the metal.
The protective coating may be achieved by adding a simple physical
barrier (Figure 9.9a) such as paint or oil, or it may involve a chemical
change of the metal surface. An oxide coating can be produced on iron by
treating it with oxidizing agents like dichromate, C Ô 2- (Figure 9.9b); a
phosphate coating such as iron(III) phosphate, F eP 04, results from
treatment of the iron with phosphoric acid, H 3PO 4 . The provision of extra
electrons may be achieved:
(a) by coating iron with a less electronegative element - zinc is used to
galvanize steel (Figure 9.9c), the zinc being removed in preference to the
iron;
(b) by connecting the iron to a piece of less electronegative element, the so-
called sacrificial anode, e.g. magnesium or zinc, which is replaced when
dissolved. This technique is used with storage tanks and ships (Figure
9.9d);
(c) by applying to the iron a current from the negative terminal of a low-
voltage DC source, the positive terminal being connected to a non-
sacrificial, inert anode (Figure 9.9e) - this technique is used on pipelines,
ships, tanks and even on the Panama Canal lock gates.
Recently microbial corrosion has been recognized as a major problem
under reducing conditions in which sulfur compounds are available to act as
electron acceptors (Eqn 9.17).
M + S O ^ + 8 H+ “ a -M " + + S2~ + 4H20 (9.17)

n
Table 9.2 Free energies of formation for the oxides of some metals
Metal oxide a i 2o 3 Fe20 3 MgO NiO Cr20 3
A G ) (kJ m o r 1) -1 5 8 0 -7 4 0 -5 7 0 -2 1 0 -1 050
I RON 157
(a) Paint
topcoat - impervious to 0 2 and water

jT primer + undercoats - bind top coat to metal
metal
(b) Oxide coating

o • o • o • o Key
• O • O • O • oxide lattice O o-
• Fe or Fe3
O • O • O • O
metal lattice
(c) Galvanization
Zn —> Zn ~+ + 2e
Fe (Fe —> Fe 3+ + 3e when Zn removed)

zinc dissolves in preference to iron
(d) Sacrificial anode
A steel tank --------j Mg —» M g2+ + 2e~

Fe j magnesium dissolves in
\L conductor
8 preference to iron
(e) Direct current DC source

-f ve
(Fe + 3 e _ —* Fe)
steel tank
\L Fe
tendency to lose electrons

reversed by impressed current graphite anode
(inert, does not dissolve)
Figure 9.9 A number of methods that may be used to prevent the corrosion of iron.
This problem can occur either externally in soils and sediments, or internally
in storage tanks and pipelines with water-oil mixtures. Methods of
protection are the same as for aerobic corrosion.
10 Aluminium
Aluminium Abundance by weight (the relative abundance is given in

parentheses): Earth, 1.8% (8 ); crust, 8.2% (3); ocean, 1 ppb
(31). ppb = k g "1.
Aluminium is the third most abundant element in the Earth’s crust and, like
oxygen and silicon, it is widely dispersed in silicate minerals. In the cases
such as feldspars and clays, in which the aluminium forms an essential
structural component, the minerals are described as aluminosilicates. In
other minerals, such as pyroxenes and amphiboles, the aluminium is only
present as an isomorphous substituent for varying proportions of silicon
and its presence is not essential for the stability of the crystal structure. The
larger size of the aluminium, compared to silicon, allows it to form stable
octahedral structures (Figure 10.1) with oxide ions, [A106], as well as
tetrahedral units. In the clay minerals (Chapter 12), the aluminosilicates
consist of layers of [A106] octahedral units and [Si04] tetrahedral units. In
both tetrahedral [A104] and octahedral [A106] units there is a considerable
degree of covalent bonding between the aluminium and the oxygen.
The proportion of aluminium in weathered material gradually increases
as weathering proceeds. This is because the solubility of aluminium is lower
than that of silicon in the pH range 4.5-10. The changes occurring during
weathering, therefore, follow the order shown in Figure 10.2, unless acid
conditions prevail. The proportion of aluminium in the soil can be used to
indicate either how intensely or for how long weathering has continued. The
build-up of iron oxides will also occur at a pH greater than 4.5, unless
reducing conditions, due to waterlogging for example, aid their removal. In
tropical climates weathering to form insoluble layers of aluminium and iron
oxides can be very rapid. If they are large enough, these aluminium-rich
bauxite deposits can be used as the starting material for the production of
aluminium.
10.1 Aluminium in industrial systems
Aluminium is second only to iron in its use as a metal (18 x 106 tonnes,
1989). The aluminosilicates and the hydrated oxide are both particularly
ALUMINIUM 159
if the oxygens are close-packed, the octahedral hole

has a radius of 102 pm
Figure 10.1 Octahedral structure involving aluminium and oxygen, and found in a variety of
minerals.
stable, whereas the metal is even less stable than metallic iron under the
conditions existing at the Earth’s surface. Therefore, the production of pure
aluminium is a very energy-intensive process that follows a quite different
route from that taken in producing iron and steel.
Chemically, the problem is to find a method of reducing the combined
aluminium(III) to free elemental aluminium(O), as the free energy of
formation (A Gy) for A120 3 is —1580 kJ mol-1, whereas A Gy for Fe 20 3
is -740 kJ mol-1. Carbon and carbon monoxide will not reduce A120 3 at
industrially feasible temperatures (less than 2000 °C). Reduction involves
the addition of electrons to the species being reduced and an electric current
can be used as the source of electrons, providing its potential (voltage) is
high enough.
The standard free energy, AG°, and the standard electrode potential,
are related (Eqn 10.1). The more negative the free energy of formation, the
greater the amount of electrical energy that is going to be required.
increasing degree o f weathering
aluminium in clays aluminium oxides

three-dimensional
aluminosilicates 2:1 clays 1:1 clays e.g . gibbsite
e.g . feldspars
N a A lS j4 0 4 A l4(Si40 10)2 A l4Si4O l0 A I20 3-3 H 20

(O H )4 (O H )8
Si /Al 3/1 2/1 1/1 0/1
iron in silicates ■> goethite FeO .O H or haematite F e 20 3

Figure 10.2 Chemical changes that occur as weathering processes.
160 MAJOR E L E M E N T S F O U N D IN THE E A R T H ' S C R US T
A G° = -n E °F (10.1)
where F is the Faraday constant (96487 C mol ').
The production of electricity is generally an inefficient energy conversion
process, especially when fossil fuels are used in power stations. By the time
losses during generation and transmission have been taken into account, only
20%-30% of the energy in the fuel is actually supplied to the consumer.
Aluminium was initially produced where there was abundant hydroelectricity
and good harbours through which to bring in the bauxite ore. In the 25 year
period from 1950, smelters using fossil-fuelled power stations were built close
to the markets, but smelters are now being built in the bauxite-producing
countries such as Australia and Brazil where there are cheap power supplies,
or on sites similar to those used initially - those with good harbours and
hydroelectricity, such as Canada. The production of 1 tonne of primary
aluminium requires more than four times as much energy as 1 tonne of
copper or zinc, and seven times as much energy as 1 tonne of raw steel.
Bauxite is mined, usually by open-pit methods, from deposits formed in
tropical conditions. The crushed rock is treated with hot sodium hydroxide
under pressure to remove impurities and pure A120 3 is produced. The
alumina, AI2O 3, is reduced to molten aluminium in large electrolytic cells.
Aluminium chloride (AICI3) cannot be used because, unlike sodium
chloride, it is largely covalent and sublimes at 180 °C.
The identified world reserves of bauxite have risen more than fourfold
since 1965, with most of the increase occurring in Australia and Guinea, so
there is no immediate prospect of shortages of raw materials. The recycling
of aluminium would give great savings in energy as remelting and re
processing would require about 10 GJ tonnes -1 rather than the 260
GJ tonnes -1 used in primary aluminium production. The major problem
with recycling is the separation of the required element from the other
components in the manufactured article. The properties of aluminium are
very markedly altered by small amounts of other metals or silicon (formed
from glass, Eqn 10.2) that alloy with it on remelting.
N a 2Si0 3 + CaSi0 3 2NaA10 3 + Ca(A10 2 )2 +2Si (10.2)

Aluminium is non-magnetic and the metal is not easily separated from
contaminants, but unless it remains as the metal during the separation stage
the energy advantage of using recycled aluminium is lost.
Aluminium has the properties of lightness, good thermal and electrical
conductivity, workability, resistance to corrosion and tensile strength when
alloyed. It is used in the construction, transport, electrical and consumer-
durables industries as well as for containers and packaging.
ALUMINIUM 161
The corrosion-resistance properties of aluminium arise from the coherent

coating of A120 3 that rapidly forms on the surface of the metal and prevents
further oxidation occurring (Eqn 10.3).
Al oxl ^ on Al3++ 3e~ removed by electron acceptor (10.3)

or corrosion
The solid AI2O 3 coating is a very poor conductor of electrons, has a low
solubility and has a crystal structure with few defects that is very closely
related to that of aluminium metal. Once the coating has formed there is no
further contact between the metal and the electron acceptor, 0 2, and there is
no possibility of electron transfer occurring through the insulating layer of
A120 3. However, under either alkaline (pH > 10) or acid (pH < 4.5)
conditions, the protective coating will be removed because soluble species
are formed; ‘corrosion’ will then occur. Similarly, sea water contains a high
concentration of chloride ions, C P , that form soluble complexes with
aluminium, and this too destroys the protective coating.
10.2 Aluminium in solution
The presence of aluminium species appears to play a part in controlling the

pH of acid soil waters in the range pH 3-6 (Figure 10.3). Increasing inputs
of acid, whether due to acid rainfall or to the decaying organic matter from
forestry, will cause increasing removal of aluminium from soils that have a
low buffering capacity. Soluble aluminium is moderately toxic to most
plants and the effects of acidification of soils are to reduce the concentration
of some essential elements and increase the concentration of toxic elements.
It has been suggested that there are three phases in the effects of acid rain on
forested areas:
(a) the trees benefit from the increased sulfur and nitrogen added to the
poor soils;
(b) continued acidification reduces the soil’s neutralizing, or buffering,
capacity and leaches out soluble metallic nutrients such as calcium and
magnesium; and
(c) the process accelerates and aluminium is extracted from the soil
minerals, making the soil toxic to the trees. At the same time heavy
metals, also toxic, are mobilized. The critical pH appears to be about
4.2, with aluminium as the main killer below this value.
Aluminium is less toxic to humans at low concentrations and the quantities
of dissolved aluminium in water are normally very low (50 fig dm-3). Water
collected in reservoirs from upland catchments is often highly coloured by
organic compounds. This colour, together with any other suspended
colloidal matter, can be removed by the addition of sodium aluminate
162 M A J O R E L E M E N T S F O U N D I N TH E E A R T H ’S C R U S T
ALTERED CLAY
MINERAL
A l(O H )3
pH ~ 5
[ A l 7 ( O H ) 17] 4+
pH < 4
3H + + 3 0 H " [A l(O H )2] +
1 h 2s o 4
3 H 20 (acid rain) ^^
[ A 1 S 0 4 ] + + 2 H 20
AIâq) + SOj-
Figure 10.3 A possible reaction sequence for the buffering of hydrogen ions in acid soils by
reaction with aluminium species. (After Ulrich, B. 1980. Production and consumption o f
hydrogen ions in the ecosphere. In Effects o f acid precipitation on terrestrial ecosystem s.
Hutchinson, T.C. and M. Havas (Eds), 255-82. New York: Plenum Press.)
(NaA102) or aluminium sulfate (A12(S04)3, ‘alum’). These soluble

aluminium compounds are hydrolysed in water (Eqn 10.4) and converted to
aluminium hydroxide (Al(OH)3), a gelatinous precipitate with a high surface
area which helps to remove the colour and colloids when the suspension is
filtered.
Al3+ + 3H C 03“ ^ A1(0H) 3+ 3 C 0 2 (10.4)
Some of the added aluminium ions remain in solution and this has caused
problems to kidney patients on dialysis machines. The Donnan membranes
used in dialysis units (Figure 10.4) do not exclude aluminium as efficiently as
do kidneys. The resulting higher intake of aluminium can eventually cause
death, and this was a major problem until the cause was realized. The
aluminium can be removed from the water used in the dialysis unit by
passing it through an ion-exchange column, but because of the large
volumes involved there is a significant increase in the cost of the treatment.
There has been a lot of speculation about possible links between
aluminium and Alzheimer’s disease. People suffering from Alzheimer’s
disease have been found to have higher than normal amounts of aluminium
ALUMINIUM 163
body fluid
Donnan membrane [
water
the Donnan membrane prevents the large organic molecules passing through,
but smaller species can penetrate the membrane - there is a net transfer of small
species from regions of higher concentration to those of lower concentration
Key
| | large organic molecules, e.g. proteins
small organic molecules, the products of metabolism,

e.g. urea, creatinine
Figure 10.4 The principle of the dialysis process used in haemodialysis of patients with
defective kidneys.
in their brains. Alzheimer’s disease produces many of the symptoms of

dementia shown by dialysis patients who have suffered from aluminium
poisoning. However, it just happens to accumulate because of some change
in the biochemistry of Alzheimer’s patients that has been brought about by
some other agent. Alzheimer’s disease is characterized by the formation of
plaques of /3-amyloid protein. It is not clear whether the /3-amyloid protein
plaques are an indicator, like the aluminium build-up, or actually directly
involved as the cause of the disease. There is still concern about the possible
chronic effects of low dosages of aluminium and this is bringing about a
reduction in the use of aluminium compounds in water treatment. One
alternative is to use iron(II) compounds which react with oxygenated water
in a similar manner to aluminium (see Chapter 9), but are less efficient.
Organic polyelectrolytes have also been used, but they can cause problems
by introducing traces of potentially carcinogenic compounds into the water.
11 Calcium and magnesium
Magnesium Abundance by weight (the relative abundance is given in

parentheses): Earth, 13.5% (4); crust, 2.1% (8 ); ocean,
1.3 g dm - 3 (5).
Calcium Abundance by weight (the relative abundance is given in

parentheses): Earth, 2.1% (7); crust, 3.6% (5); ocean,
0.41 g dm " 3 (7).
Magnesium and calcium are the first two members of the alkaline-earth
group of metals. They are both major components of the Earth’s crust, and,
because of their similar electronic structures (two electrons in the outermost
shell), their chemical reactions are similar. Together with iron, they are the
major cations found in basic igneous rocks.
Despite their chemical similarity, there is only limited substitution
between magnesium and calcium in their minerals. This is because the ionic
radius of Mg2+ is 65 pm, whereas that of Ca2+ is 100 pm. This size
difference is sufficient to prevent the large-scale replacement of one ion by
the other. It is iron(II), Fe2+ (radius 61 pm), that replaces Mg2 + ; and
sodium, N a + (radius 102 pm), that exchanges with Ca2+.
The geochemical cycles of the two elements (Figure 11.1) are similar,
except for the variations brought about by the differences in solubility
between some of their compounds. The lower solubility of calcium
carbonate (C aC 03) compared to magnesium carbonate (M gC 03) leads to
extensive sedimentary deposits of limestone (C aC 03) being formed from the
dissolved calcium that has been transported by rivers into the ocean. Some
magnesium, about 5% on average, was incorporated in these limestone
deposits as they were precipitated. In addition, dolomite (C aC 0 3 -MgC03)
may be formed as a mineral in its own right. Both calcium, as the sulfates
anhydrite (CaS04) and gypsum (CaS0 4 -2H2 0), and magnesium, as the
chloride (MgCl2 -6H2 0 ) and as sulfate (M gS04), are found in evaporite
deposits. Again the lower solubility of the calcium sulfates leads to them
being formed first. These precipitation processes all favour the removal of
calcium in preference to magnesium from sea water. There is a marked
reduction in the proportion of calcium relative to magnesium in sea water
(Ca2+ = 1.2% dissolved solids; Mg2+ = 3.7% dissolved solids) compared
CALCIUM AND MAGNESIUM 165
Mg2+ (1.3 g dm 3)
C sr+ (0.41 gdm )
in solution
Mg2+,C a 2 >in OCEAN
in solution
evaporation
weathering . solution
EVAPORITES
weathering C aS04
C aS 04.2H 20
MgCl2.6H 20
CaCO
M gS04
(C a M g )C O ,
uplift C a „ ,(P 0 4)6 C a (F ,0 H )2
Mg, Ca basic
igneous rocks
SEDIMENTARY Mg2+
ROCKS «---- - forms clays
uplift ' (limestone, dolomites,
phosphate rock)
remelting
IGNEOUS
ROCKS
MANTLE
Figure 11.1 Geochemical cycles of magnesium and calcium.
with river water (Ca2+ = 20% and Mg2+ = 3.4% of dissolved solids). The
residence times in the ocean of magnesium (15 x 1 0 6 years) and calcium
( 1 x 1 0 6 years) also reflect the lower solubility of the calcium compounds.
The reaction that removes the excess of the magnesium involves absorption
by clay minerals and the formation of new clay minerals such as chlorites
(Eqn 11.1).
Al2 Si2 0 5 (0 H ) 4 +5Mg2+ + Si0 2 +10H C 03~ — >

kaolinite
M g5Al2Si30 ,o (O H )8 +10C 0 2 + 3H20

chlorite
166 MAJOR E L E ME N TS F O U N D IN THE EA RT H S CRUST
11.1 Formation of calcareous rocks
The behaviour of calcium in the oceans underwent a major change with the
development of life-forms that incorporated Ca2+ in their skeletons.
Originally the removal of calcium carbonate from the oceans was by means
of normal inorganic precipitation reactions (Eqn 11.2) which occurred when
the combined concentration of calcium and carbonate ions exceeded the
solubility product of calcium carbonate.
C a ^ + C O ^j^C aC O jw (11.2)
The majority of limestones have been organically formed for at least the past
600 million years. The low solubilities of many inorganic calcium
compounds, especially calcium carbonate and the apatites (e.g.
hydroxyapatite, Ca 3 (P0 4 )2 Ca( 0 H) 2 ; fluoroapatite, Ca 3 (P 0 4 )2 CaF2), have
made them especially suitable for skeleton building. Skeletons are either
exterior to the soft parts - exoskeletons - as with insects and shellfish, or
internal - endoskeletons with the muscles and other soft tissues surrounding
this skeleton, as in mammals and fish. The exoskeletons of insects are
usually composed of organic polymers, such as chitin, and some sponges
have silica (Si02) skeletons; but the majority of other invertebrates (with
shells) and vertebrates (with internal skeletons) have calcium-containing
hard parts.
The solubility of calcium carbonate is controlled by the concentration of
both Ca2^ and CO2^ . As sea water is a relatively concentrated solution
containing a large number of components, species other than the free
dissolved calcium and carbonate ions are present. Of particular importance
are species called ion pairs. Ion pairs are associations between two
oppositely charged ions which form new soluble species (Figure 11.2) and
which, therefore, reduce the concentrations of the free hydrated ions. In
addition, more complex species may be produced by the association of the
metal ions with several anionic groups, e.g. HgCl|“ , the tetrachloro-
mercury(II)ate ion. The concentration of free carbonate ion, CO2^ , is
reduced to about 1 0 % of the expected value due to formation of ion pairs,
for example, 60%-70% of the carbonate is found as the MgCO^ ion pair
and 15%—20% as NaCO^. A greater proportion of the calcium (up to 90%)
appears to be present as the free ion, C a?^, with C aS04, CaHCO^ and
inorganic calcium complexes as the other major species. Theoretical
calculations of compound formation based upon thermodynamic stability
data can only be approximate because of the many interactions and our very
incomplete understanding of what species are actually present in sea water.
In general, conditions that favour the extensive production of limestone
deposits require clear waters and the absence of silicates brought into the
area by rivers. As a consequence, many limestones are relatively pure, with
CaSO'i MgCO"
CaHCOj NaCOj
@ ) 0
<W )
Ion pairs charged and uncharged,
Typical ions found in sea water found in sea water as soluble species
Figure 11.2 Examples of ion pairs found in sea water.
some being at least 98% C aC 03. These pure deposits are now much prized
as sources of lime (calcium oxide, CaO) for industrial processes such as steel
making, glass making and sugar refining. Millions of tonnes of lime are
consumed in these industries each year. Unfortunately, in the UK, the areas
of purest limestone are also areas of outstanding natural beauty and often in
national parks. There is, therefore, a conflict between the industrial require
ments that lead to large quarrying operations and the need to preserve the
few undeveloped areas left.
11.2 Water hardness
Carbonate rocks are rapidly eroded when exposed to water containing

dissolved carbon dioxide (Eqns 11.3 and 11.4), although dolomite
(C aC 0 3 M gC 03) is more resistant than limestone (C aC 03).
C aC 03(s) + C 0 2 + H20 ^ Ca2+q) + 2H C 03- (11.3)
M gC 03(s) + C 0 2 + H20 ^ Mgf + } + 2H C 03- (11.4)
The higher the concentration of dissolved calcium and magnesium in the

water, the harder the water is said to be. Hard water containing the
bicarbonates of calcium and magnesium is said to have temporary hardness
because the equilibria in Equations 11.3 and 11.4 are reversed on boiling and
the carbonates are precipitated. This removes the calcium and magnesium
from solution. If the precipitation occurs in boiler tubes, kettles or hot-water
pipes, the efficiency of heat transfer is reduced, the tubes may become
blocked and the operating costs are increased. A less common type of
hardness in fresh waters is due to the presence of sulfate ions and is called
permanent hardness, which is not all removed on boiling the water. The
solubility of calcium sulfate is lowered with a rise in temperature so there is a
slow build-up of deposits in the pipes. Both types of hardness lead to the
formation of insoluble scums with soaps.
A soap is the soluble sodium or potassium salt of a long-chain fatty acid,
such as stearic acid (Figure 11.3). The calcium and magnesium salts are
insoluble and do not have the dirt-removing properties of the sodium and
potassium salts. Therefore, their formation increases the amount of soap
that must be used and the scum may be difficult to remove from washed
clothes. Organically based detergents usually contain sulfonic acid groups
(Figure 11.3) and form soluble salts with calcium and magnesium.
Therefore, there is no scum and their effectiveness as cleaning agents is only
slightly reduced. The cleaning action is due to the hydrophobic (‘water
hating’) organic tail of the molecule being attached to the dirt or grease
particle, and the hydrophylic (‘water loving’) portion of the molecule
(a) Sodium stearate

A biodegradable soap, C 17H 35CO O "Na +
O
//
c
17 15 13 11 9 7 5 3 1 \
0~N a+
(b) Branched-chain organic detergent

An alkylarylsulfonate, RArSC>3 Na+, only slowly biodegraded
H H H H H H H H H
H,C— C — C — C — C — C — C — c — C — C —d h— S O iN a +
I I I I I I I I I A -! / i
C H j H C H 3 H CH, H C H , H CH 3|
branched alkyl group (R )
(c) a -dodecanebenzenesulfonate
11 9 7 5 3
A linear organic detergent,
(C 8H 17)C H (C 3 H 7 ) ( C 6 H 4 S 0 3 ) N a \
biodegradable
S O iN a +
Figure 11.3 Examples of soaps and synthetic detergents.

CALCIUM AND MAGNE SIUM 169
forming hydrogen bonds with water molecules. This allows the dirt particles
to be dispersed in the water and removed from the object being cleaned.
Soaps are biodegradable (broken down by microorganisms) so that excess
soap entering sewers is rapidly converted to the insoluble calcium and
magnesium salts that do not lower the surface tension of water and so do
not cause foaming. The original organic detergents were branched-chain
compounds (Figure 11.3) that were only very slowly biodegraded which
caused extensive foaming in sewage works and water systems. Straight-chain
compounds (Figure 11.3) that are rapidly biodegradable are now used to
reduce these problems.
Detergents contain other compounds - up to 90% of solid detergents are
‘other compounds’ - that may be viewed with some concern regarding their
environmental impact. One group of additives that can cause problems are
the polyphosphates. These were discussed in Chapter 7.
Although hard water causes problems due to the ‘furring’ of pipes and
kettles and the inefficient use of soaps, soft water can also cause problems.
Soft water tends to have a low pH, due to the absence of dissolved
carbonates, and it can be corrosive enough to dissolve the metal from water
pipes. Lead is soluble under these conditions and lead poisoning is a
recognized hazard in soft-water areas where lead pipes are used. In the UK,
the water authorities artificially harden the water in soft-water areas. This
may be achieved by mixing hard and soft waters, or by adding lime to the
water supply to raise the pH.
11.3 Heart disease
A number of studies carried out in the past appear to have indicated a

negative correlation between death (mortality) from heart disease and the
hardness of the water supply, i.e. the harder the water, the fewer the deaths
from heart disease. However, it has not been possible to relate any specific
‘water factors’ directly to specific heart disease effects, despite earlier views
that such a factor would be identified. This section will illustrate the extreme
difficulties that arise when attempting to relate possibly subtle environ
mental factors to the health of the population. Similar problems were
encountered with the relationship between high aluminium levels in the
brain and Alzheimer’s disease. Heart disease is the leading cause of death in
industrial countries and it has been estimated that in England and Wales as
many as 1 0 0 0 0 extra deaths per annum due to heart disease occur in men
aged 45-64 years who live in soft-water rather than hard-water areas. The
difficulty has been to determine whether there is a real connection between
the water supply and heart disease. There could be some other factor
affecting the incidence of heart diseases that also happens to correlate with
water type.
170 MAJOR E L E M E N T S F O U N D IN THE EA R T H S CRUST
In many countries, there is a geographical distribution of areas of higher

and lower incidences of heart disease that appears to correlate with
particular geological and geochemical environments. In European countries,
populations living on older rocks tend to have higher death rates due to
heart attacks. For instance, in 1967 death rates per 100 000, for both sexes
and for all ages, were 314 ± 29 for rocks older than 600 million years and
159 ± 50 for rocks younger than 180 million years. The older geological
rocks tend to contain fewer carbonates and the water supply in these areas
is, therefore, softer. Geochemically the rocks also have lower concentrations
of trace elements. In the USA, higher heart-disease death rates are
associated with rocks, soils and waters deficient in trace elements, but again
the waters are softer. In 1968-72 death rates per 100 000 whites, for both
sexes and for all ages, were 366 d= 32 (high in trace elements) and 428 ± 39
(low in trace elements) for heart diseases, but 432 ± 70 (high in trace
elements) and 424 ± 44 (low in trace elements) for other causes of death.
These results could indicate that it is the lack of some trace elements that is
related to the higher death rates, rather than the presence of calcium and
magnesium salts in the water supply. In that case, the artificial hardening of
the water supply by the addition of lime would not decrease death rates.
Adverse climatic conditions often correlate with death rates. In the UK,
the soft-water areas are in the west where the climate is wetter so the soft-
water-mortality correlation may be accidental.
A further difficulty arises because heart disease is a general term including
a number of clinically different conditions. In different countries the
associations with water supplies have been between different members of the
group, with no common pattern from country to country.
It is clear that many of the investigations have either not been planned
carefully enough or suffered from a lack of adequate data. One study was
originally interpreted as indicating a 47% reduction in mortality rates over a
10 year period when the hardness of the water were changed from 0.5 to 220
ppm. Unfortunately, the population change that had occurred was not
taken into account, and when the data was reinterpreted taking this factor
into account the reduction in death rate was only 16% compared to a 13%
reduction found for the whole of the USA during the same period.
Detailed studies of individuals and of the possible environmental factors
that may be affecting them are extremely expensive, large populations are
required to avoid statistical bias and the study must be carried out for many
years. The alternative is to make use of data already collected, such as
analyses of water supplies by water authorities and mortality data from
death certificates, together with small-scale detailed surveys. Problems arise
because (a) health authorities do not cover exactly the same areas as water
authorities; (b) populations move and the places in which people die may
not be the places in which they lived for most of their lives; (c) the death
certificate may not accurately indicate the condition of the heart in relation
to other health factors at the time of death; and (d) social and economic
factors may be difficult to identify.
The specific water factor has not been identified, although suggestions
were that:
(a) hardness may provide protection - possibly by preventing dissolution of
lead and cadmium from water pipes. Both these metals can produce
high blood pressure, one of the precursors to heart attacks;
(b) some of the trace elements in hard water may provide protection, e.g.
lithium is thought to be beneficial, at small concentrations, in reducing
anxiety; and
(c) the low concentration of trace elements in soft water may result in a
deficiency of protective agents.
12 Sodium and potassium
Sodium Abundance by weight (the relative abundance is given in

parentheses): Earth, 0.3% (9); crust, 2.8% (6 ); ocean, 1.05%
(4).
Potassium Abundance by weight (the relative abundance is given in

parentheses): Earth, 150 ppm (14); crust, 2.6% (7); ocean, 0.39
g dm - 3 (8 ). ppm = mg kg-1.
Most sodium compounds that are not silicates have high solubilities. This
means that once the primary silicate minerals such as feldspars have been
broken down by weathering, the sodium is rapidly leached out of the soils
and transferred to the ocean. The only barrier to the rapid removal in
solution is the tendency of sodium ions to be strongly adsorbed by clays and
organic materials that have surface negative charges. The sodium con
centration (mean: 6 mg kg-1) in fresh waters is lower than that of calcium
(mean: 15 mg kg-1), a consequence of the greater stability of sodium
silicates and their lower average concentration in the Earth’s crust. In sea
water, the high solubility of sodium salts is indicated by sodium’s long
residence time (210 x 106 a) and the fact that it is the major cation (10.54
g kg-1), with magnesium second (1.27 g kg-1), calcium third (0.4 g kg-1)
and potassium fourth (0.39 g kg-1).
Potassium and sodium are in the same group in the periodic table. Their
simple salts have similar solubilities but their geochemical behaviour differs
in a number of ways (Figure 12.1). Sodium and calcium undergo iso-
morphous replacement in silicates because of their similar ionic radii,
whereas potassium is found in separate primary igneous minerals (ortho-
clase feldspar and micas). The weathered potassium silicates release
potassium ions but these are even more strongly adsorbed by negatively
charged clay and organic colloids than are sodium ions. Unlike sodium, the
potassium is readily reincorporated into silicate structures with the
formation of clay minerals and its concentration in biological material is
about 15 times greater than that of sodium. As a consequence the
concentration of potassium in fresh waters is about one-third that of sodium
and its residence time in the ocean is 1 0 million years.
SODIUM AND POTASSIUM 173
IG NEO US
ROCKS
Figure 12.1 Geochemical cycles of sodium and potassium.
12.1 Clay minerals
The clay minerals are hydrous aluminium silicates (contain Al, Si, O and
OH) of small size with a layered structure. This characteristic structural
feature is made up of sheets of either tetrahedral [Si04] units or octahedral
[A106] units (Figure 12.2). The [Si04] tetrahedra are linked together by the
sharing of three basal oxygen atoms with their apexes all pointing in the
same direction. The octahedral units contain two layers of close-packed
oxygens and hydroxyls surrounding the aluminium. The relative number of
oxygen and hydroxyl groups varies to satisfy the charge-balance criteria for
the structure.
The simplest of the clay structures in shown by kaolinite
(Al4 Si4 Oi 0 (OH)8), with one octahedral sheet and one tetrahedral sheet
forming a 1:1 clay mineral (Figure 12.2a). Successive 1:1 layers are stacked
above each other and held together by hydrogen bonds between the oxygens
in one layer and the hydroxyl groups in the next layer. The hydrogen bonds
(a) Kaolinite
6(O H)
4A1
4 0 + 2 (OH)
4Si
60 hydrogen bonding between
O and OH
6(O H )
4A1 octahedral sheet
40 + 2 (OH)
4Si tetrahedral sheet
60
(b) Montmorillonite (c) Illite
60
4 (S i, Al)
4 0 + 2 (0 H )
4(A1, Fe, Mg)
4 0 + 2 (O H)
4(Si, Al)
60
exchangeable cations
and/zH 20
O O k*
60
4 (S i, Al)
4 0 + 2 (O H)
4(A1, Fe, Mg) <
CL
u
4 0 + 2 (O H) <L>
4 (Si, Al)
60
Figure 12.2 Representations of the structures of (a) kaolinite, (b) montmorillonite and
(c) illite.
prevent other groups from entering between the individual layers and keep
the structure relatively rigid. Kaolinite shows only a limited amount of
isomorphous replacement of the Al and Si, aluminium and silicon, and the
composition of kaolinite corresponds very closely to the ideal formula given
above.
Members of the other major group of clay minerals, the smectites, each
consist of one octahedral sheet sandwiched between two tetrahedral sheets
(Figure 1 2 .2 b). Montmorillonite (Al4 (Si4 O i 0 ) 2 ( O H ) 4) and illite (K 0 _ 2 A 14
(Si8 _ 6 Al0 - 2 ) 0 2o (O H )4) are the two most common members of the 2 : 1 clays.
In each case the oxygens of one 2:1 layer always face the oxygens of the next
layer and, therefore, no hydrogen bonding can take place. The layers are not
so strongly held together, and ions such as K + in illite and small molecules
such as water in montmorillonite can enter between the layers.

Montmorillonite-containing clays are described as expanding clays because
when water enters between the layers the repeat distance (Figure 12.2b) can
increase from 0.96 to 2.14 nm. During dry periods, the water will leave the
clay and it will contract again. The entry of potassium between the layers to
form illite is only reversed with difficulty. The potassium ions tend to hold
the layers together at a fixed distance apart and make the entry of water
difficult. Kaolinite and illite are described as non-expanding clays.
Montmorillonite clays never have their ideal formula and show extensive
isomorphous substitution with up to 15% of the silicon in the tetrahedral
units replaced by ions such as aluminium. In the octahedral units, there may
be up to 100% replacement of the aluminium by ions such as Mg2+ and
Fe 2 + , with smaller amounts of Zn 2 + , Ni2 + , Li + , Cr 3 + , etc. The sub
stitution of Al3+ for Si4+ and the divalent cations for Al3+ leaves a
positive-charge deficiency that may be compensated for by (a) OH-
replacing O2-, (b) excess cations entering into the one-third unfilled
octahedral positions found in the ideal structure, or (c) the sorption of
cations on to the surface of the layers. All three compensation mechanisms
occur and montmorillonite has a high cation-exchange capacity due to
mechanism (c).
The ability of a soil to exchange cations is called the cation-exchange
capacity (CEC) quoted as milli-equivalents per 100 g of soil. (1 milli-
equivalent = 1 millimole of a t/mpositive cation, e.g. Na + , which is
23 x 10~ 3 g; 1 milli-equivalent = 0.5 millimole of a ^/positive cation, e.g.
Ca 2 + , which is 20 x 10~ 3 g.) Organic materials exchange cations mainly
due to the presence of the carboxylate group, -COO~. Humus usually has a
very high cation-exchange capacity, e.g. CEC of peat = 300^100 compared
to CEC of typical soil = 10-30. Kaolinite has a relatively low CEC, which is
due to the exchange of H + ions from the hydroxyl groups on the clay
surfaces. The hydroxyl groups of montmorillonite react similarly, but the
greater degree of isomorphous substitution and the consequent excess
negative charges lead to a higher CEC.
An equilibrium state is set up in a soil in which the proportion of an ion in
solution and sorbed on to the surface of the clay or humus depends on (a)
the concentration of metal ions present and (b) the acidity of the soil. The
equilibrium can be changed by changing either (a) or (b) or both (Figure
12.3). The concentration of an ion in solution may be reduced by uptake by
plant roots. Some ions will then be released from the cation-exchange sites
to restore the equilibrium and hence more of the ion will become available
to the plant. The process will continue until there is no more of that ion
sorbed on the clay or humus. In general, a high proportion of the cation-
exchange sites on organic matter are occupied by hydrogen ions unless the
—Q Na ~ Y © k* -0 Ca2+
- e -© K *
c Mg2+potassium^ liming
C Ca2
^
L -© K * L “0
A fertilizer A A
Y
l" ° Y Y
- 0 H * -© K * - 0
Ca2
-0 N H J -© K * J-0
+ Mg(2aq), Na^q), H(+aq), NH 4(aq) + K|aq)
H+
H+ H+ H+ H+ H+
f OAY J
acid soil, metal ions in solution
Figure 12.3 Examples of how changing the concentration o f cations can change the
equilibrium between the cations held by the clay and those in solution.
pH of the soil is raised by liming. The cation-exchange sites can be an

important reservoir of essential metal ions for plants as they reduce the rate
of leaching of these soluble ions, provided that the pH is not too low.
12.2 Potassium fertilizers
Potassium is one of the three major fertilizer elements, the others being
nitrogen and phosphorus. In 1939, about 67000 tonnes of potassium was
used in fertilizers in the UK. Annual consumption is now about 350000
tonnes. In general, the potassium status of UK soils is satisfactory and only
maintenance dosages are added - enough potassium is added to compensate
for the potassium removed in the crops. This is because any excess
potassium added is largely retained in the soil by sorption on clays and
organic matter. (This is unlike the case of nitrogen, in which any excess is
leached out of the soil.) Soils generally have low anion-exchange capacities
and once the nitrogen is converted to nitrate it can be readily removed in
solution. The clay minerals have a limited anion-exchange ability through
the replacement of hydroxyl ions on crystal edges (Eqn 12.1).
clay —OH + anion — ►clay —anion + OH (12.1)

Nitrate is only weakly held at these sites. Phosphate ions, PO 4 - , are more
strongly held and also react with aluminium and iron oxides to form
insoluble compounds that prevent leaching out of the phosphate.
In areas where crops have been grown for many years without the
addition of adequate potassium-containing fertilizers, yields gradually
decrease as the potassium from between the illite layers is slowly removed. If
potassium fertilizer is then added, the increase in yield is not as great as
might be expected. This is because the potassium returns to the illite
structure rather than remaining immediately available for plant growth. As
a consequence the farmers are faced with the high costs of potassium
fertilizers without receiving a comparable increase in crop yield. This
constitutes a major problem for subsistence farmers, who cannot afford to
carry the extra costs without an immediate return. As a result, unless
external help is provided, they cannot afford to improve their impoverished
soils. High yields of any crop can be sustained only by replacing the
nutrients removed with the crop. This is expensive enough for the farmers of
the developed countries, even with high food prices and subsidies; applying
adequate fertilizer is virtually impossible for the farmers of Third World
countries who lack the same organizational back-up. Large areas of the
Earth’s surface are less productive than they might be with proper
investment and management.
12.3 Fluids in organisms
A cell absorbs required chemical species through the phospholipid

membrane that constitutes the cell wall and excretes unwanted material
through the same barrier. In the case of unicellular organisms, the
interchange is directly with the environment in which it lives, but with more
complicated organisms the majority of the cells are not in contact with the
external environment. The development of multicellular organisms has been
paralleled by the development of a body-fluid system that maintains a
controlled internal environment, transfers essential chemicals to the indivi
dual cells and removes the unwanted waste chemicals. The extracellular fluid
is usually mainly composed of an aqueous solution containing sodium,
potassium, magnesium and calcium cations, with chloride and bicarbonate
as the major anions, together with soluble proteins and organic acids. Other
soluble species are present as minor constituents.
The concentrations of ions inside and outside cells are often quite
different. Particularly marked in humans are the high concentrations of
potassium and magnesium ions inside cells and the high concentrations of
sodium and calcium ions in the blood serum (Table 12.1).
Maintaining these segregations is of great importance for the correct
metabolic functioning of organisms. For example, the difference in sodium
and potassium concentrations across cell membranes leads to electrical
potential differences across the membrane. Changes in this potential
difference by the sudden influx of sodium ions enable the transmission of
nerve impulses. Both sodium and potassium are able to pass through the cell
wall and, because of the concentration differences, the natural tendency
would be for the sodium to pass from the high-concentration solution
outside the cell to the lower-concentration solution inside the cell and for
potassium to move in the opposite direction (Figure 12.4). The maintenance
of the N a +- K + differential across the cell wall involves the active removal
of sodium from the interior of the cell by an ion-pump mechanism. It has
been suggested that up to half the basal metabolic rate in humans is
dedicated to operating this sodium pump, which is driven by the hydrolysis
of ATP.
The walls of cells act as Donnan membranes. This means that some of the
dissolved species are unable to pass through the cell wall or can only pass
through under certain conditions. Water, the solvent, passes through a
semipermeable membrane from the more dilute solution to the more
concentrated solution until the concentration of dissolved species is the same
in both solutions. This process is called osmosis. The flow of solvent can be
prevented by applying a pressure to the more concentrated solution. The
size of the applied pressure required to prevent the solvent flow is called the
osmotic pressure. The greater the concentration difference across the
semipermeable membrane, the greater is the tendency for the solvent to pass
through and the higher is the osmotic pressure. If the ionic strength inside a
cell is greater than the ionic strength in the extracellular fluid, water will tend
to enter the cell causing it to swell. Single-celled marine organisms placed in
fresh water (which has a low ionic strength) are no longer in ionic balance
with their surroundings, water enters the cells and eventually they burst.
Conversely, freshwater organisms when placed in sea water (which has a
high ionic strength) lose water and shrivel up as they dehydrate.
Multicellullar organisms have developed quite sophisticated mechanisms to
equalize ionic strengths and overcome osmotic effects either inside their
bodies or due to external influences.
Table 12.1 Concentrations of cations in human intracellular and extracellular fluids
Na + K+ Mg2 + Ca2 +
Blood serum (gdm 3) 3.3 0.2 0.03 0.1

Cellular fluid (g dm ) 0.23 4.3 0.49 0.00004
Figure 12.4 The transport of sodium and potassium ions across cell membranes by the
sodium-pump mechanism.
12.4 Radioactive potassium
The naturally occurring isotopes of potassium are (93.1%),

(0.0119%) and 1 9 K (6.9%). 40K is radioactive with a half-life of 1.27 x 109 a
and undergoing decay by either ^-electron capture or f3~ decay (Eqns 12.2
and 12.3).
gK + > — g Ar — * " A , + y (12.2)

K electron excited ground state gamma ray
«>K(^ ) 4°Ca + / ? > r _ « e ) (12.3)

beta radiation
Potassium-argon radiometric dating is widely used for estimating the age of

geological systems and events. Providing the 40Ar has not diffused out of the
mineral or rock under examination, the amount present indicates how much
40K has decayed.
The energy released by the decay of radioactive 40K is the third most
important source of radioactive or radiogenic heat in the Earth’s crust.
Uranium and thorium each provide about three times as much heat as 40K
now, because their longer half-lives have kept their present concentrations
closer to their original concentrations. There is only about 10% of the
original quantity of 40K present in the Earth’s crust now, together with
about 50% of the original 238U and 80% of the original 2 3 2 Th. This means
that the 40K must have been the major source of radiogenic heat in the early
stages of the Earth’s history. Most of the present heat flow through the crust
can be accounted for by the presence of 2 3 8 U, 232Th and 40K in the crustal
rocks. The natural background radiation on the Earth’s surface is also
largely due to the presence of these radioactive elements and their decay
products.
Part Four Minor elements and environmental
problems
In the preceding chapters we have examined elements that are major

components of the Earth and its life-forms. In those that follow, we shall
look at a number of elements that are generally present only in small
quantities in natural systems. However, because of industrial and
agricultural processes, the geochemical cycles of these trace elements have
been significantly modified, leading to concern about their polluting effects.
There is also a chapter looking at a number of persistent organic chemicals
whose concentrations in soils, water and living organisms have markedly
increased in the second half of the twentieth century. As humans have
striven to improve their living conditions, they have made increasingly large
demands upon terrestrial and biological systems. Some of these effects have
already been described; we shall now look at a number of cases which
highlight the conflict between ‘humanity’ and ‘nature’. Humans are
inescapably a part of the natural system and any disruption of ‘nature’
inevitably affects ourselves.
Chemical pollution is understood to mean a high level of some chemical
substance that adversely affects the natural environment. Pollution can be
thought of as being the presence of too high a concentration of a resource in
the wrong place at the wrong time. This emphasizes the view that pollution
involves the misuse of resources: what may be correct for one system may be
incorrect for a different system. The use of nitrate fertilizer is a good
example of a chemical that may be either a useful resource or a pollutant.
Nitrate added to the soil during the growing season is utilized by plants to
give increased growth. The same nitrate fertilizer, if allowed to enter a
water-supply reservoir, can make the water unsafe to drink also leading to
algal blooms and eutrophication in the reservoir. There is a tendency to
think of pollution as being only anthropogenic, but there are also natural
events that produce harmful effects identical to those produced by human
interference in the system. These natural events can also be classified as
pollution. Natural oil seepages and high levels of toxic metals in soils due to
the weathering of mineral deposits are two examples.
It is easy to recognize high-intensity pollution episodes such as the
London smog of 1952 or the grounding in 1978 of the Amoco Cadiz , a large
oil tanker, when 2 2 0 0 0 0 tonnes of oil was released (a much larger quantity
182 MINOR ELEMENTS AND E N VI RO NM E NT AL PROBLEMS
than the 35 000 tonnes that escaped from the Exxon Valdez when it ran
aground in Alaska in 1989). What are much more difficult to recognize are
the slower changes and modifications to ecosystems that can occur as levels
of potentially toxic chemicals build up. The problem may go unrecognized
until it is either too late to reverse the effects or too late to save a substantial
proportion of the affected population. This may be due to the natural
variations in ecosystems making changes difficult to detect and to a long
period of time elapsing between contamination occurring and the effect
becoming noticeable. In the manufacturing, chemical and agricultural
industries there have been numerous examples of substances being used that
were later shown to be health hazards. One example is provided by the
naturally occurring mineral asbestos which has now been shown to be
carcinogenic and its use has consequently been severely curtailed.
Asbestos
Asbestos exposure is associated with two types of cancer. Lung cancer is
dose related, i.e. the greater the exposure, the higher the likelihood of lung
cancer, and the lungs of these cancer sufferers have been found to contain
about 1 g of asbestos. There is a synergistic relationship with smoking. One
study of the life expectancy of workers exposed to asbestos has shown that,
with the smokers, 50% had died of lung cancer before reaching the age of 53
years; whereas with non-smokers, 50% had died of lung cancer by the age of
72 years. This form of cancer can be reduced by dust suppression and the
prevention of smoking.
The second type of cancer, called mesothelioma, is associated with much
smaller exposures (accumulations of less than 1 mg being fatal) and is not
related to smoking. What is even more worrying is that many sufferers were
not employed in the asbestos industry, but were either members of the
families of asbestos workers or lived in the vicinity of asbestos-using works.
The period between exposure and recognition of the tumours varies between
15 and 50 years, with an average of about 40 years. Mesothelioma appears
to be associated with amphibole asbestos fibres (Figure P4.1) such as
crocidolite. These are straight and more chemically inert than chrysotile,
which has a coiled configuration and which tends to disintegrate in the lungs
as magnesium is leached out of it. Research into causes and effects has been
slow due to problems in identifying the various types of asbestos and in
relating the degree of exposure to the incidence of the disease because of the
long development time. Even if all use of asbestos was now banned, the
number of people dying from mesothelioma would be likely to go on rising
due to exposure in the past 40 years.
Mesothelioma occurs in a village in Turkey where the local soft rock is
used to build houses. In the period 1970-74, 70% of the deaths were due to
MINOR ELEMENTS AND EN VIRONMENTAL PROBLEMS 183
Adverse health effects

Asbestosis lung cancer mesothelioma
prevention of enhanced by unusual cancer
Types of asbestos 0 2 uptake smoking associated with
by lungs cigarettes short straight
fibres
chrysotile
(white asbestos)
90% of
total
production
in 1975
amphiboles
amosite
anthophyllite |
actinolite > minor
tremolite usa8e
crocidolite • • •
(blue asbestos)
Key
# high probability of causing adverse effect
O lower probability of causing adverse effect
Figure P4.1 The different types of asbestos and their tendency to cause adverse health effects.
mesothelioma and 10% were due to lung cancer. Although there is no

asbestos in the dust, there are similar fibrous minerals of the correct size
(0.1 ii m diameter and 2-20 jim long) to cause cancer. It seems likely that all
fibrous materials should, therefore, be viewed with concern. Further
problems highlighted by the asbestos case are that once inhalation has
occurred there appears to be no way either of predicting whether an
individual will actually develop mesothelioma or of preventing the cancer
developing.
Although the hazards due to asbestos usage have taken a long time to
become recognized, at least they are now well documented and steps can be
taken to control the use of asbestos. Mesothelioma is so unusual that its
increased occurrence was quickly noticed. If a pollutant produces an effect
that is more subtle, such as reducing intelligence levels by 5% or increasing
the incidence of bronchitis by 5%, there is a very much smaller chance that
the change will be recognized. Therefore, the quality of life can be degraded
184 MINOR ELEMENTS AND EN VIRO NM ENT AL PROBLEMS
without the effect or the cause being identified. Quality of life is a concept
that extends to the lives and habitats of all living organisms and gradual
changes to these dynamic and often complex systems are equally difficult to
detect.
Changes in cycling rates
The natural fluxes in all elements follow a cyclical path through the same
major reservoirs. The differences between the sizes of the fluxes and the
amounts in the reservoirs reflect both the chemical properties of the elements
and the quantities of these elements actually present near the surface of the
Earth. Human activities have increased a number of the fluxes associated
with natural cycles, especially in the pathways that led from the land-based
to the ocean-based reservoirs.
Land-use has been modified by building cities and transport systems, by
agricultural developments and by deforestation. As a result erosion rates are
now estimated to be two or three times what they were before humans
changed from a mobile hunter-gatherer life-style to that of a settled
community. Although it is difficult to be precise about the actual increase in
rates of erosion, the loss of productive land has been estimated as 6 x 1 0 4
km 2 a - 1 due to desertification, 7 x 104-20 x 104 km 2 a - 1 due to defores
tation and 0.6 x 104 km 2 a - 1 due to urbanization. These figures indicate
that 0 . 1 % - 0 .2 % of the ice-free land mass is losing its productive soil cover
each year. These losses are seen to be very significant when one realizes that
the world’s population is growing at a rate of 1.7% per annum and that the
productive land area is only about one-third of the total land area. The
increased erosion rates increase the fluxes of all elements from land to ocean
and also increase the loss of volatile elements (e.g. mercury and radon) from
the land to the atmosphere.
Extraction of useful materials by mining, quarrying and subsequent
processing has a much more specific and localized effect than the general
increase in erosion from land-use change discussed above. The quarrying of
building stone, the extraction of gravel and sand for building purposes, of
shale and limestone for cement and chemicals, of phosphate rock for
fertilizer, and of sodium and potassium chlorides for chemicals and
fertilizers, have between them mobilized much greater tonnages than has the
mining of ores for metallic elements. However, we shall largely concentrate
on the metals because they are more limited resources that are posing more
acute environmental problems.
The mining of a deposit for one element may cause the release of other
elements and compounds. For example, chalcopyrite, CuFeS2, may be the
economic mineral that is being mined as a source of copper. The
concentration of the mineral in the ore is likely to be low, e.g. 2 %, and only
MINOR ELEMENTS AND ENVIRONMENTAL PROBLEMS 185
about one-third of the mineral is copper. This means that about 99.3% of
the ore body is removed from the ground, broken up and then dumped.
Elements other than the one being specifically mined are likely to be
mobilized. In the chalcopyrite case, iron and sulfur are obvious examples,
with the sulfur being converted to either sulfur dioxide or sulfuric acid.
Mining operations are transitory in nature. The lifetime of the mine is
dependent upon the economic situation and the presence of the required ore.
The term ‘cut-off grade’ is used to indicate the lowest concentration of the
required element or mineral that can be economically exploited. The average
cut-off grade varies widely from element to element - e.g. iron, 30%; lead,
2%; gold, 0.0003% - as do production rates, reserves and projected lifetimes
of these reserves. The consumption of metals is much greater in the so-called
developed countries than in the Third World countries. For instance, the
USA, with 5% of the world’s population, consumes 30% of the world’s raw
materials. If the underdeveloped areas become developed in the modern
meaning of the term, consumption rates will rise rapidly and resources will
be depleted that much more rapidly. Even with new processes, the energy
required for the extraction of metals from less concentrated ores will rise
very rapidly, creating resource pressures on all fuels, whether fossil, nuclear
or biomass.
The extraction of ores followed by the reduction of the combined metal to
its elemental form generally involves large inputs of energy and produces
environmental problems with the disposal of the wastes. Both of these
factors could be alleviated, and the resource pressure problems could be
reduced, by the recycling of the metals. As we have already seen with
aluminium and steel, there are large energy savings to be made by recycling,
but collection and separation of the required metals from the redundant
manufactured articles can be very difficult. Quite large quantities of recycled
scrap are already utilized, for instance, in Western Europe and the USA,
about 50% of aluminium, 60% of copper, 40% of lead and 25% of steel are
recycled.
Essential and toxic elements
Some elements have been found to be essential for life, but all elements are
harmful at excessive concentrations. It must always be remembered that the
chemical form of the element modifies its usefulness to an organism.
Hydrogen, carbon and nitrogen are essential to humans, but they are useless
in their elemental forms, and they are highly toxic if combined as hydrogen
cyanide, HCN. It is, therefore, an oversimplification to state that certain
elements are essential and other elements are toxic. The element must be in
an available form for it to interact with an organism. Although elemental
nitrogen comprises 80% of the atmosphere, it is not available to the
186 MINOR ELEMENTS AND EN VIRO NM ENT AL PROBLEMS
Concentration of nitrate, or any essential element,

available to plant
Figure P4.2 Idealized growth-response curve for the effect of changes in concentration of
nitrate on plant growth.
majority of living organisms and so it is neither essential nor toxic, there is

simply no interaction.
Nitrate, N 0 3~, is soluble and available to the majority of organisms. If
plants are grown under conditions in which nitrate is the only source of
available nitrogen, but in which all other nutrients are present in adequate
amounts, then a growth-response curve of the type shown in Figure P4.2
will be obtained. In the region A C there is a deficiency of nitrate and an
increase in nitrate concentration gives an increase in yield. Over the con
centration range CD there is a sufficient supply of nitrate and yield is no
longer limited by the nitrate concentration, hence the yield plateau PQ.
After Q the yield begins to drop as the concentration of nitrate becomes so
great that it interferes with other metabolic processes in the plant. At
concentrations greater than D , the nitrate is toxic and above E the plants die
as the nitrate has reached a lethal level.
If the experiment was repeated with humans, using nitrate as the only
source of nitrogen, only the portion AB of the curve would be found - the
nitrate nitrogen is for all practical purposes unavailable. If other sources of
nitrogen were available, then the human response curve would resemble
Figure P4.3. The initial plateau S T over the nitrate concentration range L M
indicates that the body can control the amount of nitrate absorbed and keep
it below a harmful level. As the concentration increases from M to N toxic
effects would cause illness and eventually death as N is the lethal level.
Curves similar to that shown in Figure P4.2 are obtained with all essential
elements when present in available forms. In fact, essentiality is recognized
by the production of this type of curve. Non-essential elements and elements
in unavailable forms would produce curves similar to Figure P4.3. The
greater the toxicity of the chemical, the shorter the stable plateau ST.
MINOR ELEMENTS AND EN VIRONMENTAL PROBLEMS 187
Figure P4.3 Idealized growth-response curve for non-essential and toxic elements.
The actual expression of the toxicity of chemical species is very difficult,

especially with regard to humans. Toxicity is generally expressed in terms of
the dose that kills 50% of a population, i.e. the LD 5 0 value. ('LD’ means
lethal dose’.) Provided a large enough population is studied, individual
variability in response, which can be very great, is taken into account.
However, toxicity effects are influenced by the mode of application (e.g.
whether by mouth, lungs, skin or injection) and by the presence or absence
of other compounds or foodstuffs. A dose of 0 . 0 2 mmol HgCl2 kg-1, which
killed 39 out of 40 rats, caused only one death out of 40 rats that were also
given sodium selenite, Na 2 Se03. LD 5 0 values are at best only indicators of
relative toxicity. Obviously, toxicity testing cannot be carried out on
humans, so there is very little detailed knowledge of toxic doses for humans.
Information gained from studies using other animals such as rats or rabbits
is notoriously difficult to interpret in relation to humans. For instance, the
rate of gastrointestinal absorption of lead (Pb2^ ) by rats is only about one-
tenth of that found in humans.
Further controversy has been generated over the effects of low levels of
potentially toxic chemical compounds. There is a lot of evidence that
elements such as lead, mercury and cadmium accumulate with time in some
organisms. However, it is not clear at what stage point T (Figure P4.3) is
reached and adverse effects are felt. The increased mobilization of elements
plus the production of compounds not usually found in natural systems put
increased strain on the ability of living organisms of all types to avoid
slipping off the S T plateau.
Despite all the publicity given to chemical pollution - local excesses of
elements - with both its actual and possible effects, there is no doubt that
deficiencies of both major and trace essential elements are a much more
188 MINOR ELEMENTS AND ENVIRO NM ENTAL PROBLEMS
widespread cause of sub-optimal growth. The essential elements are required

to make up the chemical compounds that together constitute a living
organism. There are 11 major essential elements (hydrogen, carbon, nitro
gen, oxygen, sodium, magnesium, phosphorus, sulfur, chlorine, potassium
and calcium), and there are about another 15 elements (boron, fluorine,
silicon, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,
selenium, molybdenum, tin and iodine) that are ordinarily present in plants
or animals in concentrations of less than 0 .0 1 % but which are essential to
some or all organisms - e.g. boron appears to be essential to plants but not
to animals.
Consider the distribution of the trace elements in soils (Figure P4.4).
Some forms are more available for uptake by plants than others. The soluble
ions and complex ions are directly available providing the plant root has no
specific exclusion mechanisms. The adsorbed ions are likely to be the next
most available form as in many cases they are readily displaced from their
sorption sites, particularly if conditions become more acidic and hydrogen
ions displace these cations. The availability of the trace elements dispersed in
the hydrated oxide precipitates is increased by more reducing conditions
Solid
dispersed in own compounds, dispersed in held on
silicate crystal e.g. PbS, Z n C 0 3 hydrated oxides, surfaces by
lattices, e.g. e.g. Fe and Mn ion-exchange
feldspars, clays oxide or physical
adsorption, e.g.
clays, organics
X TE X TE O Fe O Fe O -C a
• ( TE) • • TE X TE X Fe O (77?) O Fe (T j)
• • • • (te) X TE X TE O Fe O Fe O K
• • • • TE X TE X Fe O Fe O (ff) 1 Ca
increasing availability
y or x
Soluble forms L
L.
[re<H 2o )m]" :t e '
L'
hydrated ions
Key complex ions with OH

TE trace element C l-, organic acids as L
Figure P4.4 The major forms in which trace elements are found when distributed in soils.
MINOR ELEMENTS AND ENVIRONMENTAL PROBLEMS 189
(e.g. on waterlogging) or by other changes, such as increased acidity, that

also increase the solubility of the hydrated oxide. Availability of the trace
elements from their own insoluble compounds, or when dispersed in other
minerals, depends upon the relative stability of the compound or mineral.
It is clear that because a high proportion of a particular element may be
bound up in the minerals of the soil in an unavailable form, analysis of the
total element concentration does not necessarily provide a useful indication
of whether plants growing on that soil will suffer from either deficiency or
toxicity problems. How to determine the available levels of elements in soils
and sediments is one of the major problems of analytical chemistry. The
most common approach to this problem is to use different extracting
solutions that are supposed to preferentially extract particular chemical
forms from the soil. For example, ammonium acetate solutions are used to
indicate easily exchangeable metals, the N H j ions will occupy the cation
exchangeable sites (Chapter 12), releasing the metals previously bound to
these sites. Similarly, solutions of the complexing agent EDTA will remove
more tightly held ions associated with organic matter. The use of a series of
these ‘selective’ extracting agents gives a rough indication of how the metals
are bound in soils and sediments.
13 Lead
Lead Abundance by weight (the relative abundance is given in

parentheses): crust, 13 ppm (35); ocean, 0.03 ppb (46). ppm =
mg kg~'; ppb = fig kg” 1.
As can be seen from the geochemical cycle of lead (Figure 13.1), the rate of
extraction is about ten times greater than the natural rate of weathering. The
two major uses of lead are in lead-acid storage batteries, particularly for
motor vehicles, and as lead alkyl compounds added to petrol. Petrol engines
give higher-power outputs and use fuel more efficiently when operated at
higher compression ratios. Smooth running can only be achieved under
these conditions by using petrol containing more branched-chain or
aromatic hydrocarbons or by the cheaper expedient of adding lead alkyl
compounds. Catalytic convertors installed in motor vehicle exhaust systems
to cut down emissions of nitrogen oxides, hydrocarbons and carbon mon
oxide require lead-free petrol to be used. If leaded petrol is used, the lead
compounds in the exhaust emissions are trapped on the catalyst surface and
prevent the catalyst reacting with the other components in the exhaust gases.
Environmental legislation and taxation policy have resulted in an increase in
sales of lead-free petrol in the UK and Europe and the amount of lead being
released into the atmosphere is declining. The majority of the lead used in
batteries is recycled and only causes problems when the battery-disposal and
recycling processes are not effectively controlled. In contrast, about 75% of
the lead added to petrol is emitted through the exhaust and dispersed as an
aerosol in the atmosphere. As a consequence it is unlikely that there is
anywhere left on the Earth’s surface that has ‘natural’ levels of lead. Results
from Greenland ice cores indicate that there has been a 400-fold increase in
lead deposition in the ice between 800 b c and 1965. The average anthro
pogenic emission rate in the latter half of the nineteenth century was
2 2 x 1 0 6 kg a-1, due mainly to the smelting of lead ores and burning of coal.
Nowadays the rate is about 20 times higher, at 450 x 106 k ga-1.

Approximately 94% of the lead in the atmosphere is derived from anthro
pogenic sources, with an even higher proportion in urban areas where there
is heavy motor traffic.
Although lead ores may be quite rich in lead, the cut-off grade is about
2%; the average concentration in rocks (13 mg kg-1) and soils (20 mg kg” 1)
LEAD 191
ATMOSPHERE rural (0.1 \ig m 3)

urban (2 |Ag m-3)
332
'/SEDIMENTARY ROCKS
ifc .
; O "- . SEDIMENTS .J
! •• 'ytf- . • - ......- $ti*l
x 106 kg Pb a 1
x 106 kg Pb -> fluxes
( ) concentrations
Figure 13.1 The lead cycle.
is low. The enrichment factor needed to produce a lead ore is about 1500:
concentration of lead in ore 20 x 1 0 3 kg kg
enrichment factor = 1500
concentration in crust 13 x 10~6kg kg -l
When this figure is compared with the enrichment factors for iron and
aluminium, about 5 and 4, respectively, it is apparent that unusual
conditions must be required for lead-ore formation - hence the concern
about the size of future reserves.
As well as being in vein ore deposits, lead sulfide is also associated with
black shales. These fine-grained marine deposits formed under reducing
conditions in which sulfate was reduced to sulfide (Eqn 13.1) and the
insoluble sulfides of metals like lead, copper and mercury were precipitated
(Eqn 13.2).
s o 2raq) 8 e“ + 8 H 4 4H?0 (13.1)
Pb?a+q) + S fo PbS (S) (13.2)
Lead sulfide has a low solubility (10“ 2 7 mol dm-3) and the solubility of
other lead compounds is usually less than 10- 6 mol d m 3. The weathering of
lead ores generally produces immobile compounds, with low concentrations
192 MINOR ELEMENTS AND EN VIRO NM ENTAL PROBLEMS
of lead in natural waters. The majority of lead in rocks is present in silicate

structures, substituting for elements like calcium. It is unavailable to plants
until the primary mineral is broken down by weathering and in soils the lead
tends to be held strongly by organic matter. It is often concentrated in the
upper few centimetres due to incorporation in plants and then accumulation
within the decomposing remains in the humus layer. It seems likely that
some reports of surface contamination by atmospheric lead causing much
higher levels in the top layers of soil were actually misinterpretations of the
natural biogeochemical concentrating effects. About 95% of the lead being
transferred to the oceans by rivers was transported as suspended sediment
(inorganic and organic). The increase in aerial dispersion from anthropo
genic emissions has increased the atmospheric flux, leading to higher levels
of lead in rivers and some lead falling directly on the sea.
Lead was first used to produce water pipes in Roman times and until the
1950s was still used extensively in the UK. Since then lead pipes have been
largely replaced by copper ones, which are easier to fabricate and to bend;
and, more recently, in cold-water systems by plastic ones, plastic being
cheaper than copper. In hard-water areas, in which the pH of the water does
not drop below 7, lead pipes are quite stable. A layer of lead, calcium and
magnesium carbonates is rapidly built up and acts as a protective coating
against dissolution of the lead. In soft-water areas, in which the pH of the
water may be below 5, the lead is relatively soluble and water that has been
in contact with the lead for a period of time may contain over 1 mg Pb dm-3.
The EC limit for lead in drinking water is 50 /xg dm-3, but the WHO is now
recommending that the limit should be reduced to 10 fig dm” 3. This will be
very difficult to achieve if there is any lead piping in the supply system.
Water authorities in the UK now increase the pH of all acid waters by the
addition of calcium hydroxide, Ca(OH)2. This also increases the hardness of
the water. Lead can cause hypertension, one of the factors influencing heart
disease, and it has been suggested that the lower levels of heart disease in
hard-water areas may be due to lower levels of lead in the water supply. The
importance of avoiding acid water in lead pipes was illustrated during the
1983 strike of the UK water workers. The strike prevented the treatment of
many water supplies with calcium hydroxide. Within 2 weeks, the levels of
lead in the drinking water of some houses with extensive lead piping had
risen from 30-40 to 800-1200 fig dm-3. Even houses with copper pipes are
not completely free from contamination by lead because the soldered joints
between the pipes contain lead that can be mobilized by acid waters.
Dichloroethane, C 2 H 4 CI2 , and dibromoethane, C2 H 4 Br2, are added to
petrol to prevent the build-up of lead deposits in petrol engines running on
petrol containing lead-alkyl compounds. The lead combines with the
chlorine or bromine to form volatile halogenated compounds that are
LEAD 193
removed from the engine with the exhaust gases. The cooled compounds
form fine particles (mainly less than 2 /xm diameter) which can be widely
dispersed and which can easily be breathed into the lungs.
Lead is a cumulative poison. About 90% of the lead retained in the body
enters the bones, from which it can be remobilized. The WHO recommends
a maximum intake of 3 mg lead per person per week. Children and infants,
who are more susceptible than adults to lead poisoning, should have intakes
of less than 1 mg Pb per week. The average rate of absorption of dietary lead
is about 8 %, but about 40% of the fine particulate lead retained in the lungs
is absorbed (Figure 13.2). These absorption rates result in about two-thirds
of absorbed lead coming from the diet and one-third from the atmosphere.
In addition, lead intake is increased by about 5% for every 20 cigarettes
smoked per day. The absorbed lead enters the bloodstream, where over 90%
is bound to the red blood cells with a mean residence time of 1 month. The
blood-lead level appears to vary linearly with exposure and is, therefore, a
good indicator of recent exposure, with normal levels being 10-20 fig Pb per
100 cm 3 blood; 25%-40% of the lead in blood enters soft tissues, about 15%
enters bones and the remainder is excreted. The residence time in the soft
tissues is again about 1 month, with the majority of the lead being lost in
hair, perspiration and digestive secretions. The concentration in hair is a
good indicator of exposure to lead over the previous few months. Bones act
as the major reservoir for lead in the body and the residence time is 40-90
years in adults. Children absorb a greater proportion of ingested lead than
do adults, and the distribution in the body is also different. About 28% of
the lead in children is in soft tissues compared with only 5% of the lead in
adults being in the soft tissues.
Figure 13.2 The daily intake of lead by adult humans, and its distribution in the body.
Lead binds strongly to a large number of molecules, such as amino acids,

haemoglobin, many enzymes, RNA and DNA, and thus disrupts many
metabolic pathways. The effects of lead toxicity are very wide ranging and
include impaired blood synthesis, hypertension, hyperactivity and brain
damage. Effects at the molecular level, such as the interference with steps in
haem synthesis, occur at very low levels equivalent to 20-200 fig Pb kg - 1
soft tissue, which are the levels normally found in adults. If the normal body
burden in adults is of the same order as that at which harmful effects may
occur, any factor that increases lead intake must be viewed with great
concern. The widespread distribution of lead from motor-vehicle exhausts
increases atmospheric levels by factors of 2 0 (much more in urban areas);
further, the subsequent contamination of soil and crops increases the
amount of lead in food. Children, as well as absorbing a higher proportion
of ingested lead than adults, have poorer hygiene habits and consume more
dirt and dust picked up on their hands. In urban areas, roadside dirt can
contain several thousand parts per million lead (typical mean values 1 0 0 0 -
3000 fig kg-1) and samples of old paint in West London contained from
6.2% to 52.4% lead. Some children eat dirt, a habit known as pica, and they
are particularly at risk from lead paints, one piece of which may contain
enough lead to cause acute poisoning. Acute poisoning produces a rapid
onset of symptoms due to the uptake of a large dose of toxic material.
Chronic poisoning is due to the uptake of smaller doses over a longer period
of time and generally brings about a gradual appearance of symptoms.
Associated with chronic poisoning are sub-clinical effects in which there are
no obvious outer (or clinical) signs of adverse effects, but metabolic
functions at the molecular level are being disrupted to a greater or lesser
extent. Because of the lack of obvious symptoms, sub-clinical effects are
difficult to diagnose. There is a growing body of evidence that the
intelligence of children is being lowered in urban areas in which there are
high inputs of lead from motor vehicles.
Blood-lead levels are commonly used to monitor the status of lead body
burdens. The results are sometimes not very satisfactory because there is not
always a close relationship between blood-lead levels, soft-tissue levels or
concentrations that cause metabolic dysfunction. One individual with 25 fig
Pb per 100 cm 3 blood may be suffering from lead-toxicity effects, whereas
another with 70 fig Pb per 100 cm3 blood may not. As it is individuals,
rather than the statistical average members of the populations, that must be
treated, a monitoring programme should ideally pick out the individuals at
risk - otherwise either individual sufferers will be missed or resources will be
wasted on the treatment of too many unaffected people. However, the use of
blood sampling will continue as there is no other sampling technique that
yields better results and is so easy to carry out.
The analysis of low levels of lead is difficult. In natural waters, lead levels
are at the microgramme per cubic decimetre level. There are problems (a) in
LEAD 195
achieving the high degree of sensitivity required actually to detect the lead;
(b) in avoiding contamination from lead in the sampling containers, in the
filter units, in the chemicals used and in the laboratory atmosphere; and (c)
in overcoming interference from other species present in the solution (this is
especially a problem with sea water). In one interlaboratory trial, all seven
laboratories taking part reported sea water lead levels 1 0 - 1 0 0 times higher
than the correct values. In solid samples, from which the lead has to be
extracted into a solution, the errors can be just as great even though the
original concentrations may be somewhat higher. One of the commonly
used analytical techniques for lead is prone to give readings that are too high
unless great care is taken in providing careful corrections. It appears likely
that many reported analyses for lead are incorrect. However, there is now a
much greater emphasis on quality control and the use of reference samples
so that published results are generally more reliable than they were before
the mid-1980s.
14 Mercury
Mercury Abundance by weight (the relative abundance is given in paren

theses): crust, 80 ppb (63); ocean, 0.15 ppb (40). ppb = fig kg-1.
Mercury is much less common than lead in the Earth’s crust and
consequently the geochemical cycle has smaller fluxes (Figure 14.1).
Mercury is the only metal that is liquid at normal temperatures, being 13.6
times more dense than water. It has a high volatility and air that is in
equilibrium with liquid mercury will contain 14 mg Hg m ~ 3 air at 20 °C. The
maximum allowable level of any toxic vapour - the level that is thought to
be safe - is called the threshold limit value (TLV). For mercury, this
concentration is set at 0.05 mg Hg per m 3 air. All mercury spills are
potentially very dangerous.
Because of mercury’s association with lead-zinc-silver ores, the presence
of high levels of mercury vapour in the atmosphere, or in the air trapped in
soil, can be used to indicate the presence of these ore bodies. Mercury-
vapour concentrations can be determined by very sensitive portable
instruments which allow the method to be used extensively in mineral
exploration. Mercury is described as a ‘pathfinder’ element when used in this
way to indicate Pb-Zn-Ag mineralization. Most mercury compounds are
relatively volatile, even mercuric sulfide, HgS, which is the major mercury
ore mineral, cinnabar, gives 10 ng Hg m ~ 3 in dry air. Cinnabar is easily
reduced to the metal by heating in air (Eqns 14.1 and 14.2) and as elemental
mercury is also found in small amounts, the metal has been used by humans
for several thousand years.
2HgS + 3 0 2 ^ 2HgO + 2 S 0 2 (14.1)
2HgO 5^ C 2Hg + 0 2 (14.2)
The production of mercury has declined since the early 1970s. In 1971, it
was 9.6 x 103 tonnes. By 1989, it had dropped to 5.4 x 103 tonnes. This was
partly due to increased recycling and partly to the concern about
environmental pollution, which led to decreased usage. The largest single
use of mercury in 1971 was in the manufacture of sodium hydroxide and
chlorine by the electrolysis of brine. The losses of mercury from these plants
MERCURY 197
Figure 14.1 The mercury cycle.
were 150-250 gHg tonnes - 1 Cl2 produced. Strict emission controls have
since been introduced and these have resulted either in alternative processes
for chlor-alkali production or in the reduction of losses (average
3.6 gHg tonnes - 1 Cl2 in 1992) and the amounts of replacement mercury
used.
The most important difference between the lead and mercury cycles is the
importance of methylation reactions. In its natural cycle, lead remains in the
+ 2 state and little natural methylation occurs. Mercury exists in the 0, + 1
and + 2 oxidation states (Figure 14.2), and methylation (Eqn 14.3) is an
important feature of its cycle, particularly with regard to its uptake by fish
and humans.
H g 2 + nncroorgam sm s m .ro orga m sm s ^
m onomethylm ercury dim ethylm ercury

soluble in w ater insoluble in water
volatile
Methylmercury is the major mercury species found in fish and about 90% of
the CH 3 H g+ eaten is absorbed by humans. There are a variety of
mechanisms by which microorganisms can bring about the formation of the
very toxic methylmercury species (Figure 14.2). Transformation to mono
methylmercury is more important under aerobic conditions than under
anaerobic conditions. This is because the presence of sulfide ions (S2~) in
reducing environments favours the production of insoluble mercury(II)
sulfide. Rates of methylation of insoluble mercury species are very much
198 MINOR ELEMENTS AN D EN VIRO NM ENT AL PROBLEMS
major species in bold type natural and

H g” anthropogenic
C H .H g C H , biological sources in soil,

C H 3H g + marsh, fresh and ocean
waters
Figure 14.2 Mercury species found in air, water and sediments or soil.
slower than with soluble species. The methylation of mercury is especially

important in rivers and lakes that have a low pH either continuously or
intermittently. This is because:
(a) more Hg2+ is solubilized by ion exchange from sediments at high
hydrogen-ion concentrations and the rate of synthesis of methylmercury
by microorganisms is, therefore, enhanced;
(b) the low pH favours methylmercury synthesis rather than dimethyl-
mercury synthesis;
(c) the lower population of higher organisms means that each individual
absorbs a greater proportion of the methylmercury produced.
In very productive water bodies (that have a higher pH) there is a much
greater dilution of the methylmercury as it is spread through a much larger
number of individuals.
MERCURY 199
As well as the microorganisms that produce methylmercury there are

many microorganisms that break down methylmercury, so normal levels do
not rise very high in water bodies. The concentration of methylmercury in
the water reflects the balance between methylation and demethylation
reactions. The concentration of methylmercury in aquatic organisms varies
from species to species but appears to be related to metabolic activity and
average lifespan. Methylmercury makes up 60%-90% of the mercury in fish
because the degree of absorption is high and the rate of elimination is
usually very low. Under similar conditions only 10%—15% of the inorganic
mercury is absorbed and elimination of Hg2^ occurs freely.
There have been a number of tragic episodes of organo-mercury
poisonings in Japan, Guatemala, Iraq and Pakistan and these awakened
interest in mercury as an environmental pollutant. In each case the causative
factors were the consumption of food contaminated by industrially
produced organo-mercury compounds. For instance, over 3000 people died
in Iraq in 1971-72 as a result of eating seed grain treated with methyl
mercury fungicides. Investigations resulting from these cases led to the
realization that methylmercury compounds could be produced in natural
systems. This was an important discovery as it had been thought previously
that the majority of mercury released by human activities would be either
sorbed on to inorganic solids or converted into insoluble mercury(II) sulfide,
or both. These mechanisms would effectively remove mercury from
interactions with ecosystems. Biomethylation means that the mercury,
rather than being locked up indefinitely, can be remobilized and is available
for uptake by aquatic organisms. At present the intake of mercury from fish
is the only major source of human dietary mercury, but the use of fishmeal
for feeding livestock and poultry could result in high levels of methyl
mercury in milk, meat and eggs.
The target organ of methylmercury in humans is the brain, where it
disrupts the blood-brain barrier, upsetting the metabolism of the nervous
system. In addition, mercury forms very strong bonds with sulfur groups in
proteins and enzymes, disrupting various enzymatic systems and synthetic
mechanisms. The main toxic effects of inorganic mercury are that it tends to
disrupt the functions of the kidneys and liver. Compared with inorganic
mercury, methylmercury can much more easily cross the placenta and affect
the foetus. In the poisoning case in Minamata, Japan, in which a factory
released methylmercury into an estuary and so contaminated fish, 2 2 infants
with serious brain damage were born to mothers who showed slight or no
symptoms of mercury poisoning.
The WHO has suggested that the intake for adults should be less than 0.3
mg total mercury per person per week, of which no more than 0 . 2 mg should
be methylmercury. Drinking water normally contains well below the
guideline (1 /igH gdm -3), and plants do not appear to take up much
mercury from the soil. The average intake is about 0.07 mg Hg per person
200 MINOR ELEMENTS AND EN VIRONMENTAL PROBLEMS
per week. However, people who eat a lot of fish may consume much more -
for instance, levels of 0.6 mg Hg kg - 1 fish could provide 0.15 mg methyl
mercury in one meal.
Despite the increased dispersion of mercury by mining, the use of mercury
compounds and fossil-fuel combustion, there is little evidence of worldwide
contamination on the same scale as has occurred with lead. For instance,
polar ice cores that showed lead levels increasing from 10 ng kg - 1 in 1750 to
about 2 0 0 ng kg - 1 in 1960, but indicated mercury levels of about 1 0 0 ng kg - 1
since 800 b c . The difference between the two metals can be explained by the
much larger natural atmospheric component of mercury due to terrestrial
degassing, masking the effects of the anthropogenic inputs. With lead, a
much greater tonnage is put into the atmosphere by anthropogenic sources
than by natural sources. The evidence that mercury is actually causing
widespread health problems is very sparse. The people who are definitely at
risk are those working in mercury-using industries, where health and safety
regulations should be enforced to protect them. Fish eaters may be at risk,
but even here there are many people who have consumed fish containing
0.5-1.0 mg Hg kg - 1 who do not appear to be adversely affected. The known
chronic or acute toxicity cases in Iraq, Guatemala and Pakistan have
involved seed grain treated with organo-mercury fungicides that has been
eaten rather than planted, and the Japanese cases produced methylmercury
contents of 20 mg Hg kg - 1 in the fish. The optimistic view is that stricter
environmental standards and future vigilance will prevent the widespread
problems that are more likely with lead and possibly cadmium.
There are very sensitive methods available that will detect mercury at
levels in the microgramme per kilogramme range, but the high volatility of
many mercury species causes difficulties. Samples must be collected in a
manner that will avoid contamination, and the sample must be repre
sentative of the mass being investigated. The sample must be stored and then
converted into a form suitable for analysis. Each stage can cause problems.
During storage mercury can be lost from the sample by diffusion of gaseous
forms into the air above the sample or out of the container, or there may be
sorption of species on to the container walls. An aqueous solution stored as
collected for 21 days lost 77% of the original mercury by sorption on to the
container walls and a further 18% by volatilization. Another sample of the
same solution to which potassium dichromate and nitric acid were added
only lost 1% by sorption and 1% by volatilization in the same time. The
potassium dichromate oxidizes volatile species to mercury (II) ions and the
hydrogen ions from the acid compete for the sorption sites on the container
walls. Solid samples usually have to be dissolved before the analysis can be
carried out and losses of mercury can easily occur, especially if the process
requires heating. Closed containers or very efficient condensers can
overcome this problem.
15 Zinc and cadmium
Zinc Abundance by weight (the relative abundance is given in

parentheses): crust, 70 ppm (24); ocean, 11 ppb (22). ppm =
mg kg-1; ppb = /xg kg- '.
Cadmium Abundance by weight (the relative abundance is given in

parentheses): crust, 0.2 ppm (64); ocean, 0.11 ppb (42).
Zinc is an essential element, but cadmium has no known useful biological

function in humans. The cycles of zinc and cadmium (Figure 15.1) are very
closely inter-related because natural zinc minerals and most anthropogenic
fluxes contain small amounts of cadmium. Zinc, cadmium and mercury are
in the same group in the periodic table because they all have similar
arrangements of electrons in the outermost shells. However, the inner
electron structure of mercury differs from that of zinc and cadmium and,
therefore, its chemical properties differ also. The properties of zinc and
cadmium, though, are very similar. The hydrated zinc ion ( Z n ^ )
is relatively more stable than the hydrated cadmium ion (C d2^ ) . As a
consequence, when there is competition between zinc and cadmium to bind
to sites in insoluble species, cadmium tends to bind more strongly than zinc,
especially if a metal-sulfur bond is formed. Cadmium, therefore, displaces
zinc from many of the zinc-containing enzymes.
The mobilization of zinc and cadmium by human activities outweighs
natural cycling processes. The increased quantities of cadmium mobilized
are partly related to demand for cadmium itself, but also to increased use of
zinc and phosphate fertilizers. Cadmium is used in electroplating (in which it
forms a bright corrosion-resistant finish), in plastic stabilizers, in pigments,
in solder and in nickel-cadmium batteries. Zinc is used to prevent corrosion
(by galvanizing), in alloys, in paints, in dyes and in tyres. Cadmium is
obtained as a by-product from zinc refining (Eqn 15.1) but the complete
removal of all the cadmium from ‘bulk’ zinc is uneconomical.
ZnS ^ S 0 2 + ZnO C 0 2 + Zn/Cd ^ Zn + Cd (15.1)

O2 heat
Dispersal of zinc, therefore, leads to dispersal of cadmium.

202 MINOR ELEMENTS AN D EN VI RO NM ENT AL PROBLEMS
Figure 15.1 The zinc and cadmium cycles.
Phosphate fertilizer contains 5-100 mg Cd kg - 1 and this increases soil and

plant levels when these fertilizers are used. It has been estimated that in the
UK, the average addition of cadmium to crop lands is 0.4 mg m - 2 a - 1 (air
deposition, 41%; phosphate fertilizers, 54%; sewage sludge, 5%). However,
when sewage sludge is used over 90% of the added cadmium can come from
the sludge. The lower average figure is because sewage sludge is only applied
to about 5% of the land in the UK. The high values in sewage sludge reflect
industrial and domestic usage of cadmium.
15.1 Sewage-sludge disposal
The problems of sewage-sludge disposal are becoming increasingly great for

a number of reasons. As with most environmental problems, increased
populations and the desire for higher standards of living have converted a
relatively small-scale problem into a major resource conflict. This is
summarized below.
Problem How to dispose of human excreta.
Solution Collect the wastes and spread them on land.
Problems Pathogenic bacteria, viruses, parasites cause endemic diseases.
Pollution of watercourses causes diseases. Larger population
ZINC A N D C A D M I U M 203
centres make collection and disposal more difficult. The smell of

the collected material may be offensive.
Solution Build a system of water closets and sewers.
Problems The untreated sewer effluent uses up the dissolved oxygen in
rivers, killing all higher aquatic life-forms. The smell and visible
appearance of rivers detenorates. The contamination of water
supplies of downriver communities occurs.
Solution Build sewage treatment plants (Figure 15.2).
Problems The cost increases very rapidly as the type of treatment is
uprated from primary to secondary to tertiary. The final water
quality depends upon the degree of treatment. The solids still
have to be disposed of.
Solution The solids can be dumped on land, as they contain useful
nitrogen, phosphorus, potassium and organic matter, to replace
fertilizers.
discharge
raw sewage discharge to sea to sea or rivers, discharge
(99% H 20 , or rivers, natural natural processes to sea
1% solids) processes purify slowly purify more rapidly or rivers, 4pure’
solids sludge solids chemically

(6% solid, 94% H 20 ) (1% solids) contaminated
1
landfill water reduction dump or incinerate
^ j .. ^ . methane
incineration dumping digestion -------►(usefu, fud)
i / \ i
ash land solids
/
landfill
/
fertilizer
x
landfill dump or
incinerate
Figure 15.2 Flow diagram for sewage treatment.

Problems Urban and industrial areas produce sludge with high toxic-metal
contents (Table 15.1). Therefore, only limited amounts can be
applied without damaging crops or consumers and they may still
contain pathogenic organisms.
Solution The solids could be dumped in the sea away from the coast.
Problem The toxic contents will affect marine organisms.
Solution The sludge could be incinerated.
Problems This is costly because a lot of energy is needed to remove water
before the sludge will burn. Air pollution may occur if gases are
not properly cleaned. Ash will contain even higher
concentrations of toxic metals and must be dumped in special
sites to prevent pollution of watercourses.
Final Reduce the population; reduce the industrial contamination of
solution? the effluent; and use smaller quantities of potentially toxic
compounds.
Interim Maximize the use of natural systems to detoxify contaminants
solution? and remove other toxic substances by treatment, preferably at
source where their concentration is highest and other impurities
lowest.
It should be noted that metals such as iron, zinc and copper are essential
elements but they become toxic if present in too high a concentration. The
effects of dumping sludge on land are still not clearly understood. Uptake of
the metals by plants is dependent upon their availability and mobility
(Figure 15.3). Soils with a high pH and a high cation-exchange capacity will
tend to immobilize most added metals. However, a later change in
conditions, particularly a drop in pH, could cause the release of the metals.
It is important to limit the build-up of potentially toxic elements even if they
are initially found in unavailable forms. There are now limits recommended
by the EC for the maximum concentration of some metals in soils that have
Table 15.1 Comparison of metal concentrations in dry sewage sludge and soil (concentrations
in mg kg-1)
Concentration in sewage sludge

Mean soil Mean sludge concentration
Metal Mean Range concentration Mean soil concentration
Hg 2 0-5 0.25 8
Cd 20 0-300 0.4 50
Cu 250 1-3000 50 5
Cr 500 10-5000 50 10
Pb 700 50-5000 25 28
Zn 3000 500-25 000 100 30
Fe 16000 2000-42 000 30000 0.5
ZINC AN D CA DM IUM 205
P
Mobile and available forms
hydrated ions, A /"*), or soluble complexes, [A # LJ, L
where M is any metal 1 A
A/ (aq) + (MLrl ------------------ ►
N
/ i
2 T
3 /
Potentially available forms /
insoluble complexes, [MLy], /
or forms attached to clays' /
and organic matter /
s _ M+ kM + M4
U
L
■M + “► [M Ly] + O C LAY OR
D ORGANICS
G
E -M +
Unavailable forms 4'
insoluble compounds, MO + MS + MX
often oxides or sulfides
Key
1 uptake by plant
2 changes in form due to action of

microorganism s or changes in pH or Eh
3 soluble forms pass directly into solution
4 formation o f insoluble compounds
Figure 15.3 The availability of metals from sewage sludges.
had sewage sludge added to them. For soils of pH 6-7, the allowed
maximum concentration for cadmium is 3 mg kg - 1 and for zinc and lead
300 mg kg - 1 each. In areas with naturally high background concentrations
of these elements very little sewage sludge can be disposed of by dispersal on
land. Because cadmium is chemically similar to zinc, it is also readily taken
up by plants and enters the edible portions. This is an important difference
from lead, which is not easily accumulated by plants. The concentrations of
lead in the edible portions of plants are much lower than soil-lead levels.
Cadmium concentrations in plants are much closer to soil levels, although
this varies very much from species to species, and the relative uptake of
cadmium is reduced as the concentration of cadmium in the soil increases.
The soikgrass cadmium ratio changed from 3.3 to 11.4 to 157.1 as the soil-
cadmium levels changed from 3 to 24 to 440 mg Cd kg - 1 soil in a study
carried out at Shipham in Somerset, UK.
15.2 Toxicity of cadmium
The toxic effects of cadmium received widespread attention as a result of

some Japanese developing Itai-Itai byo (‘ouch ouch’ disease). The name
came from the severe pain developed by the sufferers as lumbago-type pains
progressed to become severe bone damage with multiple fractures of the
softened bones. Death was attributed to kidney failure. The victims were
mainly post-menopausal women suffering from malnutrition, low vitamin D
intake and calcium deficiency. These contributing factors mean that Itai-Itai
disease is not typical of cadmium toxicity. The main target organs for
cadmium are the kidney and liver, with critical effects occurring when a
content of 200 /ig Cd g - 1 (wet weight) is reached in the kidney cortex. The
body burden of cadmium increases with age, as the half-life in the body is
about 20-30 years. Normal dietary intakes are in the range 0.21-0.42 mg per
week which are close to the WHO recommended maximum (0.4-0.5 mg per
week). The closeness between actual intakes and suggested maxima is one of
the reasons for the concern over cadmium levels in soil, water and food.
Smokers are especially at risk because of the cadmium content of tobacco.
The smoking of 20 cigarettes per day corresponds to an oral intake of 40 fig
Cd from food, i.e. the cadmium uptake is doubled.
The problems in Japan arose from a lead-zinc mining and smelting
operation upstream from where the victims lived. There was aerial pollution
from cadmium-containing fumes and particulates, plus water pollution due
to cadmium-containing sediments and mine wastes. Rice grown in paddy
fields flooded by the river contained up to 3.4 mg Cd kg - 1 rice. Because of
its lower boiling point, cadmium is more concentrated, relative to zinc, in
the atmospheric emission from zinc smelters than it is in the ore or in zinc
metal. In the UK, the position of zinc smelters is clearly marked in
geochemical maps as cadmium anomalies.
15.3 Zinc
Zinc is an essential component of about a hundred enzymes in total, though

the number of zinc-containing enzymes in vertebrates is much smaller.
Normal zinc levels in plants are 25-150 mg kg - 1 with concentrations above
400 mg kg - 1 being toxic. Human adults contain 1.4-2.3 g zinc, about half
the amount of iron. Zinc deficiency in humans leads to dwarfism, reduced
rates of blood clotting and wound healing, skin abnormalities and other
problems.
Both zinc and cadmium are found associated with a soluble low-
molecular-weight protein called metallothionein which is characterized by a
high cysteine content. The large number of sulfhydryl groups, -SH, bind the
heavy metals tightly. One action of metallothionein is to detoxify cadmium,
ZINC A N D C A D M I U M 207
mercury and lead by binding very strongly to these metals through metal-
sulfur bonds so that they are no longer available to interfere with other
metabolic processes. Unfortunately the amount of metallothionein available
is too limited to prevent the toxic effects of large intakes of the heavy metals.
16 Uranium
Uranium Abundance by weight (the relative abundance is given in

parentheses): crust, 1.8 ppm (51); ocean, 3.3 ppb (27). ppm =
mg kg-1; ppb = /ig kg"1.
Uranium is preferentially concentrated in the Earth’s crust. There is a

relationship between the type of igneous rock and its uranium content. Acid
igneous, or granitic, rocks have the highest concentrations (2 - 1 0 mg kg-1),
basaltic rocks contain lower concentrations (0.3-0 . 8 mg kg-1) and
ultrabasics contain less than 0.1 mg kg-1. There is a wider range of con
centrations amongst sedimentary rocks. The highest concentrations are in
black shales and phosphate rocks (10-300 mg kg-1) with limestones
containing 2 mg kg - 1 and sandstones less than this. Whereas the con
centration of uranium in sea water is relatively constant, there are wide
variations in fresh waters (0 - 2 0 0 ppb) depending on the country rocks and
the amount of weathering that is occurring.
The most widely distributed uranium mineral is uraninite, U 0 2, which is
associated with the final stages of granitic magmatic intrusions and
hydrothermal sulfide deposits. Uraninite is easily weathered under slightly
acidic oxidizing conditions to form the soluble uranyl ion U O ^ . The UO^+
ion combines with the carbonate ion to form very strong complexes such as
[U 0 2 (C 0 3)3] and these enhance its mobility. The leached uranium may
precipitate in the presence of phosphate, vanadate or other ions to form
brightly coloured (yellow, green, red) secondary minerals. Coloured
compounds such as these have been used in the glazes on ceramic and other
pottery items.
Uranium is a member of the actinide group of metals (Figure A.2) and
has the very high density of 19 g cm - 3 (lead has a density of 11.3 g cm-3).
Uranium is one of those elements that has no known stable isotopes. The
stability of the nucleus is dependent upon the attractive forces between the
nucleons (protons plus neutrons) outweighing the repulsive forces due to the
positive charges of the protons (see Chapter 3). If there are 84 or more
protons in the nucleus, the repulsive forces cannot be completely balanced
by attractive forces and the nucleus is unstable. The degree of instability is
indicated by the half-life (^ /2) of the radioactive isotope (radioisotope). The
longer the half-life of the radioisotope the greater the stability. For example,
URANIUM 209
238U ( / 1 /2 = 4.5 x 109 a) is more stable than 235U ( t{j2 = 7.13 x 108 a) and
234U ( t \/2 = 2.48 x 105 a). The composition of naturally occurring uranium
is 99.27% 2 3 8 U, 0.72% 235U and 0.0056% 2 3 4 U, reflecting the relative rates
of decay. In fact, the half-life of 234U is so short that the only reason there is
any still present in the Earth is because it is being constantly produced by
the breakdown of other radioisotopes.
All the naturally occurring heavy radioisotopes, i.e. those with atomic
numbers of 82 (lead) and above, are members of a radioactive decay series
(Figure 17.1) commencing with one of the three relatively stable
radionuclides U, * U and Th (thorium). The series terminates with
one of the stable isotopes of lead 2 0 6 Pb, 207Pb and 2 0 8 Pb. The original
concentration in the Earth of 235U must have been 80 times greater than it is
now. Similarly, twice as much 238U and 25% more 232Th (t\/2 =
14.05 x 109 a) would have been originally present. These values can be
calculated from the half-lives of the isotopes. The original unstable nuclide
undergoing radioactive decay is called the parent and the product is called
the daughter. In a decay series, each daughter becomes the parent of the
following daughter element, e.g.
238U (parent) — > 234Th (daughter) (16.1)
then,
234Th (parent) — ►234Pu (daughter) (16.2)
etc.
The relative abundances of daughters and parents are kept constant by
the equilibrium between the rates of formation and decay, unless there are
other removal mechanisms (e.g. leaching) operating. The majority of the
naturally occurring radionuclides (of which there are more than 60) are
members of the three decay series illustrated in Figure 17.1. These together
with 40K (see Chapter 12) are mainly responsible for the natural background
radioactivity on the Earth’s surface (Table 17.1) and the radiogenic heat
flow through the crust.
16.1 Nuclear energy
Uranium is now in demand as an energy providing fuel. Whilst the

radioactive decay process releases energy as more stable nuclides are
formed, the rate of release is very slow. For example, 1 mole (235 g) of 235U
would release about 4 x 10 1 1 J, but, because it would take over 700 million
years to release half of this energy, the average energy release over this
period would only be about 300 J per year . However, if 235U is bombarded
with neutrons of the correct energy (Figure 16.1) it will split into two lighter
2 10 MINOR ELEMENTS AND ENVIR O NM E NT A L PROBLEMS
nuclei (Eqns 16.3 and 16.4) and release more neutrons plus about 2 x 1013
Jm ole - 1 almost immediately. This process is called nuclear fission (see
Chapter 3).
235U + 'n — > 142Ba + 91Kr + 3‘n +energy (16.3)
235 U + 'n — > l40Xe + 94Sr + 2'n +energy (16.4)

You should note that the reactions illustrated by Equations 16.3 and 16.4
are not the only ones that can occur. A wide range of new nuclides are
produced.
The fission process depends upon the bombarding neutron being captured
by the uranium nucleus (Figure 16.1). Slower (lower energy) neutrons have a
much greater chance of being captured than the faster (higher energy)
neutrons. Slower neutrons induce a higher proportion of nuclear fission
reactions than do fast neutrons. The slow neutrons are often called thermal
neutrons.
More neutrons are released than absorbed. With 235U an average of 2.5
neutrons are released per fission reaction (Eqns 16.3 and 16.4). These
neutrons have high energies and they need to be slowed down to increase
their chances of initiating another fission reaction. When neutrons collide
with nuclei, if they are not absorbed, they lose some energy. The lighter the
nucleus that they collide with, the greater the loss of energy by the neutron.
Carbon (as graphite) or hydrogen (in water) are normally used as
‘moderators’ to slow down the neutrons in nuclear reactors. Carbon is a
more effective moderator than water, but graphite is potentially more
hazardous, if overheating occurs (as in the Chernobyl accident, Section
16.3).
Figure 16.1 The nuclear fission process. Step A: a low energy neutron, n, is captured by the
nucleus of a 235U atom to form the intermediate 236U. Step B: the unstable nucleus splits into
two smaller nuclei FI and F21 plus two or three high energy neutrons (prompt neutrons). Step
C: in about 1% of the reactions there is a delay of up to 80 s before one of the nuclei, e.g. F21,
converts to a new nucleus, F22, with the release of another neutron (a delayed neutron).
URANIUM 211
If all the neutrons produced from each nuclear fission reaction were used
to initiate another fission reaction, there would be a very rapid increase in
the number of fissions. This would give an uncontrolled release of energy
from an uncontrolled chain reaction (Figure 16.2) and result in an
explosion.
Uranium-235 produces an average of 2.5 neutrons per fission, therefore,
1 fission — > 2.5 fissions — > 6.25 fissions — ►15.6 fissions, etc., i.e. 2.5”
neutrons are produced after n sets of fission reactions. Because of the time
needed for the neutrons to slow down before they can induce fission, the
average time between steps in a fission reaction is about 10- 4 s. This means
that ten steps would take a thousandth of a second and after 7 ms (70 steps,
2.57 0 fissions) 2.8 tonnes of 235U would have been consumed and 2.5 x 1017
J released. A thousandth of a second later (now 80 steps, 2.58 0 fissions)
nearly 27000 tonnes would, theoretically, have undergone fission. In
practice, this great mass of 235U could not be brought together in one place.
The total world discovered reserves are estimated to be 20-30 thousand
tonnes. The energy released would blow apart the unreacted uranium before
all these fission steps could occur. A smaller mass of 235U can produce an
uncontrolled, but limited, chain reaction. Even here the average of 2.5
neutrons that are released per fission would not all take part in the chain
reaction. This is because the neutrons have high energies when first
produced and they may well escape from the mass of 235U before they have
slowed down enough to be captured. However, it is possible to design a
situation where the number of neutrons producing fissions increases at each
step and an explosion occurs (as with an atomic bomb). A mass of about 15
kg (the so-called critical mass) of 235U is required to achieve a self-sustaining
uncontrolled fission reaction.
To control the fission process, the population of slow (low energy)
neutrons that initiate further fission reactions must be kept constant at a
Figure 16.2 Uncontrolled chain reactions. There is a rapid increase in the number o f nuclear
fission reactions as the majority o f the released neutrons initiate the splitting of further 235U
nuclei.
value very close to one thermal neutron per fission. This produces a
controlled chain reaction (Figure 16.3).
In practice, the controlled chain reaction is achieved by arranging the way
that fuel rods (usually made of uranium oxide) are packed in a moderator.
The moderator slows down enough neutrons and the geometrical packing
ensures that not too many of these slow neutrons escape without inducing
fission reactions. Finer control of the number of fission reactions is achieved
by introducing or withdrawing neutron-absorbing control rods. These
control rods usually contain boron or cadmium which are very efficient
neutron absorbers. This use of 2 3 5 U, moderator and control rods is the basis
of nuclear reactors that produce controlled amounts of energy. When power
output needs to rise some of the control rods are raised out of the nuclear
reactor, allowing more thermal neutrons to initiate fission reactions and
release more energy. By dropping in all of the control rods the number of
thermal neutrons can be reduced to such a small value that the chain
reaction no longer continues.
A containment vessel is built around the reactor. This protects the people
operating the nuclear reactor against the harmful effects of the radiation (ce,
(3 and 7 ) emitted by the radionuclides and the neutrons from the fission
process. Usually a thick concrete and steel structure is used to absorb the
emissions. The vessel also acts to prevent the escape of matter if there is an
accident.
The very rapid multiplication in the number of slow neutrons would
appear to make the control of the fission reactions almost impossible.
Unless control processes reacted in milliseconds to an increase in neutron
numbers, the reaction would run out of control. Fortunately, almost 1% of
the neutrons are released after delay times of 0.1-80 s (Figure 16.1). The
reactor can be designed so that without these delayed neutrons the chain is
Fission fragments
©
'©
©© ©©
Thermal
t / /
neutron
Neutrons absorbed,
lost or involved in
non-fission reaction
Figure 16.3 Controlled chain reactions. The number of neutrons initiating the splitting of 235U
nuclei is just sufficient to maintain a steady-state. The numbers o f neutrons are controlled by
the use of neutron-absorbing control rods, the geometry o f the fuel rod distribution and the use
of a moderator to control the energy of the neutrons.
URANIUM 213
not self-sustaining. The number of extra delayed neutrons is allowed to rise

or fall by use of the control rods so a steady-state controlled chain reaction
is achieved.
The explosion at Chernobyl was caused by changing the conditions so
that the control of the chain reaction depended on controlling the rapid
release neutrons. The operators failed to do this and the energy release
became too rapid. The main explosion that occurred was due to the
combined effects of a chemical reaction involving hydrogen gas and steam
that were produced as the temperature increased.
Having obtained a steady production of heat energy inside the reactor, it
is necessary to transfer this heat outside. This transfer will prevent the
reactor over-heating and allow some use to be made of the energy. A
coolant is circulated inside the reactor. This may be carbon dioxide (most
UK reactors) or water (most USA reactors and Sizewell B) or water-steam
(some in former USSR). If water is used as the coolant it is usually also used
as the moderator. The coolant is generally pumped through a heat
exchanger where it converts water outside the reactor into steam. This steam
then drives a turbine, as in a conventional fossil-fuelled electricity power
station. By keeping the coolant isolated from the steam driving the turbines,
no radioactive materials which the coolant has picked up should escape
from the reactor. Water-steam systems drive the turbines with the steam
generated in the reactor. The turbines, therefore, become contaminated and
must be kept inside the containment vessel.
Pure 235U is not used in nuclear reactors. Generally, a mixture of the
oxides of 238U and 235U is used. In most reactors the mixture is enriched in
235U so that the nuclear fuel contains 2.5%-4% 235U in the oxide compared
to the naturally occurring proportion of 0.72%. 238U does not easily
undergo nuclear fission reactions. It absorbs neutrons and will prevent
sustainable chain reactions in most reactor designs unless 2 3 5 U-enriched fuel
is used. Therefore, 238U is described as being non-fissile (does not support
fission reactions) and 235U is said to be fissile (does support fission
reactions). This means that the majority of naturally occurring uranium can
not be utilized directly as a nuclear fuel.
When 238U absorbs neutrons a series of reactions occurs, involving
emission of 7 and (5~ radiation, which may lead to the formation of
plutonium, 239Pu (Eqn 16.5).
238U + ln — > 239U — > 239Np —-> 239Pu (16.5)
uranium uranium neptunium plutonium
These fission products are also able to absorb neutrons, but the majority are
like 238U and are non-fissile. They make the chain reactions more difficult to
achieve. However, 239Pu is fissile and is a potentially valuable by-product of
the absorption of neutrons by 2 3 8 U.
All nuclear reactors that contain 238U will produce some 2 3 9 Pu. The
quantities produced will depend upon the design of the reactor. The
attractive features of 239Pu are that it is a more efficient absorber of slow
neutrons than 235U and it is easily separated from 238U and 235U by
chemical means to give a high purity product. The chemical similarities of
the two isotopes of uranium make them difficult to separate. The very
efficient neutron absorption and the relatively low mass required makes high
purity 239Pu the preferred fissile material for nuclear weapons. 239Pu has a
half-life of 24 x 103 a and the associated radiation makes it very toxic.
The fact that Pu can be produced from U has lead to the concept of
the breeder reactor. In the breeder reactor a layer of 238U surrounds a core
of 239Pu or 2 3 5 U. The fast neutrons released by the fissile core are absorbed
by the non-fissile 238U and this is converted into fissile 2 3 9 Pu. This
conversion of the non-fissile 238U into a useable fuel would mean that
almost all of the available uranium would be suitable for nuclear power
production instead of only the 0.7% that is 2 3 5 U. This would extend the life
of nuclear energy fuel reserves by several hundred years. Unfortunately, the
time taken to double the amount of fissionable fuel is about 30 years and
breeder reactors have not been shown to be commercially viable. Breeder
reactors both produce and consume 2 3 9 Pu, whereas the common nuclear
reactors are called ‘burner’ reactors because they use up the ~ U (the ~ Pu
formed is an unavoidable by-product).
The products of nuclear fission are radioactive isotopes, with atomic
numbers in the range from 35 (bromine, Br) to 60 (neodynium, Nd), that
decay at varying rates. In addition, many different isotopes of the actinide
elements are formed in a similar way to Np and Pu (Eqn 16.5) by
neutron bombardment. As these products build up they gradually reduce
the efficiency of the chain reaction, because they absorb neutrons and they
need to be removed from the reactor. In most cases the fuel rods are left in
the reactor for about 3 years before being withdrawn and replaced with
fresh uranium oxide fuel rods. The long-term disposal of the radioactive
isotopes in the withdrawn fuel rods (the ‘spent’ fuel) is a major problem that
has yet to be solved. At present, the ‘spent’ fuel is either stored or the unused
fuel may be recovered by chemical separation methods and the waste
products stored in water-cooled tanks. Although many of the initial
products have very short half-lives, an appreciable number of longer lived
isotopes are produced, e.g. 90Sr (strontium, t\/2 28 a), 137Cs (caesium, f 1 /2 30
a), 93Zn (t l/2 9.5 x 105 a), 242Pu ( t l/2 3.8 x 105 a), 135Cs ( t l/2 2.3 x 106 a).
The initial radioactivity drops very rapidly, but after a few years remains
fairly constant because of the long-lived isotopes. As the short half-life
nuclides decay, a lot of energy is released, hence the need for water cooling.
With the passage of time the intensity of radiation and energy output
decreases and it should be possible to incorporate the waste in a solid matrix
and bury it. The problems are connected with ensuring that the solubility of
URANIUM 215
the solid is low enough to prevent the leaching out of radionuclides into
ground water.
The amount of energy released from nuclear fission (a reaction involving
changes inside atomic nuclei) is about a million times greater than the
energy released from combustion (a chemical reaction involving changes
outside atomic nuclei). For example, 1 tonne of coal releases about 3 x 1010
J, whereas 1 tonne of 235U releases 9 x 1016 J. As well as the identified
reserves of 20 000-30 000 tonnes of 2 3 5 U, it is estimated that there may be a
further 100000-150 000 tonnes of, as yet, undiscovered reserves. Uranium
ores generally contain 0.1 %—3% U 0 2 /U 3 0 8. After mining and milling,
physical and chemical concentration methods are used to produce
reasonably pure U 3 0 8 called ‘yellow-cake’. The U 3 0 8 is then treated with (i)
nitric acid; (ii) hydrogen fluoride, HF; and (iii) fluorine, F2, to produce the
gaseous uranium hexafluoride, U F6. As the density of 2 3 5 UF 6 is slightly less
than that of 2 3 8 U F6, the two can be separated by either (a) diffusion through
porous membranes which increases the concentration of 2 3 5 U F 6 by 0.2% of
its original concentration per pass, i.e. 0.7% becomes 0.7015%. Over a
thousand stages are needed to achieve the desired enriched fuel
concentration of 2 3 5 U; or (b) multi-stage centrifugation which has now been
developed into a more efficient method than diffusion. The enriched U F 6 is
hydrolysed and reduced to solid uranium oxide, U 0 2, ready for fabrication
into fuel rods. There are releases of radioctivity and production of wastes
with each step in the process, but the most damaging are likely to be the
large quantities of mine tailings that contain long-lived radionuclides in a
possibly easily mobilised form.
Nuclear energy is used to generate about 80% of the electricity in France
and over 20% of the electricity in the UK and the USA. There are over 400
large electricity generating nuclear reactors operating in various countries.
Some of these reactors are now coming to the end of their operating life and
the problems of decommissioning them are becoming imminent.
16.2 Radioactive wastes
Radioactive wastes pose risks due to the radiation and energy that they
release as well as being potentially chemically hazardous. The relative risk
that radioactive wastes pose is considered to be a function of the quantity of
activity that a given amount of waste generates and its chemical form. The
wastes may arise in either a controlled or an uncontrolled manner. Examples
of uncontrolled wastes are the fall out from the testing of nuclear weapons
or the accidental release of radionuclides, such as in the explosion at one of
the Chernobyl nuclear reactors (affecting hundreds of thousands of people)
and the removal and dismantling of a radiocaesium source from a hospital
in Brazil (causing the radiation-induced deaths of four people plus the
contamination of 85 houses).
216 MINOR ELEMENTS AND EN VI RO NM E NT A L PROBLEMS
In addition to the radioactive waste associated with nuclear power

reactors, there are many other sources of waste containing varying amounts
of radioactivity that can be described as controlled wastes. It should be
possible to control what happens to these materials. The ease of detection of
radioactivity makes radionuclides very useful in the study of biochemical
pathways and other tracer experiments. The ionizing properties of the
radiation can also be utilized in radiotherapy, static elimination above
rapidly moving sheet materials (like paper and plastic), thickness gauges
(especially for sheet materials), sterilization of equipment and food, smoke
alarms, etc. As a consequence, radionuclides have many uses in industry,
medicine and other scientific studies. The different types of controlled
radioactive waste can be subdivided into three groups based on the level of
activity in the wastes.
High level waste
This arises from the reprocessing of spent fuel and includes unprocessed fuel
rods that are being stored. The level of energy release from high level wastes
is so great that a method of cooling the wastes must be provided.
As indicated earlier, the unused uranium and freshly generated plutonium
can be recovered from the spent fuel rods for future use. In the USA, spent
fuel rods from civilian reactors are stored underwater without reprocessing.
In those countries, like the UK and France, where reprocessing occurs, the
fuel rods are stored in cooled tanks for at least a few months to allow the
shortest-lived isotopes to decay. The spent fuel can then be separated from
the cladding materials that hold the fuel rods together. The fuel is dissolved
in hot nitric acid. The uranium and the plutonium is removed using a
solvent extraction system. The remaining acid aqueous solution contains
97%-99% of the fission products. The rest of the unwanted fission products
are distributed through other parts of the reprocessing system. The high
level of activity associated with the waste solution generates a lot of heat and
it must be stored in efficiently cooled tanks. About 100 m 3 a - 1 of high level
waste is produced in the UK from reprocessing. Whilst reprocessing reduces
the activity being stored it increases the volume by about 50%.
After 50 years, the quantity of cooling required is reduced by about a
factor of ten because the short-lived radionuclides have decayed away. A
few years after production the liquid waste has reduced its activity enough
to allow it to be converted into a solid borosilicate glass. The drums
containing this solid waste can be stored in such a way that a flow of air is
sufficient to cool them. This process reduces the volume of waste by a half to
a third, reduces its potential mobility and should make long-term storage
easier to manage. Reprocessing also reduces the amount of activity that has
to be stored as waste compared to leaving spent fuel rods unprocessed.
URANIUM 217
However, it does increase the chance of releases of radioactivity to the

environment when the spent fuel rods are being transported to the
reprocessing plant, and during the reprocessing, especially as gases and
liquids are formed. In addition, there are concerns that the production of
weapon grade plutonium could lead to this material being diverted for
unauthorized use. With the reduced need for nuclear weapons by the major
powers, the separated plutonium must be disposed of or stored.
The plutonium, if it is not used in fast breeder reactors, can be used to
replace part of the 235U in the fuel in some designs of burner reactor. A
reactor such as Sizewell B would use about 42 tonnes of uranium oxide,
containing 1.3 tonnes 2 3 5 U 0 2, per year for each GW electricity produced.
This would give about 1.7 tonnes of fission products and 0.3 tonnes 239Pu in
the spent fuel. The 0.3 tonnes plutonium could be converted into 0.33 tonnes
P u 0 2 which would replace a similar weight of U 0 2 in fresh fuel rods.
This, in turn, would reduce the amount of uranium ore that had to be mined
by about 50 000 tonnes per year.
The decommissioning of nuclear weapons means that the plutonium that
was in the weapons is now becoming available for other uses. In order to
prevent it becoming available for future weapon fabrication there is a need
to find a way of disposing of it. One option would be to use the plutonium in
fast breeder reactors, but these are not commercially available. A second
option is to use it as a substitute for 235U in the enriched oxide fuel rods as
described in the previous paragraph. However, with at least 100 tonnes
239Pu available in 1997, and more due to be released, there are problems in
transporting, processing and then consuming these large quantities in a time
scale of less than 30-50 years. In addition to the plutonium, there will be a
need to dispose of the hundreds of tonnes of highly enriched 235U that will
no longer be required for weapons. This can also be converted to the oxide
and mixed with unenriched U 0 2 to fabricate fuel rods. Again the disposal
will take several decades and the uranium will need to be stored safely before
it is used. On the positive side, the release of this fissionable material will
reduce the need to mine uranium ores, but the cost of the conversion of the
weapons grade material to fuel is likely to be high.
Intermediate level waste
This is produced as solids and liquids by nuclear power stations, fuel

reprocessing, reactor decommissioning, defence establishments and the
radioisotope industry. This waste does not require heat generation to be
taken into account when the storage or disposal facilities are designed. At
present, about 3000 m 3 a ” 1 are produced in the UK. As the decom
missioning of old nuclear power plants becomes necessary, the quantities of
intermediate level waste will rise. The majority of this material will come
218 MINOR ELEMENTS AND E N VI RO NM E NT A L PROBLEMS
from the dismantling of the reactor core (after removal of the fuel rods) and
associated ancillary structures and equipment.
Intermediate level waste contain a wide range of radionuclides, often with
long half-lives. Examples include 14C ( / 1 /2 5.7 x 103 a), "T c (technetium,
t\f 2 2.1 x 105 a), 129I (iodine, / 1 /2 1.6 x 107 a). They need to be safely stored
for the foreseeable future in a manner that will prevent the escape of the
radioactive chemicals. In some cases, the wastes have been incorporated into
cement-based matrices and placed in stainless steel drums in controlled
access locations. In the past, some of this material has been dumped at sea
by a number of countries.
Low level wastes

This group contains by far the greatest volume of material. These low level
wastes come from industrial, medical, military and scientific uses of
radioactive substances. The maximum activity allowable in low level wastes is
4 GBq tonnes” 1 (gigaBecquerel per tonne) for a emitters or 12 GBq tonnes- 1
for beta and 7 emmitters. The lower limit for waste to be classified as
radioactive is 0.4 MBq tonnes-1. The activity of 40K (beta emitter) in normal
soils is 0.1-0.7 MBq tonnes- 1 and the normal activity range for a emitters
(238U and 2 3 2 Th) is 0.02-0.12 MBq tonnes-1. Fly ash from coal-fired
electricity power stations can have activities of 0.5 MBq tonnes- 1 for (5
emissions and 0.4 MBq tonnes - 1 for a emissions due to the normal
concentrations of 4 0 K, 238U and 232Th in the coal.
In many cases the materials contain extremely small quantities of
radioactivity. The types of materials that come under this heading include
disposable gloves and other similar protective clothing that may or may not
be contaminated; broken glassware and disposable plastic containers that
were used to store radioactive substances; wash liquids used in the cleaning
of vessels etc. Also included are gaseous emissions from nuclear reactors,
reprocessing plants and storage facilities that are deemed to have a low
enough activity to allow direct discharge to the atmosphere. The two main
gases are 85Kr (krypton, t\j2 10.3 a) which is inert, and remains as a gas, and
3H {t\j2 12.3 a) which is incorporated into the hydrological cycle as 3 H 2 0 . It
is estimated that those living closest to nuclear power stations may receive a
dose of about 0.1 mSv a - 1 (milliSievert per year) (this compares with the
average total dose of 2.5 mSv a-1, Table 17.1).
The disposal of these low level wastes is often to landfill sites, usually
involving co-disposal with other non-radioctive materials to further dilute
the activity. Low level waste from the nuclear industry in the UK is
landfilled in a controlled access site. Liquids may be pumped out to sea,
again having been diluted in the effluent with non-radioactive solutions. The
levels in liquid effluents was much higher in the 1970s than now.
Improvements in clean-up technology by the use of ion-exchange resins,
URANIUM 219
precipitators and ultra-filtration has reduced the activity levels in the

discharges to the Irish Sea from the Sellafield nuclear reprocessing and
storage plant, a-discharges were between 80 and 190 TBq a ' 1 and Remis
sions were 5000-9000 TBq a 1 in the period 1971-75. By the 1990s, the
discharges were about 0.7 TBq a - 1 for a-emitters and 300 TBq a - 1 for (3-
emitters.
Environmental impact
The environmental impact of these three groups of waste is a complex

function of (a) how widely they are dispersed; (b) their chemical form;
(c) their activity; (d) their half-life; (e) the type of radiation they emit; and
(f) the energy of the emitted radiation.
The special hazard associated with the radioactivity of the waste declines
with time, therefore, the hazards are reduced after a period of safe storage.
This implies that controlled waste just needs to be stored and the hazard is
naturally removed. Unfortunately the half-lives of some of the radioisotopes
are very long - thousands or millions of years. Even with moderately short
lived radionuclides such as 137Cs and 9 0 Sr, the time taken before they decay
to background levels will be several hundred years (99.9% of the radio
isotope is destroyed over a period equivalent to ten half-lives). Considering
the events of the past 1 0 0 years, the provision of a safe store that will last for
even 300 years without disruption by human, meteorological or geological
events is a daunting prospect.
High level wastes pose the greatest immediate danger because without
constant maintenance the stores will rapidly deteriorate due to the corrosive
nature of the liquid waste and the radiation damage caused by both solid
and liquid wastes. A breakdown in the cooling system will lead to over
heating. This can lead to release of radioactive materials by gas explosions
(as occurred in Kychtym, USSR in 1957) or leakage of liquids and entrained
solids. The very high activity levels of these wastes would make liquid leaks
difficult to clean up and, depending on the force of the explosion,
widespread contamination of surrounding areas could occur.
With medium level wastes, especially if they are incorporated in a solid
matrix, passive storage is possible. Low level wastes pose the same problems
as all potential chemically harmful wastes. Organisms, especially filter
feeders and bottom-living fish and crustaceans, can accumulate the radio
nuclides that are discharged in a similar manner to the way they accumulate
metals such as lead and mercury. The consequence is that the concentrations
in these members of the food chain are very much greater than the levels in
the original diluted effluent. If the radionuclides remain bioavailable, rather
than being immobilized in the sediments then there will be a long-term
hazard. The potential chemical toxicity being enhanced by the metabolic
damage that the ionizing radiation can produce.
16.3 Fate of dispersed radioactive wastes
Ideally, controlled wastes should not cause the release of radionuclides to

the environment outside of the storage areas. Although, as we have seen,
gaseous and liquid emissions do occur when a dilute and disperse method of
disposal is used in place of continuous storage.
In addition to these planned releases, there have been, and will continue
to be, uncontrolled releases from the use of inappropriate landfill and
surface storage conditions for intermediate and low level wastes. There are
many areas in different countries that are causing water pollution problems,
often associated with the processing and use of radionuclides by military
installations. The quantities and types of radionuclides are site specific as are
the possible mobilizing/immobilizing chemicals that have been co-deposited.
Further complications to predicting the impact of the releases from these
sites are introduced by the possible reactions that can occur as the leachate
from the sites moves through the surrounding rocks, soils and watercourses.
Examples include changes in oxidation state, interactions with natural
complexing agents and ion-exchange with clays and organic materials. The
problems caused by these releases are likely to be of a local nature and may
be damaging, but they are of a similar magnitude to the problems caused by
non-radioactive chemical pollution from restricted area sites. Nuclear
weapon testing and accidents associated with nuclear power production
have lead to the uncontrolled releases of radionuclides on a global scale. The
principles that apply to these systems also apply to localized releases and
will be discussed in the following section.
The chemical reactivity of a radioactive isotope is the same as the
reactivity of a stable isotope of the same element. Therefore, 131I will be
concentrated in the thyroid along with non-radioactive iodine; 90Sr will
enter bones along with non-radioactive strontium (strontium ions, Sr2 + ,
substitute for Ca 2 + ); 137Cs will be distributed throughout soft tissues
because non-radioactive caesium ions, Cs +, substitute for K + . In the case of
1 3 1 1 , its impact on the environment will be rapidly diminished if it is stored
for a short period before it is released. It has a half-life of 8.1 days (forming
a stable isotope of the inert gas xenon, I3 1 Xe) which means that after 3
months of storage (equivalent to 11 half-life periods) 99.95% of the original
quantity will have decayed. This contrasts to 90Sr (t X/2 28a) and 137Cs (t i/2
30a) where 3 months storage will have very little effect in reducing the
amount present. Therefore, the risk that 131I poses is short lived, but during
this period the potential hazard is great. 131I is easily absorbed, is
concentrated in one organ of the body and has a high activity. The release of
a large number of high energy electrons, /?“ radiation, over a short time
period can cause great damage to the surrounding cells and may induce
cancerous growths in the thyroid. The effective half-life, î/ 2 >eff (Eqn 16.6),
of an element such as iodine in an organism is a function of both the natural
URANIUM 221
turn-over rate, the ‘biological half-life’ (*(i/2 )bioi) of the element and the
radioactive half-life (r(i/2) rad) of the radioisotope being considered.
f ( l / 2)biol X * ( l / 2)rad
*(l/2)eff = 7 - ----------- — ----------T ( 16 . 6 )
(/(l/2)biol ' *(l/2)radj
The effective half-life for 131I in the thyroid is from 6 to 8 days (the period
increases with a person’s age). This compares with effective half-lives of
about 100 days for 137Cs (mainly found in soft tissues) and 15.5 years for
90Sr (mainly found in bones). The turn-over of iodine can be artificially
increased by the taking of iodide containing tablets. This effectively flushes
out the iodine (radioactive and non-radioactive) already in the thyroid.
The incorporation of radionuclides into human tissue will depend upon
how the radionuclides are dispersed and the transfer routes between the
atmosphere, water, soil, plants, animals and fish.
Deposition from the atmosphere by either dry or wet deposition (Figure
6.5) will lead to the contamination of vegetation, soil and water-bodies. In
the case of iodine the main route to humans is via milk. Grazing animals eat
the contaminated vegetation and within 2 days the milk will be con
taminated. Milk is rapidly distributed to the consumers, so that even though
131I has a short half-life it rapidly enters the human food chain. Children
drink more milk than adults and are particularly at risk. 131I deposited in the
soil will be very much less of a hazard because it will have largely decayed
away before it can be transferred from soil to plants to animals or humans.
However, if 129I ( / 1/2 17 x 106 a) was released in appreciable quantities, it
would pose a long-term threat. Caesium and strontium would also first
appear in milk, but the longer half-lives and different chemistries would lead
to a different, subsequent set of interactions. Caesium would follow
potassium and be taken up readily by plants and be distributed throughout
the flesh of animals. About 99% of the caesium in the fall-out from nuclear
weapon testing consisted of 137Cs and 1% 136Cs ( t i/2 13 d), but the fall-out
from Chernobyl contained about 6 6 % 137Cs and 33% 134Cs (t\/2 2 a). In the
short term, the higher activity of 134Cs makes it more of a hazard than 1 3 7 Cs.
In clay soils Cs will be bound up by the clay minerals (Chapter 12) and be
largely unavailable for plant uptake. In peaty soils the Cs will be much more
available and, if potassium is also low, the lack of competition from K will
enhance the availability. In the UK, after the Chernobyl accident, sheep
grazing on high ground in the Lake District and North Wales were found to
have activity levels of over 1000 Bq kg ” 1 Cs in their flesh. The distribution of
the Chernobyl fall-out was very variable, being related to rainfall and wind
direction. The subsequent effects of the deposited Cs on the human food
chain were also patchy, depending on quantities deposited and soil
conditions. Sheep grazing over soils where Cs availability was high could be
moved to lower ground that had relatively uncontaminated pastures and
222 MINOR ELEMENTS AND EN VIRONMENTAL PROBLEMS
where the soils had bound up the Cs. Feeding here flushed out the 137Cs and
134Cs so activity levels fell below 1000 Bq kg-1. It is also possible to bind the
caesium to hexacynoferrates (Eqn 16.7) by feeding ammonium ferric
hexacyanoferrate(II), AFCF, to the animals. The caesium binds to the
hexacyanoferrate which, not being digested by the animal, is excreted.
137 Cs+ + (NH 4 )3 Fe 3 [Fe(CN ) 6 ] 3 — l3 7 Cs+(NH 4 )2 Fe 3 [Fe(CN) 6 ] 3 +NH+
(16.7)
Strontium follows calcium and is generally more available from soils than
Cs, except in the case of calcareous soils where the large excess of calcium
dilutes the amount of Sr available to plants. Because most of the Sr in
animals is stored in the bones there is less available to humans compared to
Cs. However, the long half-life and the concentration in human bones,
where it can disrupt the cell regeneration processes in the bone marrow,
increases the hazard posed by Sr.
Since 1945 when nuclear explosions were first carried out, there has been a
testing programme of nuclear devices (both fission and fusion). Whereas the
first tests were carried out in the atmosphere, most tests since 1980 have
been underground, so minimizing the dispersion of radionuclides. Fission
devices are based on the use of highly enriched 235U or 239Pu to produce an
uncontrolled chain reaction. This causes the emission of a large variety of
fission product radionuclides as well as unreacted U or Pu. The fusion
reaction used in hydrogen bombs produces large quantities of the /^“-emitter
tritium, 3H (Chapter 3). To initiate the fusion reaction a fission reaction has
to be used, therefore, the explosion produces a similar range of radio
nuclides as a fission device in addition to the tritium.
The yields of fission products from the tests can only be estimated because
the actual size and design of the tested devices was usually kept secret. In
general, the closer to the ground the device was when it was exploded the
larger was the amount of radioactive material that was dispersed. There
were two periods, 1954-58 and 1961-62, when particularly large yield
programmes were carried out with 179 tests in the first of these periods and
128 tests in the second. In 1963, the peak year for the effects of radionuclides
from the testing programme, the mean dose was about 7% of the annual
mean irradiation from natural sources. The level has dropped in 1997 to
below 1 % of natural background levels.
The accident associated with nuclear power generation that has had the
greatest direct global environmental impact occurred in 1986 at Chernobyl,
then in the USSR and now in the Ukraine. In an earlier accident at Three
Mile Island in the USA in 1979, the majority of the released radioactive
material was contained within the containment vessel of the reactor. About
1012 Bq of short-lived radionuclides (mainly 1 3 3 Xe) escaped. Whilst the
health effects from this accident were minor, the change in the American
URANIUM 223
public’s perception of the safety of nuclear power was so great that the
expansion in the nuclear power programme came to an end. Many plants
were left unfinished because of the opposition to the building of nuclear
reactors. The reaction at Chernobyl destroyed the containment vessel and
released about a million times more radioactivity than the Three Mile Island
accident. The actual Chernobyl releases are not known but have been
estimated to be in the range of 1 x 1018—3 x 1018 Bq. This is similar to the
quantity of activity released in the nuclear weapon testing programme in
1961-62.
The Chernobyl power station complex consisted of four similar 1000 MW
graphite-moderated, water-cooled reactors. Each reactor was physically
very large due to the 2 0 0 0 tonnes of graphite they contained, with 1661 fuel
rods containing a total of 190 tonnes uranium oxide. The use of a graphite
moderator meant that the fuel needed to be only slightly enriched in 2 3 5 U.
This made it easier and cheaper to produce. The fuel rods were encased in a
zirconium alloy. The use of water cooling with graphite makes the reactor
inherently less safe than using carbon dioxide (as in the UK Magnox and
Advanced Gas Cooled reactors). The cooling water is both a moderator and
a neutron absorber. The main moderator is the graphite and the loss of
water makes little difference to the moderation processes. However, if the
water boils and the space around some fuel rods contains steam, the
absorption of neutrons is markedly reduced. The number of slow neutrons
entering the fuel rods increases and the fission process starts to run away.
Unless neutron absorbing control rods are rapidly inserted and extra
emergency cooling is applied the temperature will rise rapidly.
On 25 April 1986, an experiment was started to test whether an emergency
power supply could be maintained when the reactor was running at a very
low rate. This involved ignoring a number of mandatory safety regulations
so that the emergency cooling system was cut off and almost all the control
rods were withdrawn. At 1.23 a.m. on 26 April, the water surrounding some
of the fuel rods boiled, forming steam and reducing the neutron absorption
capacity of the system. Within 4 s the temperature had risen to over 2000 °C
and there had been two explosions. The first explosion was confined within
the reactor and involved the overheating and bursting of some of the fuel
rods. The second explosion was so powerful that it lifted off a 1000 tonnes
lid from the reactor vessel and ejected some of the reactor core. This second
explosion was produced by reactions between steam and core materials. In
particular, the zirconium alloy that was released when some fuel rods
disintegrated liberated hydrogen when it reacted with steam at temperatures
above 1200 °C (Eqn 16.8).
Zr + 2H20 -►Z r0 2 + 2H 2 (16.8)
224 MINOR ELEMENTS AND EN VI RO NM ENT AL PROBLEMS
The energy from this reaction helped to force the temperature up even
further and a hydrogen and steam explosion occurred. With the destruction
of the containment vessel, air was able to enter and radionuclides were able
to escape. The graphite moderator continued to burn until it was damped
down on 6 May 1986. Radioactivity continued to escape throughout the
period. During this 10-day period the core was sprayed with water. In
addition, a mixture of clay and dolomite (to form a physical barrier), boron
carbide (to absorb neutrons) and lead (to absorb 7 radiation) was dumped
into the reactor. The majority of the contents of the reactor stayed within
the structure, but melting occurred so that a 130 tonne, highly radioactive,
molten mass flowed down below the reactor and solidified in the lower levels
of the building. After some decontamination of the outer structure of the
reactor, it was encased in a large concrete ‘sarcophagus’, that was completed
by the end of 1986. However, this building was put up very rapidly in
adverse conditions and developed cracks and holes that allow air flow into
and out of the remnants of the old, physically unstable reactor. There is now
a need for another protective cover to seal off the old sarcophagus and the
reactor in order to ensure that there are no further releases of radioactivity if
the old core material becomes disturbed.
As a consequence of the accident a 30 km exclusion zone has been set up
around the reactor and 115 000 people have been moved to other areas.
However, the other three nuclear reactors on the Chernobyl site have been
brought back into operation after decontamination. The employees travel
into work from outside the exclusion zone. About 28 000 km 2 of land and
2225 settlements containing about 850 000 people in Belarus, Ukraine and
Russia are designated as being contaminated with caesium activity in excess
of 185 kBq m~2. A further 77 000 km 2 of land had activity levels of 37-
185 kBq m - 2 of caesium. Although the damaged reactor is situated in the
Ukraine, it is close to the border of Belarus. As a consequence of the
meteorolgical conditions, over 60% of the fall-out landed on Belarus, with a
further 30% falling on Russia and most of the rest on the Ukraine.
The range of radionuclides ejected from Chernobyl was similar to the
range from a nuclear weapon, but the relative proportions of the nuclides
were different. The chemical explosion dispersed much of the more volatile
contents of the reactor and left behind most of the non-volatile fuel and
metallic element fission products. The more volatile components were
released in a number of forms. 85Kr and 1 3 3 Xe, radioisotopes of the inert
gases krypton and xenon, escaped as elemental gases. The majority of the
iodine appeared as Csl and the excess caesium mainly formed CsOH with
some CsTe, ceasium telluride, also being present. The iodine and caesium
contaminated aerosols reached altitudes of 6-9 km, with traces being found
in the stratosphere. Winds from the southeast transported these fine
particles distances of 1200 km in 36 h. During the 10-day emission period,
URANIUM 225
variable wind directions and strengths gave an irregular distribution and

contamination pattern.
The non-volatile components of the fuel rods were released in proportion
to their occurrence in the destroyed fuel rods. The combined action of the
oxygen in the air, that entered the burning reactor, and the high
temperatures led to an increase in volatility. At the relatively low
temperature of 500-800 °C the U 0 2 pellets would be converted into fine
aerosols of U 3 0 8 (Eqn 16.9) that the hot air could carry outside of the
reactor core. Above 1500 °C the U 3 Os becomes volatile and would leave as a
gas before condensing on cooling.
3U 0 2 + 0 2 — > U 3 Os (16.9)
When 1000 °C was reached, volatile oxides of ruthenium were produced
(Eqns 16.10 and 16.11). Again, on cooling, these will condense to form very
fine particulates and the ruthenium oxides were found widely distributed
throughout northwest Europe.
2Ru + 3 0 2 — ►2R u0 3 (16.10)
Ru + 2 0 2 —* R u 0 4 (16.11)
So called ‘hot particles’ of material, which were highly radioactive, were
formed by either the splitting and disintegration of the fuel rods or by
condensation of evaporated products of the fire. The explosions and
subsequent heat of the fires caused contaminated particles of both the
original reactor structure and the materials added to fight the fire to be
mobilized. Whilst the majority of these ‘hot particles’ were deposited within
the 30 km zone, a significant number were detected in areas as far apart as
Greece and Sweden. The particles could be of very different chemical
compositions, reflecting the source material. Some were totally composed of
fuel and fission products, e.g. uranium, americium, neptunium and
plutonium. Others were clay particles with coatings of condensed
ruthenium, caesium and cerium compounds, etc. About 70% of the ‘hot
particles’ were found in the top 1 cm layer of the soil, but in peaty soils
penetration was deeper and particles have been found down to 30 cm. In
forests and gardens, the initial contamination of the soil was less than in
open areas. After the autumn leaf fall, the ground levels were increased as
the particles trapped in the foliage were transferred to the litter layer. The
high activities associated with these particles means that they were of special
concern when airborne and could have been breathed in and trapped in the
respiratory system.
The secondary transfer of the radionuclides has been found to occur via
dust clouds in dry weather. This has led to measurable changes in the region
30-60 km from the reactor. There has been a decrease in 137Cs activity in
226 MINOR ELEMENTS AND EN VIRONMENTA L PROBLEMS
areas with very high levels and increases, of the order of 1 0 %, in areas of
lower activity. Similarly, a forest fire caused radioactive material to undergo
secondary dispersion to areas up to 14-40 km away as the smoke was blown
over the surrounding countryside.
The severity of the effects of radiation damage vary very much from one
species to another. In the case of plants, the descending order of
susceptibility to damage was:
pines > deciduous trees > oaks grass lichens
and in the case of animals the order was:
mammals > birds > fish insects — > invertebrates.
The exposure of the vegetation to the radionuclides has lead to a number of
recognisable effects. Initially there was positive selection of genotypes and
individuals that showed low sensitivity to the radiation. The proportions of
different species in the ecosystem changed as the radiosensitive species were
suppressed. Changes in succession and evolution were produced when the
rate of mutational change was increased and plant immune systems were
suppressed.
In each group of animals there were positive correlations between
radionuclide levels in the animals and the degree of contamination of the
environment in which they lived. Compared to the initial peak levels, there
was generally a tenfold reduction in radioactivity in the animals 1 year after
the accident. There was then only a very slow, or no, decline over the next 5
years. Because the human population moved away from the more
contaminated areas, there were increases in the population of many animals.
This has made the study of the effects more difficult to identify.
Human populations who eat local produce are more at risk than those
who receive their food from a wider range of sources. For instance, in
Finland there was a lower reduction in 137Cs levels in ‘wild foods’, such as
mushrooms, berries, fish, deer and moose than in agricultural products.
With about 25% of the 137Cs in the diet coming from fish this kept the mean
ingested dose at 0.4 mSv for a 4-year period. More than 1.5 million people
received high levels of 13 ll as a result of the accident with 62% receiving 1 0 -
50 mSv, 34% 50-100 mSv and the remainder 100-170 mSv. There has been
an increase in the number of thyroid cancer cases. However, because there
has also been significant population movements it is difficult to relate health
changes to the effect of the accident as clearly as might have been expected.
17 Radon
Radon Abundance by weight: crust, 4 x 10 13 mg kg
Radon is responsible for about half of the total radiation dose of 2.5 mSv
that it has been estimated that the average person in the UK receives (Table
17.1). It has also been estimated that exposure to radon is responsible for
about 2500 UK deaths from lung cancer each year. Radon is a member of
the inert, or noble, gas series (helium, argon, neon, xenon, krypton and
radon). It has a very low chemical reactivity and under normal natural
conditions it is an unreactive, odourless, colourless gas (boiling point 211 K,
-6 2 °C), with a density almost eight times greater than that of air.
Table 17.1 The average annual radiation dose received by the population of the UK
Annual radiation dose
Source (mSv) (Percentage of total)
Natural sources
Radon-222 1.175 47
Radon-220 0.1 4
Food and drink 0.3 12
Cosmic rays 0.25 10
Buildings, ground, etc. 0.35 14
(non-radon nuclides)
Sum of natural sources 2.175 87
Anthropogenic sources
Medical (X-rays, radiotherapy) 0.3 12
Fall-out from 0.01 0.40
bomb tests
Miscellaneous 0.01 0.40
(smoke detectors, TV screens, old
luminous clocks, etc.)
Work 0.005 0.20
Nuclear-power industry 0.001 0.04
Sum of anthropogenic sources 0.326 13.03
Total all sources 2.501 100

228 MINOR ELEMENTS AND EN VI RO NM ENTAL PROBLEMS
Radon is like uranium in having no known stable isotopes. The longer the
half-life, /1/2, the greater the stability, e.g. j^pRn ( / 1/2 = 3.82 d) is more stable
than 8 6 °Rn (h /2 = 55.6 s), with g^Rn (h /2 = 3.96 s) the least stable of the
three naturally occurring radon isotopes. The half-lives of these three
isotopes are so short that the only reason that there is any radon still present
in the Earth is because it is being constantly produced by the breakdown of
other radioisotopes. All the naturally occurring heavy radioisotopes, i.e.
those with atomic numbers of 82 (lead) and above, are members of a
radioactive decay series (Figure 17.1). These series commence with one of
the three relatively stable radioisotopes 2 3 8 U, 235U and 232Th and terminate
with 2 0 6 Pb, 207Pb and 2 0 8 Pb, respectively.
(a) The uranium radioactive decay series that produces radon-222

238 t j
92 u
4.47 x 109 a
Sfn.
24.1 d
2iopb Three decay steps ^

82
22.3 a a,P STABLE
RADON 229
(b) The thorium radioactive decay series that produces radon-220

232 xh
9 0 Tn
14.05 x 109 a
Four decay steps
0.15 s
Three decay steps

a£ P b - ^ P b
a, 0
10.64 h STABLE
(c) The actinium (or uranium-235) radioactive decay series that produces radon-219
%5U
704 x 106 a
3m
25.6 h
Five decay steps
«,P
2£R»
3.96 s
2i 5P°
1.8 x 10-3 s
Three decay steps

&P>> ■
2
►
^Pb
82 r °
36.1 min STABLE
Figure 17.1 The three naturally occurring radioactive decay series that produce radon. The
half-life of each nuclide is given below its symbol. Vertical arrows indicate a emission and
horizontal arrows indicate f3 emission. Where several steps are grouped together both a and (3
emissions occur.
230 MINOR ELEMENTS AN D EN VI RO NM E NT A L PROBLEMS
17.1 Radon in buildings
The parent of 222Rn is g^Ra (radium) which has a half-life of 1602 years and
is widely distributed in rocks, sediments and soils along with the other long-
lived members of the 238U series. The radioactive decay of the radium
atoms, whose compounds are usually solids, produces radon gas that can
diffuse through the rocks and soils into the atmosphere. If there is a building
over these deposits, the radon will enter that building unless there is a gas-
impermeable barrier. The quantity of radon reaching the atmosphere will
depend upon the quantity of radium in the rocks and soils, how near the
surface the radium is and how permeable the rocks and soils are. If the
permeability is low because there are few connecting pores, fissures and
cracks, the radon could have largely, or completely, decayed away before it
reached the surface. With a half-life of 3.82 days, over 99% of a given
emission of radon will have decayed inside a month. The immediate
daughter products are very short-lived a-particle emitters (Figure 17.1) and
they are transformed into g2 °Pb, a f3 emitter, which has a half-life of 22.3
years. The lead is adsorbed on to solid surfaces, which prevents its escape
into the atmosphere. Once the radon reaches the atmosphere it, and its
daughters, can be breathed in. The lead then becomes much more important
because the solid radioactive particles are trapped in the lungs, whereas the
gaseous radon is breathed out again.
Measurements of radon concentrations in houses have been made since
the 1970s. The number of houses surveyed has been increased as it became
apparent that relatively high concentrations of radon were much more
common than had at first been thought. The UK action level for the annual
average radon concentration in houses was reduced from 400 to 200 Bq m - 3
in 1990 (the US action level is 150 Bq m~3). It has been estimated that
70 000-100000 homes in England will be above this level (mainly in
Cornwall, Devon, Somerset, Northants and Derbyshire) and 2000 homes in
Scotland (mainly in the Grampians and Highlands). The action level of 200
Bq m - 3 implies a lifetime risk that 1% of non-smokers breathing this air will
die of lung cancer due to exposure to radon and its daughters.
The problem is probably greater now than it was in the past because
houses are better insulated and have fewer draughts. However, it could be
that the problem has only recently been identified because extensive radon
measurements have only been carried out recently. A reduction in the
number of air changes in a house will allow the radon seeping through the
floor to build up, as there will be less dilution with ‘fresh’ air from outside
the house. The daughter elements, especially 2 1 0 Pb, accumulate on the
household dust particles suspended in the air and deposited on surfaces.
Exposure to radioactivity is increased every time dust is disturbed in a room
and the fine particles enter the air that is breathed. The concentration of
radon outside the building drops very rapidly as it leaves the soil and winds
RADON 231
mix the gas with air. In a house there are weaker air currents and radon
levels are about 50% greater in ground-floor rooms than in first-floor
rooms. The small pressure differences between the inside and the outside of
buildings tend to draw in the radon preferentially from the surrounding
ground. The amount of radon entering the living space of houses can be
reduced by interception so that is well below the action level. A hole filled
with coarse porous material is constructed in the ground under the house.
This hole acts as a sump and the gas enters this first. The radon can then be
sucked out of the sump by means of a tube and a fan connected to the
outside of the house. The ground floor can be further insulated from radon
entry by installing a continuous sheet of heavy-duty polythene over the floor
(if the house has already been built) or under the floor (if the house is being
built). In older houses, cracks in and around the flooring can also be sealed.
In areas such as southwest England that are known to be at risk, building
regulations now require radon protection measures to be installed in all new
buildings.
17.2 Biological effects
The properties of alpha, a , particles (helium nuclei) are such that they are
only a health hazard if the emitter is in contact with living tissue. The
relatively large, positively charged a particles rapidly lose their energy to
surrounding atoms. This means that they do not penetrate the skin and are
stopped by a few centimetres of air. However, if the a emitter is in the body,
e.g. on lung tissue, all of the energy is released in a very small volume. The
chances of this energy breaking chemical bonds in molecules or causing
ionization or forming reactive free radicals are relatively high. All of these
changes have the potential to disrupt the normal metabolism and produce
changes which may either be easily reversed or affect cell replication and
induce cancerous growth. For these reasons a particles are given a weighting
factor that is ten times greater than that given to beta minus, (3~, particles
when comparing their potential for inducing biological damage. (3~ particles
are electrons. They have a lower mass (approximately 1:7300) and,
therefore, travel faster and further before losing the same amount of energy
as an a particle. This means that the density of radiation damage inside the
body from ingested (3 emitters is lower than from a emitters of the same
energy because the energy from the a-particles is released in a smaller
volume. The sievert, Sv, is a dose equivalent unit that attempts to take
account of the different effects of different types of radiation on body tissues
so that comparisons can be made between different radiation sources. Table
17.1 indicates the average background radiation dose that the UK
population receives. The actual dose any individual will receive depends
upon where they live and work. Levels of radon in the home can make a
great difference, as will building materials; for example, clay bricks

(containing radioactive 4 0 K) are five times more radioactive than sandstone
blocks. An increase in altitude of 2000 m doubles the dose received from
cosmic radiation. The medical use of X-rays has produced a significant
increase in dose. The use of radioisotopes and gamma, 7 , ray irradiation,
particularly for cancer therapy, can lead to very high dosages being given to
individuals. A single whole-body dose of 250 mSv might cause a reduction in
white blood cell count, whereas a dose of 2-5 Sv is likely to kill 50% of those
exposed within 60 days. More controversial are the detrimental effects
caused by lower dose rates. It is generally assumed that there is a linear non
threshold dose-effect relationship in which all doses greater than zero
received during a lifetime contribute to causing biological effects. There is
then a finite probability of the occurrence of a detrimental effect, such as
cancer, that is proportional to the dose received. It should be remembered
that because all life-forms contain a ‘natural’ level of radioactivity it is not
possible to have a zero effect, if the non-threshold theory is correct. It has
been estimated that living in a house with a radon concentration equivalent
to 20 Bq m ~ 3 gives an effective dose of 1 mSv a-1. This would produce a
lifetime risk of one in 1 0 0 0 of developing cancer for non-smokers and a one
in 100 chance for smokers. A 1997 review of eight studies comparing lung
cancer development with estimated radon exposure suggested that 25 year’s
exposure at the UK action level of 200 Bq m ~ 3 would increase the chances
of developing lung cancer by about 50% and at the USA action level of 150
Bq m - 3 there would be a 13% increase. The methods by which these sorts of
estimates are arrived at are of variable precision and depend upon various
assumptions about the interpretation of the data upon which they are based.
The larger the dose the greater the risk and the more reliable the risk
estimates are likely to be.
18 Hazardous organic compounds
18.1 Synthetic organic compounds
The large-scale production of synthetic organic chemicals commenced in the

middle of the nineteenth century. Initially coal was the major raw material
for the production of coal-tar oil from which most of the early organic
compounds were extracted or synthesized, but gradually oil and natural gas
have become the favoured starting materials. With increasing knowledge of
chemical structure and increasing technical ability the range of compounds
synthesized has widened and become more divergent from naturally
available substances. Some of the synthesized compounds such as PCBs and
CFCs were manufactured because they were very stable. It is now realized
that this stability, which made them so suitable for their intended usage (e.g.
PCBs as coolant-insulator fluids in electricity transformers), is causing
problems when they are released into the general environment. They are
very persistent because microorganisms and other agents that normally
bring about the biodegradation of natural organic materials are either
unable to break down these stable molecules or can do so only extremely
slowly. Similarly, inorganic reaction mechanisms may be ineffective, for
instance with CFCs in the troposphere (see Chapter 2), or produce
unwanted products (chlorine from CFCs in the stratosphere). The concen
tration of these organic compounds in air, water, soil and organisms is
generally very low (of the order of parts per billion or trillion). However,
their persistence, possible biomagnification and potential toxicity is a cause
of great concern.
When considering the risks posed by these synthetic organic chemicals it
is useful to remember that many naturally occurring organic chemicals are
also extremely toxic. Very few naturally occurring organic chemicals have
been tested in the same way as the synthetic chemicals. Of the small number
that have been tested using animal cancer bioassays, about half were found
to be carcinogenic. The concentrations of these natural carcinogens in food
are generally thousands of times greater than the concentrations of synthetic
chemicals, e.g. orange juice (30 ppm); apples, potatoes (50 ppm); brewed
coffee (90 ppm); lettuce (300 ppm); raspberries, strawberries (1000 ppm);
comfey tea (3000 ppm). Alcohol (ethanol) is carcinogenic and its potency, as
determined in rodent tests, can be compared with that of the most potent of
the dioxins (TCDD, see section 18.2). If the permitted level of ethanol
234 MINOR ELEMENTS AND E N VI RO NM E NT A L PROBLEMS
ingestion was set so that it would have the same deleterious effect as the
acceptable daily maximum dose of TCDD, then the recommended level
would be 1 x 1 0 ~ 4 g of alcohol per day (one glass of wine or a half-pint of
beer every 350 years!). Another naturally occurring compound, indole
carbinol, reacts in a similar manner to TCDD with regard to stimulating
carcinogenesis. Cabbage, cauliflower and broccoli contain 50-500 ppm of
indole carbinol. One helping of broccoli gives an effective dose of this
potential carcinogen that is 1500 times greater than the maximum
recommended TCDD dose (these figures take into account the relative
potency and lifetimes in the body of the two compounds). The widespread
occurrence of relatively high concentrations of natural toxins should not be
ignored when considering the extent of the risk posed by the ingestion of
synthetic organic chemicals.
Tens of thousands of new compounds are synthesized each year and
hundreds of new compounds are manufactured and sold in varying
quantities from a few grammes to thousands of tonnes. It is not possible to
highlight more than a few groups that illustrate the factors that are causing
concern.
18.2 Dioxins
The dioxins are two groups of compounds that are found as impurities in
the manufacture of some chlorinated organic compounds or when
chlorinated compounds are burnt at relatively low temperatures (less than
1000 °C). These two groups are (a) the polychlorinated dibenzo-/>-dioxins
(PCDDs) (Figure 18.1) and (b) the polychlorinated dibenzofurans (PCDFs)
(Figure 18.1). There are 75 members of the PCDD group and 135 members
of the PCDF group. One member of the PCDD group is also referred to as
dioxin. This is 2,3,7,8-tetrachlorodibenzo-/?-dioxin (Figure 18.1).
The toxicides of the individual members of the two groups are very
different. The most toxic compounds have four chlorine atoms (tetrachloro)
in the 2, 3, 7 and 8 positions (Figure 18.1); 2,3,7,8-tetrachlorodibenzo-/?-
dioxin (2,3,7,8-TCDD) is extremely toxic to laboratory animals (e.g. LD 5 0
guinea pigs 0 . 6 /ig kg - 1 body mass), and is considered to be the most
dangerous of all the dioxin group.
The least toxic compounds have from one to three chlorine atoms
(monochloro to trichloro) and are considered to be relatively harmless.
Whilst many of the dioxins are extremely potent carcinogens for animals
their effects on humans are less certain. In 1976, there was an explosion at a
chemical works in Seveso, Italy, that contaminated an area of about 3
square miles (7.8 km2) with dioxins. Many animals died but the 36000
people in the affected area of the town survived, although 193 suffered from
severe chloracne (a skin disorder). Only one case of chloracne had not
HAZARDOUS ORGANIC COMPOUNDS 235
(a) Dibenzo-/wUoxin (b) Dibenzofuran
(c) 2,3,7,8-TetrachIorodibenzo-p-dioxin
Figure 18.1 Structures of (a) dibenzo-/?-dioxin and (b) dibenzofuran indicating the eight
positions that can have chlorine atoms attached to form the two groups of polychlorinated
compounds described as dioxins. (c) The structure of 2,3,7,8-tetrachlorodibenzo-/?-dioxin,
TCCD.
cleared up 10 years later. There appears to have been no major long-term

health effects. It is still possible that cancers linked to the exposure of the
population to dioxins could develop because the induction period could be
20 years or more. However, there has been no convincing evidence that
dioxins are especially potent carcinogens for humans. The mean dose of
TCDD to the children that developed chloracne was 3.1 fig kg - 1 body
weight, much higher than that which was so deadly for guinea pigs. Studies
of people exposed to dioxins either from handling contaminated chemicals
or due to accidental release have not yet shown dioxins to be unusually
dangerous. For example, rats were 4-90 times more likely to develop
tumours than humans even though the humans had similar or greater
exposure to TCDD. However, some US soldiers, who were in Vietnam at
the time a herbicide called Agent Orange was sprayed over large areas of
country, are showing effects that are being related to the use of the
herbicide. Agent Orange contained a mixture of the ?z-butyl esters of
chlorinated phenoxyacetic acids plus traces of dioxins (0.5-50 ppmv, with
most at the low end of the range). There is now thought to be good evidence
that cancer of the connective tissues, diseases of the lymph tissues and
glands, and chloracne are related to exposure to Agent Orange and similar
herbicides. ‘Background’ concentrations of TCDD in human fat, where it is
stored in the body, range from non-detectable to 20 pg kg-1. Children with
236 MINOR ELEMENTS AND EN VI RO NM ENT AL PROBLEMS
chloracne at Seveso had a mean TCDD concentration of 22000 pg kg - 1

(range 800-28 000 pg kg-1). The half-life of dioxins in humans is about 7
years. Over 98% of human intake is via food, especially from beef and milk.
Airborne dioxins are deposited on fodder and soils from where they can
enter the food chain. The half-life of dioxins in soil has been estimated to be
about 1 0 0 years.
The dioxin group of compounds are produced in a number of processes
involving the use of chlorine and chlorine compounds. The dioxins are by
products of these reactions. Which of the 210 dioxins are actually formed,
and in what quantity, depends on the process conditions. As a consequence,
the potential hazard due to these impurities also varies. Chlorophenols such
as the familiar T C P ’ (trichlorophenol) are widely used as wood
preservatives, bactericides, insecticides and herbicides. They are also
intermediates in the production of paper, paints and textiles. Polychlorin
ated biphenyls (PCBs) are another group of chlorinated organic compounds
that contain small quantities of dioxins. The combustion of chlorine-
containing mixtures in municipal and industrial waste incinerators will
produce dioxin compounds unless the operating conditions are very care
fully controlled. This means that older municipal incinerators can be
significant local sources of dioxins, emitting between 1000 and 7500
ji g tonnes - 1 solid waste incinerated, depending upon its composition. The
tightening of the UK emission standards for solid waste incinerators
emissions is expected to reduce total UK incinerator emissions in 1998 to 15
g a - 1 toxic equivalent value (TEQ) (see later).The 1994 emissions levels were
460-560 g a - 1 (TEQ). The new standards will be that emissions should be
below 1 ng m - 3 and for them to aim for 0.1 ng m-3. Incinerators need to be
designed so that (i) the combustion gases are above 850 °C for at least 2 s in
the presence of over 6 % dioxygen (this destroys any PCDD and PCDF
formed from chlorine-containing compounds); (ii) reduce particulate
emissions; and (iii) reduce flue gas temperatures after the boiler to below 250
°C (the combined effects of traces of organic compounds, chlorine and
metals can produce PCDDs and PCDFs on the surface of particulates at
temperatures in the 250-400 °C range. Therefore, even though no PCDD or
PCDF leaves the furnace, the compounds can be formed in significant
quantities in the flue gases). Many plastics, e.g. polyvinyl chloride (PVC),
contain organochlorine compounds that can be involved in dioxin
production. Leaded petrol contains chlorine-containing compounds such as
ethylene dichloride as a scavenger for the lead produced during combustion.
Therefore, vehicle exhaust emissions and used lubricating oil also contain
small quantities of dioxins. As the use of unleaded petrol increases this
source of dioxins is becoming less important.
Because the various members of the dioxin group of compounds have
very different toxicities, it is important to know the compound profile of the
dioxin mixture as well as the total quantity of dioxins present. With 210
compounds to be considered this leads to some practical difficulties in

presenting the results, as well as carrying out the analysis. One attempt to
take these problems into account involves the use of the concept of the TEQ
value. Each of the dioxins is assigned a ‘toxic equivalent factor’ (TEF). The
TEF for 2,3,7,8-tetrachlorodibenzo-/?-dioxin (2,3,7,8-TCDD) is 1 because it
is considered the most toxic of the dioxins. Other compounds are assigned a
figure between 0 (the mono-, di- and tri-compounds) and 1 depending upon
their toxicity relative to that of 2,3,7,8-TCDD. For example, the
pentachlorodibenzo-/?-dioxins (PeCDDs) have a TEF of 0.5 if the chlorines
are in the 1,2,3,7, 8 positions, but a TEF of 0 for the other PeCDDs. The
pentachlorodibenzofurans (PeCDFs) also have a TEF of 0 unless chlorines
are in the 2,3,4,7, 8 positions (TEF 0.5) or in the 1,2,3,7, 8 positions (TEF
0.05). The quantitative composition of the mixture of dioxin compounds is
determined and the result for each component is multiplied by the relevant
TEF. These values are than added together to give the TEQ. The resulting
single-figure TEQs allow easier comparison of the emissions from different
sources. For example:
Source A:
Emission of
1 g 2,3,7,8-TCDD + 4 g PeCDD = 5 g dioxins day - 1
TEQ = (1 x 1) + (4 x 0) = 1 g day - 1
Source B:
Emission of
0.75 g 2,3,7,8-TCDD + 2 g 2,3,4,7,8-PeCDF = 2.75 g dioxins day - 1
TEQ = (0.75 x 1) + (2 x 0.5) = 1.75 g day - 1
This indicates that although source B is emitting a lower quantity of dioxins,
the danger from this source is potentially greater. However, it must be
remembered that (a) the TEF values are only approximations for the
relative toxicides of the individual compounds; and (b) the simple addition
of the values may not be a good representation of the combined effects of a
complex mixture of dioxins.
Dioxins are contaminants in chlorophenols, halogenated herbicides such
as 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 2,4-dichlorophenoxy-
acetic acid (2,4-D), and in PCBs. They are, therefore, found wherever these
chemicals have been used or disposed of. They are further distributed by
incomplete combustion of chlorinated organic compounds. Very sensitive
methods of analysis have been developed so that it is possible to identify
dioxins at extremely low concentrations. We know that dioxins are present
at these very low levels (e.g. 9 pg TCCD kg - 1 milk in the UK), but do not
know what the safety level is. It has been estimated that the present human
exposure level TEQ is about 1 pg kg - 1 body weight per day with about 30%
of this as TCDD.
238 MINOR ELEMENTS AND ENVIRONMENTA L PROBLEMS
18.3 DDT and related compounds
The insecticidal effects of 1,1,1 -trichloro-2,2-di-(4-chlorophenyl)ethane,

originally called dichlorodiphenyltrichloroethane (i.e. DDT, Figure 18.2)
were first exploited in the 1940s. It was used in high concentrations through
out the world, especially where malaria was endemic. It has a relatively low
toxicity for humans and it was extremely effective. In the early 1960s,
concern was expressed about the persistence of DDT and some of its
degradation products, DDE and DDD (Figure 18.2), together with evidence
that these compounds were building up in some organisms. For example, in
an area sprayed with DDT to control Dutch Elm disease, the concentration
of DDT in robins was 20-30 times higher than in the earthworms that they
ate. There was a 70% decline in robin population in the sprayed area. Egg
shell thinning and the failure of fledglings to develop, especially amongst
birds of prey, have been related to the presence of chlorinated pesticides
such as DDT in their diet.
The use of DDT and related products was banned in the USA in 1972 and
other developed countries later, but it is still widely used (over 40 000 tonnes
per year) in developing countries where its low cost and low human toxicity
are thought to outweigh its disadvantages. The first cases of insects
becoming resistant to DDT were noted as early as 1948. As time has passed
Cl
(a) DDT
C l - C — Cl
/ \
Cl Cl
(b) DDD (c) DDE
Figure 18.2 Structures of (a) l,l,l-trichloro-2,2-di-(p-chlorophenyl)ethane, DDT; (b) 1,1-

dichloro-2,2-di-(/?-chlorophenyl)ethane, DDD; (c) l,l-dichloro-2,2-di-(/?-chlorophenyl)ethene,
DDE.
more and more of the target groups have developed resistance. The
persistence of DDT and its wide-scale use encouraged the development of
resistant strains of insects and other pests. The DDT kills off the susceptible
individuals in the pest population and also the natural predators. Any
naturally resistant pests are then able to develop rapidly because of the lack
of natural competitors. The persistence of compounds such as DDT keeps
down the susceptible population and allows the tolerant individuals to
become dominant. The resistant strains generally have some biochemical
mechanism that enables them to detoxify the insecticide. For example, DDT
can be detoxified by enzyme conversion to DDE (Figure 18.2), a compound
that has a very low toxicity for insects. DDT affects the nervous system by
interfering with the sodium balance in nerve membranes. The skin of
animals prevents intake through absorption, but insect cuticles have a high
permeability. This is why DDT appeared to be so safe to use. However, the
persistence of DDT in soils and on foliage meant that it could enter food
chains and be constantly recycled. The preferential solubility of DDT in fats
(it is described as being lipophilic) meant that it was stored in fatty tissue
and not readily excreted. This leads to biomagnification. The toxic effects on
the organism may result after a relatively long period of time either through
levels rising above a threshold that induces adverse effects or because some
stress event causes the chemical to be released from the fat. The effects of
stopping the input to the sea are shown off the coast of California where sea
lion blubber in the early 1990s contained 5 mg (DDT/DDE) kg - 1 compared
to 760 mg (DDT/DDE) kg - 1 in 1970. The 5 mg kg - 1 level is probably still
too high to ensure that there are no continuing ill effects, but the numerous
examples of overt damage to the sea lions are no longer found.
18.4 Polychlorinated biphenyls, PCBs
The polychlorinated biphenyls (PCBs) are a group of compounds that

contain from one to ten chlorine atoms attached to various carbon atoms in
the biphenyl molecule (Figure 18.3). There are 209 possible members of the
PCB group and industrial processes produce various mixtures whose
compositions depend upon the conditions of manufacture. In addition to
the various members of the PCB group the commercial products usually
contain small quantities of dioxins as impurities.
The PCBs are chemically stable and have a high electrical resistance.
These properties made them appear to be ideal components for use in
electricity transformers (which lower or raise the voltage of power lines) and
capacitors (which help maintain constant voltage during power trans
mission). They have also been widely used as additives in lubricating and
cutting oils, hydraulic fluids, heat-transfer fluids, etc.
3' 2' 2 3
5' 6' 6 5
Figure 18.3 Structure of the biphenyl molecule. Each of the numbered positions can have a
chlorine atom attached to i t . The resulting polychlorinated biphenyls, PCBs, can have from one
to ten chlorine atoms per molecule depending upon the conditions under which they are
produced.
Production of PCBs came to an end in most countries in the late 1970s. In

the mid-1960s analytical methods that were capable of detecting small
concentrations of PCBs became available. It was soon clear that PCBs were
being transferred from the industrial and urban areas of use to places like
the Arctic and Antarctic that were far removed from any local source. Of
even greater concern were the findings that the PCBs were accumulating in
animal fatty tissues. PCBs were found to be transferred particularly
efficiently through aquatic food chains so that the highest concentrations
were found in marine mammals such as seals and whales (5-50 mg kg - 1
blubber), otters (5-200 mg kg - 1 fat) and fish-eating birds. The concentration
in the body fat may be 1 0 million times greater than the concentration in the
water in which the mammals live. There appears to be a strong link between
high concentrations of PCBs in body fat and low rates of reproduction in
animals such as seals, beluga whales and otters. However, high levels of
PCBs are usually also associated with high levels of other organic chemicals,
so it is not clear whether it is one chemical (which may or may not be a PCB)
or a mixture of chemicals that are responsible for the effects. Also, because
the PCBs are mixtures of different compounds, varying effects may be due
to differing mixtures. There is a weaker link between high PCB concen
trations and damage to the immune system of marine mammals. Relatively
high levels of PCBs (10 fig dm-3) may be found in human breast milk. There
have been suggestions that the higher PCB concentrations may cause
reductions in reproductive efficiency (see section 18.6) and impair the
learning ability of children, as well as having potential carcinogenic activity.
The evidence is not clear because of the low concentrations and the long
time period over which such effects may occur.
Disposal of PCBs can be achieved by high-temperature incineration
(temperature greater than 1200 °C for more than 2 s in the presence of excess
oxygen). This process is feasible for industrial and commercially held stocks
of PCB-containing equipment and contaminated liquids. It is not feasible
for contaminated solids such as soils, if large tonnages are involved. Even
high-temperature incineration can cause problems unless the equipment is
carefully operated and maintained. There are possibilities of producing
dioxins and not completely destroying all of the PCBs unless the correct
combustion conditions are fully achieved. Costs are very high - several
thousand pounds per tonne! Large quantities of PCBs have been placed in
landfill sites from which they can escape via the atmosphere or through
ground water. Much work has been carried out on the development of
microorganisms that will breakdown PCBs in situ. Unfortunately, the great
variability in natural conditions and competition from other micro
organisms has prevented the transfer of successful laboratory-tested
biotechnology systems to natural systems in a reliable manner.
A total of about 1.2 Mtonnes of PCBs were manufactured throughout the
world before production ceased. Over 30% of this output has been
estimated to have been released to the environment, mainly to landfill sites.
Probably half of the PCBs is awaiting disposal after use. Provided all of
these stocks are successfully destroyed, probably by incineration, the global
levels of PCBs should remain relatively constant over the short term. There
should then be a slow decline as the compounds are slowly decomposed and/
or buried in sediments. The wide distribution of equipment containing
PCBs, the poor storage of PCB-contaminated oils and the high cost of
effective incineration make it likely that there will be further releases of
PCBs to the global environment.
18.5 Polynuclear aromatic hydrocarbons, PAHs
The polynuclear (or polycyclic) aromatic hydrocarbons contain two or more

fused aromatic rings (Figure 18.4). Eight of the PAHs are considered to be
possible or probable carcinogens. The compounds are a by-product of
incomplete combustion. Natural sources include forest fires, prairie fires and
volcanic eruptions. Anthropogenic sources include motor vehicles (parti
cularly diesel engines), coking ovens, asphalt manufacture, fossil-fuelled
furnaces, cigarettes and barbecues. PAHs may be formed from any
hydrocarbon source if the conditions of incomplete combustion due to lack
of oxygen are met.
Straight-chain saturated hydrocarbons, such as methane or ^-octane, are
least likely to form PAHs whereas cyclic hydrocarbons, as found in diesel
and fuel oil, are more likely to produce PAHs. The closer the structure of the
hydrocarbon to that of the PAHs the easier it is for PAHs to be formed.
The increasing use of fossil fuels has increased the exposure of humans to
PAHs. In the UK, before the introduction of the Clean Air Act (1956),
domestic coal fires were a major source of PAHs which tended to be
adsorbed on to the surface of soot and smoke particles.
The relationship between soot and cancer in chimney sweeps was
recognized in the nineteenth century. Urban levels of PAHs, having fallen
following the introduction of the Clean Air Act, have risen again, especially
because of the emissions from poorly maintained diesel-engined vehicles.
242 MINOR ELEMENTS AN D E N VI RO NM E NT A L PROBLEMS
Benzo(a)pyrene
Chrysene
Figure 18.4 Structures of chrysene and benzo(a)pyrene, two examples of the polynuclear
aromatic hydrocarbon, PAH, group of compounds.
PAHs such as benzo(a)pyrene appear to exhibit low acute toxicity but

have very significant chronic toxicity, i.e. a single large dose will not cause
immediate adverse effects but continuous low doses will probably induce
cancer. For non-smokers, food is normally the main source (over 95%) of
the carcinogenic PAHs (average daily intake about 3 /ig) unless they spend a
lot of time in the presence of smokers or in polluted urban atmospheres. In
these cases their intake may be increased by another 2-5 /ig d-1. Smoking 20
unfiltered cigarettes a day will also increase the daily intake by 2-5 /ig.
Concentrations of PAHs in food vary quite considerably with unwashed,
leafy vegetables (20-40 /ig kg-1), unrefined grains (10 /ig kg-1), charcoal-
broiled and smoked meats and fishes ( 1 0 - 2 0 /ig kg-1) being major potential
sources. Leafy vegetables and grains are contaminated by surface
adsorption of atmospherically deposited PAHs. The route of ingestion needs
to be taken into account when looking at potential risk.
Generally intake via the lungs, as with cigarette smoke and atmospheric
contamination, leads to a greater percentage absorption into the body than
does contamination of solid food. The carcinogenic properties of PAHs are
believed to be due to metabolites formed in the body as the compounds are
broken down.
There are great difficulties in deciding the degree of risk posed by the very
low concentrations of PAHs or other chemicals. It is known that chemicals
show an effect at a particular concentration that is generally much higher
than the concentration found in normal environmental samples. Are the
same effects shown at the lower levels? How can the cause of cancer, say, be
identified when the population is exposed to a large number of possible, and
different, trigger chemicals that may be of natural or anthropogenic origin?
In addition, there may be synergistic effects between these chemicals which
can considerably increase the risks posed by the individual chemicals
separately. The long gestation time between exposure and clinical
appearance of the cancer may well make it impossible to be certain of the
cause. The outstanding work of analytical chemists in developing methods
for the recognition and determination of extremely low concentrations of

various elements and compounds has made us aware of their presence.
Unfortunately our knowledge of toxicology has not kept pace and we are
not able to quantify the risk that these low levels of chemicals pose.
18.6 Endocrine-disrupting chemicals
There have been many reports that provide evidence that chemicals that can
interact with hormone (endocrine) systems are widely distributed. The sources
of the disruptors may be natural systems or synthetic chemicals. The
interactions can result in the cell’s endocrine signalling mechanism indicating
that there appears to be too much or too little of the required hormone. As a
consequence, metabolic pathways depending on hormone signals are
disrupted. Examples of the effects include the development of female
genitalia in male fish exposed to nonylphenol (Figure 18.6) and a variety of
reproductive and sexual development dysfunctions shown by alligators in
Lake Apopka, Florida, exposed to dicofol (a pesticide similar to DDT).
Natural hormones are used by organisms to regulate various changes in
cells and tissues. The relative levels of a variety of hormones can trigger the
starting, or the stopping, of a wide range of different cellular activities some
of which are linked to the reproductive cycle of the organism.
Human oestrogen, oestradiol-17/3 (Figure 18.5), differs from the other
steroid hormones such as testosterone (Figure 18.5) because it has a
phenolic A-ring.
Most oestrogenic chemicals, whether synthesized or natural, also have a
phenolic group. Other factors that can play a major part in controlling the
overall oestrogenic activity of a chemical include the configuration (three
dimensional shape) of the molecule and the distribution of any substituents.
For example, diethylstilbestrol is an active oestrogen whereas dimethyl-
stilbestrol shows very little activity (Figure 18.5); endosulfan-a is
oestrogenic, but does not contain a phenol group (Figure 18.6). The
intracellular steroid hormone receptors and signalling pathways can
effectively discriminate between normal hormones such as testosterone and
oestradiol-17/3, but they are less effective at discriminating between
externally derived hormone-like chemicals. This lack of discrimination can
be used to allow drugs to beneficially modify cell activity, but it also means
that the cells are susceptible to accidental disruption from environmentally
distributed chemicals.
Oestrogenic activity in cells is triggered by oestrogens entering the cells
and binding to oestrogen receptor proteins (ORP). This leads to the
production of proteins, via genes, that promote the cellular and/or tissue
response that the hormone concentration change initiates. The mechanism
can allow very specific changes to occur in an organism at the required time
244 MINOR ELEMENTS AND EN VIRO NM E NTA L PROBLEMS
OH OH
HO
(a) Oestradiol - 17(3 (b) Testosterone
OH
(c) Diethylstilbestrol (d) Dimethylstilbestrol
OH
HO
(e) Ethinyloestradiol
Figure 18.5 Structures of (i) two natural human hormones (a) oestradiol-17/3, (b) testosterone;
and (ii) some pharmaceutical hormones (c) diethylstilbestrol, (d) dimethylstilbestrol,
(e) ethinyloestradiol.
and under the required conditions. However, the presence of an endocrine-

disrupting chemical can interfere with the smooth running of the system.
The response of an oestrogen receptor protein to a chemical may be positive
(the chemical triggers a reaction) or it may be negative (the chemical blocks
a reaction). The blocking of the receptor by anti-oestrogens has been one of
the routes followed in the chemotherapy of breast cancer.
The oestrogen receptor proteins may be activated indirectly. Some
chemicals can bind to certain cell surface receptors. This then triggers a
series of signals that eventually leads to the activation of the ORP without
the original chemical actually binding to the ORP. The requirement for
(a) Nonylphenol (b) Bisphenol A
OH
HO
(c) Coumestrol (d) Endosulfan - a
Figure 18.6 Structures of some compounds with oestrogenic properties: (a) nonylphenol;
(b) bisphenol A; (c) coumestrol (a plant hormone); (d) endosulfan-a.
structural similarity with oestrogens need not apply to the same extent for
chemicals activating the ORP indirectly. This opens up the possibility of
having a very wide range of chemicals that could be endocrine disruptors.
As interest in endocrine-disrupting chemicals has grown, it has become
clear that there are a very large number of such chemicals to be found in
different environments. Natural animal products such as meat and milk
contain traces of the hormones that the animals use themselves to control
various processes. Many plants contain oestrogen-like chemicals, phyto-
oestrogens, as a normal part of their composition. Significant quantities are
found in grains (barley, oats, rice, rye, wheat); soya beans; vegetables
(beans, carrots, peas, potatoes); fruit (apples, cherries, plums); coffee; fungi,
etc. These phytoestrogens generally have low activities compared to
oestradiol-17/? and are rapidly metabolized indicating that they pose a low
risk. However, disruptive effects have been induced by genistein (found in
soya bean products), coumestrol (a common plant component, Figure 18.6)
and zearalenone (a mycotoxin), amongst others. There is not enough
evidence to indicate whether additions to natural background levels or diet
changes will be harmful.
246 MINOR ELEMENTS AND EN VI RO NM E NT A L PROBLEMS
Amongst the synthetic chemicals, there are the purposely produced

hormones, such as the oestrogens used in birth control pills and the growth
promoters for farm animals. Whilst the majority of the oestrogens used in
oral contraceptives are metabolized, it has been shown that some is excreted
unmetabolized (1% in the case of ethinyloestradiol, Figure 18.5). These
artificial oestrogens are not readily broken down during sewage treatment
and they have been identified in streams and rivers below sewage works.
Concentrations of 10 ng dm - 3 of ethinyloestradiol prevented egg production
in minnows in a laboratory study. Levels found in UK waters have been as
high as 15 ng dm - 3 near the outfalls of sewage treatment works. Other
examples of chemicals that have been shown to be endocrine disruptors in
animal or cell culture studies include:
(i) alkylphenol polyethoxylates - surfactants, used in cleaning products
and to help paints and pesticides stick to their target surfaces. These
compounds appear to be 1 0 0 0 - 1 0 0 0 0 times less active than oestradiol-
17/3. They do not bioaccumulate and are rapidly metabolized and
excreted by humans;
(ii) bisphenol A (Figure 18.6) - used in resins that coat the inside of cans
and in white dental fillings. The bisphenyl A leaches out into food in the
cans and it has been found in the saliva of dental patients after they
have had a filling. Again the present indications are that it has a low
activity;
(iii) dioxins - (section 18.2) 2,3,7,8-TCDD has been shown to disrupt
reproductive capability and sperm production in male rats and womb
functions in female monkeys. It acts as an anti-oestrogen, inhibiting the
operation of the hormone, but it operates mainly through non
oestrogen pathways rather than through the ORPs;
(iv) organochlorine pesticides - these include DDT (section 18.3), dieldrin,
dicofol, lindane, and so on, and their breakdown products such as
DDE (Figure 18.2). The breakdown products of these compounds tend
to bioaccumulate and high concentrations have been found in aquatic
animals such as the Florida alligators with reproductive problems. The
long lifetimes of this class of compound and their biomagnification
potential means that though they are 1 0 0 0 - 1 0 0 0 0 times less active than
natural hormones, they can reach high enough levels to be a potential
problem either on their own or by adding to the effects of other
endocrine disruptor chemicals;
(v) nonylphenol (Figure 18.6) - an anti-oxidant added to plastics to
improve their flexibility. As well as being leached out of these plastics in
small quantities, nonylphenol is a possible breakdown product of
alkylphenol ethoxylates. It has been found (together with octylphenol,
a related compound) in relatively high concentrations in effluents from
sewage works. Downstream from these outfalls male rainbow trout

have been shown to be producing vitellogenin which is a protein
normally only found in female egg-laying fish;
(vi) phthalate esters - plasticizers used in food packaging plastics. High
levels have been shown to reduce testosterone levels and shrink testes in
rats and mice;
(vii) polychlorinated biphenyls - (section 18.4) like dioxins their actions are
mainly through non-oestrogen pathways and there is concern because
of their long lifetime in the environment and their tendancy to be
biomagnified.
There are great difficulties in identifying cause-effect relationships
between exposure to potential endocrine disruptor chemicals at the levels
found in environmental systems and the occurrence of reproductive
problems, sexual dysfunction, breast or testicular and other forms of cancer.
Laboratory screening tests carried out with cultures of cells do not provide
information about how the chemicals are absorbed or distributed between
organs or metabolized or excreted by the whole organism. As already
indicated earlier in this chapter, the possible protagonistic and antagonistic
effects between the wide range of chemical species that an organism comes
into contact with means that providing unambiguous proof will be very
difficult. The arguments are about how strong the links have to appear to be
before action is taken to ban a particular chemical or its dietary source.
Appendix
Chemical compound formation
Atoms consists of a small nucleus (radius about 10” 1 4 m) containing

protons, each of which has a positive charge and a mass of about 1 atomic
mass unit (1.67 x 10- 2 4 g), and neutrons, each of which has no charge and a
mass similar to that of a proton. An element is characterized by the number
of protons in its nucleus. This number is called the atomic number. Each
oxygen atom (atomic number 8 ) contains eight protons; each nitrogen atom
(atomic number 7) contains seven protons. If an oxygen nucleus lost a
proton it would then be a nitrogen nucleus.
A change in the number of protons leads to a change in the chemical
properties (and name) of an atom. The number of neutrons in a nucleus
does not so directly affect the chemical properties of an atom; a given
element may have atoms with different numbers of neutrons present in their
nuclei. These atoms, with the same numbers of protons, the same chemical
properties but different numbers of neutrons, are called isotopes of the
element.
Outside the nucleus there is a much larger volume of space (approximate
radius 10“ 10 m) that contains electrons. Electrons have a negative charge of
the same size as the positive charge on a proton, but are much smaller in
mass (0.91 x 10- 2 7 g) than either the proton or the neutron. A free atom in
its lowest energy state (its most stable state) is electrically neutral and the
number of electrons outside the nucleus is the same as the number of
protons inside the nucleus. If the atom loses an electron, it will be positively
charged (electron deficient); it will then be called a cation. If an atom gains
an electron it will be negatively charged (excess electrons) and will then be
called an anion.
It has been discovered that each electron in an atom has a distinctive
energy, different from that of each of the others. However, these energies
can only have certain specified values (Figure A.l). The chemical properties
of atoms (and also molecules and ions) are determined by the energies of the
electrons they contain. As is indicated in Figure A .l, the energy levels form
groups whose members differ in energy by small amounts, e.g. 2 s and 2 p
form a group. These groups of levels with similar energies are frequently
called shells. The various shells are often referred to by the letters K , L, M,
N, etc., that were introduced before many of the detailed features of atomic
APPENDIX 249
Specific energy levels or orbitals -

General each can contain two electrons
energy range (energy level symbol, e.g. 4s) Shells
7 P ' I
- — 5f
l^1 -------------- 6p
*51 - 5d
— 6s
- 4f O'
-------------- 5p
- 4d
— 5s
j -------------- 4p
-3d
— 4s t
----------- 3p
M
-3 s I
-------------- 2p
— 2s u
— Is K
T h e lo w er e n erg y o rbitals are filled first.
T h e lo w e r the e n e r g y o f the e le c tro n s the m ore sta b le the structure.
Figure A .l The arrangement of electron energy levels in atoms.
structures were known. It is the distribution of the electrons between the

levels in the outermost (highest-energy) shell that largely determines the
chemical properties of the atom.
The periodic table (Figure A.2) is a method of arranging the elements in
order of increasing atomic number so that those elements with similar
electronic structures, and hence similar chemical properties, are grouped
together. Elements in the same vertical groups have the same outer shell
structure (valence), e.g. ns 1 for lithium, sodium, potassium, rubidium,
caesium and francium; and ns2 np 4 for oxygen, sulfur, selenium, tellurium
and polonium. (Note that the superscript indicates the number of electrons
in a particular energy level.) Elements in the same period have valency
electrons of the same general energy, although the number of electrons
increases from left to right across the table. The group helium, neon, argon,
krypton, xenon and radon is called the ‘noble’ or ‘inert’ gases and its
members have a particularly stable electronic structure of full energy levels
so rarely react.
Although individual atoms will normally have their electrons in the lowest
possible states available to them, combining together two or more atoms
may allow the electrons to rearrange themselves so that there is an overall
reduction in energy of the electrons (and of the atoms) in the new combined
state. For instance, the combined energy of two separate atoms of oxygen is
to
Uy
electronegativity increases o
APPENDIX
* lanthanide 58 59 60 61 62 63 64 65 66 67 68 69 70 71
series Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
** actinide 90 91 92 93 94 95 96 97 98 99 100 101 102 103

series Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
Figure A.2 The periodic table of the elements showing the general trends in electronegativity changes.
APPENDIX 251
greater than the combined energy of the two atoms linked together in the
dioxygen molecule. The formation of dioxygen (Eqn A.l) is favoured.
However, the combined energy of two dioxygen
O+ O -^ 0 2 (A.l)
molecules is lower than the energy of four oxygen atoms combined together
in a tetraoxygen (0 4) molecule. Therefore, neither reaction A.2 nor A.3
occurs.
4 0 — ►0 4 (A.2)
02 + 02 04 (A.3)
Chemical reactions involve changes in the energy of the electrons and do not
involve changes in the energy of the nucleus.
Examination of the compounds formed by oxygen with carbon, nitrogen
and sulfur has shown that they, like dioxygen, consist of molecules with the
atoms held together by the sharing of electrons, i.e. they have covalent bonds.
However, close study shows that atoms of different elements have different
degrees of attraction for the shared electrons. Perhaps we should not be
surprised by this, when we consider the differently sized positive nuclear
charges of the different elements, and the different electron energy
distribution associated with each. Of all the elements, fluorine has the
strongest attraction for the shared electrons; oxygen has the next greatest
attraction. Electronegativity is defined as the power of an atom in a molecule
to attract electrons to itself. The order of electronegativities for a number of
elements is:
F > O > Cl > N > S > C ~ H > Si > Al > Mg > Ca > Na > K
The elements that are more electronegative than hydrogen form compounds
with oxygen that are gases at 293 K (normal room temperature), whereas
the elements that are less electronegative than hydrogen form solid
compounds with oxygen.
Consider what happens to the shared electrons in a molecule as the
relative electronegativities of the atoms change (Figure A.3). When the
electronegativities are the same, A-A (e.g. O with O), the electrons are
evenly shared in covalent bonds and mainly occupy the space between the
two nuclei. The bonding electrons are said to be ‘localized’. One result of
this is that molecules containing three or more atoms will have a specific
shape depending upon the relative localized positions of the bonding
electrons (Figure 3.5). The final geometry of the molecule, which is generally
the arrangement with the lowest energy, is determined by various inter
actions between bonding and non-bonding electrons and by inter-nuclear
repulsions.
252 APPENDIX
<0) 0 > G > O ®

anion cation
electronegativity difference increases
_____ __________ ___ __________ __________________ ►
ionic character increases
order of electronegativity: A > B > C > D
Figure A.3 The effect of changes in electronegativity on the electron distribution between two
atoms bound together.
As the electronegativity difference increases, the charge imbalance

increases, and an electrostatic attraction develops that is non-localized. The
greater the size of the electrostatic force, the higher the melting and boiling
points of the compound and the greater its ionic character. With large
differences in electronegativity, there can be complete transfer of an electron
to form a negatively charged anion and a positively charged cation. These
changes in numbers of electrons mean that anions are usually larger than
cations. The system reaches its lowest energy state, and greatest stability,
when each cation is surrounded by the maximum number of anions and
each anion is surrounded by the maximum number of cations (Figure A.4).
This maximum depends upon the charges and sizes of the ions involved. The
result is a structure that can be compared to sets of spheres packed together
as closely as possible, with oppositely charged ions being in contact and ions
of like charge being out of contact. The relative sizes of the anions and
cations determine the packing arrangement. The relative sizes can be
compared by means of the radii of the ions, and the geometrical
arrangement can be predicted from the radius ratio of the ions, where
radius of cation . t
radius ratio = — - -------— :— (Table A .l)
radius ot anion
Table A .l Relationships between the radius ratio (radius o f cation:radius of anion), the co
ordination number of the cation (number of surrounding anions) and the geometrical
arrangement of the structure
Radius ratio Co-ordination number Shape
0.155 3 Planar trigonal

0.225 4 Tetrahedral
0.414 6 Octahedral
0.732 8 Simple cubic
1.0 12 Close packed
APPENDIX 253
cation anion
(smaller) (larger)
(a) Attractive forces act in all directions
(b) Anion surrounded by cations
(c) Cation surrounded by anions
Figure A.4 Spatial relationships between ions in compounds.
We now have a picture of compounds formed by elements of very

different electronegativities that do not contain simple discrete molecules,
but that are extended three dimensional arrays of charged spheres. These are
described as ionic compounds and the non-directional, electrostatic
attractive forces are called ionic bonds (or electrovalent bonds).
The differences in electronegativities between the elements can be related
to their positions in the periodic table (Figure A.2). If we ignore the noble-
gas group we find that electronegativity increases from left to right across
the periods and from bottom to top up the groups, so that the elements at
the top right-hand side are the most electronegative and the elements at the
bottom left-hand side are the least electronegative, i.e. most electropositive.
Therefore, by comparing the positions of two elements in the periodic table,
we can gain a good idea of how ionic or covalent a bond between them will
be. A large difference, say more than five places, will indicate ionic chara
cter, whereas a smaller difference will indicate covalent character. There are,
of course, some compounds that show intermediate character.
Glossary
accuracy The difference between the observed value and the true value. A
statement of accuracy can only be made if the true value is known: in
environmental measurements it is often very difficult to know what the
true value is.
acid rain (acid precipitation) Rain (precipitation) whose pH is less than 5.6,
the normal equilibrium value for carbon dioxide and water. The pH is
reduced due to the presence of acids (mainly sulfuric and nitric) produced
by the combustion of fossil fuels or released by natural events such as
volcanic eruptions.
aerobic conditions Environmental conditions in which dioxygen is present,
anaerobic conditions Environmental conditions in which dioxygen is
absent.
anion A negatively charged chemical species. In the simplest case an atom
has gained one or more extra electrons, e.g. chloride, C P , oxide, O2-; but
the anion may contain several atoms such that the group has an overall
negative charge, e.g. nitrate, NO^, acetate, CH 3 COO~ . If the anion is in
a mobile state (in solution or molten) it will be attracted to the anode
(positive electrode) when an electrical potential difference is applied. No
movement occurs when in a solid,
aromatic compound (aromatization) A planar cyclic organic compound in
which there is a delocalized bonding-electron system. The system is
composed of carbon atoms which apparently have alternating single and
double bonds, C-C = C; however, the chemical properties show that the
molecules have greater stability than this alternating structure should
give. One pair of electrons in each double bond is thought to be spread
over the whole aromatic portion of the molecule, C —C—C.
autotrophs Organisms that can produce organic molecules from inorganic
sources. The majority are photosynthetic autotrophs and utilize the
energy in sunlight, but some can obtain all their required energy from
inorganic chemicals and are called chemosynthetic autotrophs.
Avogadro’s number 6.023 x 1023. The number of atoms in 12.00 g of l£C;
or, more generally, the number of particles in one mole of any substance.
GLOSSARY 255
Becquerel The SI unit of activity of nuclides that are unstable and,

therefore, radioactive.
1 Becquerel (1 Bq) = 1 disintegration per s
This means that 1 Bq represents one nucleus disintegrating each second.
It is a much smaller unit of activity than the previously used unit which
was the Curie (Ci), where
1 Curie = 3.7 x 1010 Bq = 3.7 x 1010 disintegrations per s
biomagnification The increase in concentration of a chemical that occurs in
a living organism because the rate of excretion is lower than the rate of
ingestion. This can result in the concentration of a compound being very
much higher in the organism than in the environment in which the
organism lives. A further effect may be that there is an increase in
concentration up the food chain as each succeeding member feeds on
organisms containing increasingly high quantities of the chemical,
biota A general term denoting all living matter. Biomass is the mass of
biologically derived material, and this may be subdivided into living
biomass and dead biomass,
buffer A solution that shows only a small change in pH when an acid or
alkali is added to it (see Chapter 4).
catalyst A substance that accelerates the rate of a chemical reaction, but
which itself remains unchanged at the conclusion of the reaction. The
catalyst reduces the energy barrier that holds back a reaction. It does not
increase the ultimate yield, but it does shorten the time taken to obtain
the products. The catalyst can be continuously reused unless it is
‘poisoned’.
cation A positively charged species generally formed by the loss of one or
more electrons from an atom of a metal, e.g. sodium, Na + , calcium,
Ca 2 + . If in a mobile state, a cation is attracted to the cathode (negative
electrode) when an electrical potential difference is applied,
cation-exchange capacity A measure of the number of negatively charged
sites that are capable of reversibly binding cations. In soils, these sites are
associated mainly with organic matter and clays (see Chapter 12).
cell The fundamental unit of structure of living organisms. The major
division into two cell types is based on whether (a) a separate nucleus
containing the genetic material is present (the eukaryotes - includes all
modern multicellular organisms), or (b) the genetic material is not
separated by a membrane from the rest of the cell contents (the
prokaryotes).
complex ion or molecule A central atom or ion (generally a metal) attached
to more atoms or groups of atoms than would be expected from the
charge on the central atom or ion, e.g. Fe3+ in [FeCl4]~, tetrachloro-
256 GLOSSARY
iron(III)ate. The atoms, etc., surrounding the central atom or ion are
called ligands. Some ligands contain more than one atom that can be
attached to the central atom or ion and these tend to form stronger
complexes called chelates. For example, ammonia (NH3) has one binding
atom, the nitrogen, and can form the complex [Cu(NH 3 ) 6 ]2 + with copper.
Glycine (NH 2 CH 2 C 0 2 H), on the other hand, can bind through the
nitrogen and through one of the oxygens: it can, therefore, form a
chelation complex with copper, [Cu(NH 2 CH 2 COO)3]_. The complex
should always be surrounded by square brackets [ ] when the formula is
written.
consumers see food chain and heterotrophs.
covalent bond The chemical bond formed between two or more atoms by
the sharing of electrons. Each covalent bond can be considered to contain
two electrons. The bonding is directional in space and a molecule or
group containing at least three atoms bound together by covalent bonds
will have a characteristic shape. There may be up to three covalent bonds
joining two atoms.
crystal lattice The geometrical structure in which the positions of the
atoms, ions or molecules in a crystal are represented by points. The
crystal lattice is made up of repeating units of lattice points, each of
which is called a unit cell. The arrangement of atoms, ions or molecules in
the crystal is influenced by the relative sizes of, charges of and degrees of
covalent bonding between the components.
depression of freezing point The lowering of the freezing (melting) point of
a solvent that occurs when a substance is dissolved in the solvent to form
a solution. The larger the concentration of substance dissolved in the
solvent, the greater is the depression of freezing point. This phenomenon
is made use of when adding antifreeze to radiator water and when salting
roads to prevent ice formation.
Dobson units A measure of the quantity of ozone in the atmosphere. One
Dobson unit (1 DU) is the amount of ozone in the vertical column of air
that, if concentrated at sea level at normal temperature and pressure,
would occupy 0.1 mm. The normal amount of ozone in the atmosphere
gives values in the range 300-350 DU.
Donnan membrane A membrane that allows some solutes (dissolved
species) as well as solvent to pass through. Other solutes are prevented
from passing through. A true semipermeable membrane will only allow
solvent to pass through. Most natural membranes, such as cell walls, are
Donnan membranes rather than semipermeable membranes (see Figure
10.4).
dry deposition The removal of material from the atmosphere by contact
with solid surfaces on which the material falls or against which it blows.
The surfaces are much more effective as removal agents if they are wet.
GLOSSARY 257
electronegativity The power of an atom in a molecule to attract electrons

to itself. Non-metals have higher electronegativities than metals. When
writing a formula it is usual to place the less electronegative elements first
followed by the more electronegative elements, e.g. potassium sulfate,
k 2 s o 4.
electronic structure The arrangement of electrons in the various available
energy levels (also termed orbitals) in atoms or molecules. The electrons
tend to occupy the lowest available energy levels and it is the re
arrangement of the electrons amongst the various energy levels that is
responsible for the energy changes associated with chemical reactions,
electrostatic attraction The attraction that exists between a positive and
negative electrical charge,
endothermic Absorbing heat from the surroundings by a system
undergoing a chemical reaction or some other change. A positive
enthalpy change is described as being endothermic.
energy The capacity to do work. An object or system can possess potential
and kinetic energy. Potential energy arises from a system’s composition
(e.g. chemical energy, thermal energy) and also from the system’s relative
position (e.g. water at the top of a waterfall compared with water at the
bottom). Kinetic energy arises from the motion of an object. The total
amount of energy in a system and its surroundings remains constant,
enthalpy, H A measure of the total energy in a system at constant pressure.
The heat absorbed or evolved in a chemical reaction at constant pressure
is the enthalpy change. It is possible to measure enthalpy changes, A //,
but not the absolute enthalpy (see entropy and free energy),
entropy, S A measure of the ‘unavailable’ energy in a system. In an isolated
system any spontaneous process leads to an increase in entropy, i.e. the
new arrangement is more probable than the old and there is a lower
degree of order. The energy used to bring about this increase in entropy is
not available for doing external work. Reduction in entropy can only
occur in a non-isolated system when energy is imported, but the part of
the system that exported the energy has to undergo a change in entropy
to compensate for the export (see enthalpy and free energy),
enzyme A protein-based molecule that has the ability to increase the rate
of some chemical reactions by acting as a catalyst. As with catalysts in
general, the enzyme only increases the amount of product produced in a
given short period of time, it does not increase the final theoretical yield
(see section 4.3).
equilibrium constant The constant that expresses the relationship between
the concentration of products and reactants in a chemical reaction that
has reached equilibrium. The higher the value of the equilibrium constant
for a given reaction, the higher the proportion of products there will be
when equilibrium has been reached (see equilibrium reaction).
258 GLOSSARY
equilibrium reaction A chemical reaction that will proceed until the

concentrations of reactants and products are in equilibrium. The quantity
of reactants being converted to products is equal to the quantity of
products being reconverted to reactants. Provided that the system
remains closed (nothing is added or removed) the reaction will proceed
without perceptible change. The only way to use up more reactants is to
change the conditions. This may involve the removal of one of the
products from the reaction system,
errors Differences between true values and observed or measured values.
Errors may be divided into random errors and systematic errors. Random
errors are fluctuations that only fit a pattern to the extent that they can be
described by a ‘Gaussian’ or ‘normal’ distribution curve (Figure 1.7a). If
enough values are measured there is no bias in the results and the mean
(the average of all results) is identical to the mode (the most common
value) with both being equal to the true value. The size of the random
errors can be evaluated by taking a sufficiently large number of
measurements (see standard deviation). System atic errors are those that
bias the results in one direction due to factors such as (a) incorrect use of,
or faults in, a measuring instrument; or (b) incorrect assumptions in any
theory used to calculate a quantity from the experimental results (e.g.
assuming that it is the concentration of an element that describes its
distribution in rocks when it is actually the logarithm of the concentration
(Figure 1.7)). Systematic errors can only be reduced by employing the
best possible techniques and instruments. They will only show up if the
true value is known, and are not revealed by statistical tests of precision,
exothermic Evolving heat to the surroundings by a system undergoing a
chemical reaction or some other change. A negative enthalpy change is
described as being exothermic,
fault A fracture surface in the Earth’s crust along which there has been a
relative displacement of the rocks on either side. Movement of the rocks
along the fault occurs when the forces being applied overcome the
resistance to displacement and an earthquake results,
fermentation An enzyme-controlled reaction causing the breakage of
bonds in organic molecules and the release of energy. Fermentation does
not involve dioxygen in the electron-transfer process,
ferromagnesian silicates Silicate minerals containing iron and magnesium
in varying proportions. The minerals are dark coloured,
food chain A scheme of feeding relationships that unites the member
species of a biological community. In the case of a grazing food chain, the
first member (or first trophic level) is some autotrophic organism such as a
plant, this is then consumed by a herbivore (second trophic level) and
then successive sets of predators (carnivores) complete the chain. The
herbivores and carnivores are heterotrophic organisms. Saprophytic (or
GLOSSARY 259
detritus) food chains derive their energy and chemicals from dead matter
and the inter-relationships of the members of this food chain are not
those of prey-predator.
free energy The Gibbs free energy, G, is a measure of the available energy
in a system at constant pressure. As with enthalpy is it only changes in free
energy, AG, that can be measured. The relationship between enthalpy, //,
entropy, S , and free energy, G, is given by the following relationship:
G = H - ST
‘available energy’ = ‘total energy’ —‘unavailable energy’
where T is the absolute temperature (degrees Kelvin). If a reaction shows

a decrease in free energy (i.e. if the value of AG is negative) the reaction
will proceed spontaneously because the products are more stable (in a
lower energy state) than the reactants and energy will be released.
However, the term ‘spontaneous’ just means that the reaction is thermo
dynamically favoured and there may be, in practice, a kinetic barrier that
prevents the reaction occurring at a measurable rate,
free radical A species containing a single unpaired electron. Such species
tend to be chemically reactive,
heterotrophs Organisms that cannot utilize only inorganic molecules to
synthesize organic molecules. They obtain their energy from organic mole
cules. Those heterotrophs that obtain their energy from living organisms
are called consumers, whereas those that obtain their energy from dead
organisms or dispersed organic compounds are called decomposers.
hormones Chemicals which co-ordinate and control many functions in
mammals, where they are produced by endocrine glands. Examples are (i)
the hormones produced by the thyroid gland that regulate the growth
and differentiation of cells, plus the control of the basic metabolic rate;
and (ii) the hormones produced by the pituitary glands control male and
female sexual developments. Other organisms, including plants, also use
hormones to control various functions,
inorganic See organic.
ion pair Two single oppositely charged ions that are associated together as
a distinct unit in solution. The charge of the ion pair is the sum of the
charges on the two individual ions and, therefore, may be negative, zero
or positive.
isomorphous The replacement of one atom or ion in a crystal structure by
another atom or ion of similar size in such a way that the geometrical
arrangement of the crystal lattice remains intact. The charges on the
exchanged ions may or may not be the same.
260 GLOSSARY
isotopes Atoms that have the same atomic number (number of protons)
but different numbers of neutrons in the nucleus. The chemical properties
of isotopes are the same, but there are slight differences in physical
properties and rates of reaction,
kinetic energy The energy associated with the motion of a body where
kinetic energy = 0.5 x mass of body x velocity2
kinetics Information about the rates of reactions. The rate of reaction may
or may not be dependent upon the concentrations of all the reactants.
Differences arise because of differences in reaction mechanisms (how the
reactants come into contact and how bonds are broken or formed).
Whereas thermodynamics provides information about energy changes
associated with chemical reactions and indicates the probability that a
reaction may occur, it does not tell whether the reaction will occur at a
measurable rate. For example, diamonds are thermodynamically un
stable compared to graphite at 20 °C, but they are kinetically stable
because of the great amount of energy required to rearrange the carbon
atoms from the diamond lattice to the graphite lattice. In general, the
higher the temperature the more rapidly a reaction will occur,
mean The average value of a set of results obtained by dividing the sum of
the values by the number of results.
Mohorovicic discontinuity The region below the Earth’s crust in which
there is a sharp increase in the velocity of shock waves. This increase is
thought to be associated with changes in composition and mineral
phases. The zone is taken to be the base of the crust and lies at about 6
km below the ocean bottom and 40 km below the continental surface,
molar concentration The concentration expressed in terms of the number
of moles of a substance present. The mole is the amount of substance
containing Avogadro’s number of particles of that substance. In general,
the value of the mole is obtained by adding together the atomic masses of
all atoms in the chemical formula and expressing the result in grammes,
e.g. 1 mole of nitrogen oxide, NO, contains (14 + 16) = 30 g of NO.
molarity, M The number of moles of substance contained in 1 litre (1
dm-3) of solution.
molecule A combination of atoms in fixed numbers to give a discrete
structural entity with no overall electrical charge. The molecule may
contain atoms of only one element, e.g. dioxygen, 0 2, or atoms of several
elements, e.g. trichloromethane, CHC13.
monomers The individual units that are linked together to form polymers,
e.g. amino acids in proteins.
GLOSSARY 261
non-polar Having no electrical charge. Used to describe many covalent

organic molecules. Non-polar compounds are insoluble in polar solvents
such as water but dissolve in non-polar liquids such as benzene and
trichloromethane.
normal distribution A distribution of frequency of occurrence of measured
values that follows a Gaussian distribution curve (see Figure 1.7a).
organic/inorganic A distinction that was first introduced to distinguish
between those compounds and molecules that were thought to be formed
only by living organisms (i.e. organic ones) and those in which living
organisms played no part (i.e. inorganic ones). Nowadays organic
compounds are those containing carbon, usually hydrogen, and varying
amounts of other elements. It is not a distinct class as the boundary
between the two groups is not now clearly defined, e.g. hydrogen-
carbonate, H C 0 3~, and hydrogen cyanide, HCN, are both classified as
inorganic compounds,
oxidation (oxidized species; oxidizing agent) The removal of electrons from
a species. The species that has lost the electrons is said to have been
oxidized. An oxidizing agent is an electron acceptor as it brings about the
oxidation of the species from which it accepts electrons. Oxidation
requires both an electron acceptor and an electron donor (species being
oxidized); therefore all such reactions are redox reactions as both
reduction (of the electron acceptor) and oxidation (of the electron donor)
occur.
oxidation potential The measure of the tendency of a substance to donate
electrons (be oxidized) to some electron acceptor. It is the reverse of the
reduction potential, i.e. numerically the values are the same but the signs
are changed (see reduction potential),
phase A homogeneous region in a system, being one of the states of
matter. The number of phases is the number of separate physical states in
the system, e.g. gas, liquid or solid. Different crystal structures of a
substance are also described as being different phases,
photodissociation The breakage of chemical bonds by the absorption of
electromagnetic radiation in the visible and ultraviolet portion of the
spectrum.
photosynthesis The process by which some organisms (e.g. plants) absorb
solar radiation and utilize carbon dioxide and water to produce organic
molecules.
plane polarized light Light that vibrates in only one plane. Light normally
vibrates in all planes parallel to the direction of propagation. A molecule
containing an asymmetric centre can cause the inclination of the plane of
polarization of the light to be rotated.
262 GLOSSARY
polar Having some electrical charge. Used to describe ionic substances or

covalent molecules in which the electrons in the covalent bond are
unevenly shared (e.g. H 2 0; Chapter 3) so that one part of the molecule
has a slight negative charge and another part has a slight positive charge,
polymer A substance containing a number (often large) of repeating
structural segments or sequences. The polymer is formed by the binding
together of small units (monomers) to form chains. The chains may be
cross-linked, giving two or three dimensional structures. Natural poly
mers include proteins and cellulose. Artificial polymers include plastics
such as polythene and fibres such as nylon,
precision A measure of the reproducibility of an observation, i.e. the size of
the difference between any one measured value and a number of repeated
measurements of the same parameter. The precision is dependent on the
size of the random errors inherent in a measurement. It is not directly
related to the accuracy of a measurement as it does not take into account
non-random errors,
producers Autotrophic organisms that produce the organic molecules, with
their associated energy content, which are then used as a food source by
higher members in the food chain,
rain out The removal of gases, dust, etc., from inside clouds by
incorporation in rain or other precipitation (wash out),
redox reaction A reaction involving the transfer of electrons from one
species to another (oxidation, reduction),
reduction (reducing agent; reduced species) The addition of electrons to a
species. The species that has accepted the electrons is said to be reduced.
A reducing agent is an electron donor as it brings about the reduction of
the species to which it has donated the electrons. Reduction requires both
an electron acceptor (species being reduced) and an electron donor,
therefore, all such reactions are redox reactions as both reduction (of the
electron acceptor) and oxidation (of the electron donor) occur,
reduction potential The measure of the tendency of a substance to accept
electrons (to be reduced) from an electron donor. The higher the potential
in volts, the more readily the substance is reduced. If the reduction
potential is positive the reaction is described as being thermodynamically
spontaneous, i.e. it is energetically favoured. The value of the reduction
potential is dependent upon the concentration of species and the
temperature. To aid comparisons, the standard reduction potential is
often quoted, having been determined under standard conditions of unit
activity (for solutions) or 1 atmosphere pressure (for gases) at 25 °C.
respiration An energy-generating process utilized by various living
organisms in which either inorganic or organic compounds act as electron
donors (are oxidized) and inorganic species act as electron acceptors. If
GLOSSARY 263
dioxygen is the electron acceptor the process is described as aerobic

respiration. Other electron acceptors include sulfate and nitrate (see
Figure 6.4).
sensitivity A measure of the ability of a technique or instrument to detect
small changes. Essentially it is the ability to differentiate between a small
real change and a random fluctuation. High sensitivity, therefore, implies
high precision.
Sievert The SI unit that represents the effective amount of radiation energy
absorbed by live tissue. The unit takes into account the different types of
radiation (a , /?, 7 , etc.).
1 Sievert (1 Sv) = 1 J kg - 1 x radiation quality factor
The previous unit was the rem, where

1 Sievert = 100 rem
significant figures The number of figures in a numerical value, which

indicate the precision with which a measurement is made or a value is
known. For example, a value of 11 has two significant figures, indicating
that the value is closer to 11 than to 10 or 12, i.e. it lies between 10.5 and
11.5. Writing the value as 11.1, with three significant figures, indicates
that the value lies between 11.05 and 11.15. Often when averaging values
or using a calculator to determine a value, the apparent number of
‘significant’ figures is increased. The mean of 11, 12, 11 is 11.3333.
However, this should be reported as 11 because the act of calculation
cannot increase the precision of a measurement. Similarly the mean of
1 1 .1 , 1 2 , 1 1 would be 1 1 as the least precise figures determine the overall
precision. Zeros used to place the decimal point correctly are not counted
as significant, e.g. 0 . 0 0 1 1 has only two significant figures,
silicates Minerals based on the [Si04] structural unit (Chapter 8 ).
solar radiation Electromagnetic radiation emitted by the Sun. Because of
absorption by molecules in the Earth’s atmosphere, only a small
proportion of the radiation reaches the Earth’s surface (Figures 2.6, 2.8
and 4.14). The energy of the radiation is proportional to the rate of
vibration (frequency), with different frequency ranges being given
different names, e.g. visible, IR, UV (Figure 2.6).
sorption The enrichment of one or more components of a particular fluid
phase (gas or liquid) in another phase. If the enrichment only occurs on
the surface between the phases, the process is called adsorption; but if the
enrichment occurs in the bulk of the receiving phase, the term absorption
is used. ‘Sorption’ is a general term; ‘adsorption’ and ‘absorption’ are
specific.
264 GLOSSARY
standard deviation A measure of the precision of a set of readings. The

smaller the standard deviation, the smaller the variation. The formula for
calculating the standard deviation can be found in a statistics textbook
and it is an automatic function on many calculators. For a normal
distribution, 6 8 % of all results will lie within one standard deviation of
the mean and 99.7% will lie within the range of the mean ± 3 x the
standard deviation (see Figure 1.7).
stereochemical Differing spatial arrangement of the atoms or groups in
compounds that can affect the chemical and physical properties of the
compounds. The compounds are identical apart from these spatial
differences about a fixed point,
stereoisomerism Two or more forms of a compound or other species that
can exist because of spatial differences in the arrangement of atoms or
groups of atoms either (a) about a plane (geometrical isomerism ); or (b)
about an asymmetric centre (optical isomerism).
synergistic Increasing the effect of two or more components by an amount
that is greater than the sum of the individual effects. There is an
enhancement of the effects of one chemical due to the presence of other
chemicals.
transpiration The evaporation of water from the leaves of plants (the water
having passed through the plant),
wash out The removal of gases, dust, etc., from below clouds in the
atmosphere by rain or other precipitation falling from the clouds to the
ground (rain out).
wet deposition Removal of material from the atmosphere by the combined
action of rain out and wash out. Also called ‘precipitation scavenging’.
Index
References to figures are indicated by giving the page number in bold type.
Similarly tables have page numbers indicated in italics. Items which appear
in the glossary are referred to by the entry G.
Accuracy 10– 13, G phosphate 125, 177

Acetic acid see Ethanoic acid toxicity 161–2
Acid 56–9 weathering 131– 140, 158–9
igneous rock see Igneous rock Aluminosilicates 131, 153, 158–9, 162,
rain see Sulfur 173– 5
strong 57–9 Amino acid 34, 36– 7, 89–90, 103–4 ,
weak 57–8 106, 193
see also pH Ammonia 7, 89–91, 93– 5, 100– 1, 107
Activity 56, 144– 5 Ammonification 95
Acute poisoning 194 Ammonium
A denosine^'–diphosphate 66–7, 94, chloride 58
123 hydroxide 58
A denosine^'–triphosphate 66–9, 123, ion 18, 58, 92, 94, 110– 11
178–9 nitrate 96, 101
ADP see Adenosine–S'–diphosphate sulfate 101, 118
Aerobic respiration see Respiration A nion–exchange capacity 176
Alcohol see Ethanol Antarctic
Algae 6, 125–6 ice effect on sea level 86
blue–green 9, 24, 93, 125 ozone levels 26– 8
Algal blooms 102, 125–6, 181 Polar Vortex 27–9
Alkalinity 57–8, 116– 17 A nti–oestrogens 244, 246
see also Bases Apatite 123, 165–6
Alkylphenol polyethoxylates 246 Arctic ozone levels 28
Alligators, reproductive Arc–trench system 4, 6
dysfunction 243, 246 Arom atization 78, 80
Alpha particles 40– 1, 212, 218– 19, 230 Asbestos 134, 182–4
biological effects 231 Atmosphere
Aluminium composition 2, 5, 79, 81, 83, 87
abundance 2, 158 in geochemical cycles 13– 16, 44, 184
extraction, production 159–60, 185 and oxygen 17–31
minerals structures 131–2, 158–9, pollutant 59–60, 95– 100, 113–28,
173–5 190, 192, 200, 221–2, 236, 241
oxide 159–61, 77 primitive 9– 10, 20– 1
266 ENVIRONMENTAL CHEMISTRY
Atmosphere (contd) Cadmium 125, 171, 187, 201–6, 212

radiation absorption 24–6, 30– 1, 44, cycle 202
79–88 Caesium
stratosphere 5, 24– 30 com pounds 224
troposphere 5, 31 fall out 219–22, 224– 5
see also Greenhouse effect; Individual half–life 214, 221
elements; Ozone layer uptake 219, 220–2
ATP see Adenosine–S'–triphosphate Caesium–134 221
A utotroph 7, 8 , G Caesium–136 221
Caesium–137 214, 219–22, 225–6
B horizon see Soil Calcium
Bacteria 6, 93, 102, 156 abundance 2, 164– 5
Basalt 5, 12, 131 and cadmium 206
Base carbonate 45–7, 61, 64, 115, 119–20,
strong 57–8, 64 164, 166–7
weak 57– 8, 64 cycle 164–5
Basic igneous rock see Igneous rock essential 178, 188
Bauxite 133, 158, 160 in ion pairs 166–7
Becquerel G ion size 17, 132, 165
Benthos 62, G and lead 192
Benzo(a)pyrene 242 occurrence 2, 164– 5, 172
Beta particles or radiation oxide 120, 125, 130, 154, 167, 176
minus 39–43, 179, 212– 13, 218–20, phosphate 123– 5, 166
222, 230– 1 in silicates 130–3, 172
plus 40 in solution 45–7, 118– 19, 166– 8
Biodegradable 168–9, 233 sulfate 118, 120– 1, 128, 133, 168
Biolimiting elements 26–7, 125–7, G weathering 115– 17, 135–40, 161,
Biomagnification 233, 240, G 164– 7
Biomass 61–2, 91, 125–6, 197, G see also Flue gas desulphurization;
Biomethylation 197–9 Limestone
Biosphere 2, 12, 15, 150 Cancer
Biota 61–2, 112, 125, G food risk 226, 2 3 3 ^
Bio–unlimited elements 127 organics 233– 5, 240–2, 247
Bisphenol A 245–6 radon induced 227, 230–2
Blast furnace 153–4 C arbohydrate
Blood 59, 102, 119, 150–2, 178, 193–4, and electron release 92–4 , 110
206 and photosynthesis 7–9, 22–4 , 65– 73
Borates 65 and respiration 18– 19, 67–9
Boron 188, 212, 224 structure 3 3 ^
Borosilicate glass 216 Carbon
Breeder reactor 214, 217 cycle 18, 61–2, 92
Bromine, ozone destruction 24–6, dioxide
29 in atmosphere 7, 9, 66–7, 79, 83
Buffer 58–9, 63– 5, 115– 17, 161–2, G –bicarbonate–carbonate
Burner reactor 214 system 63– 5, 14, 166–7
in blood 150– 1
C3 plants 88 greenhouse effect 79–88, 99
C4 plants 88 photosynthesis 9, 22–4, 65–73
INDEX 267
in rain 45, 115 Chloracne 234– 6

essential 33, 185, 188 Chlor–alkali production 196–7
in fuels 61, 77–9 Chloride 4 5 ^ 7 , 54, 155, 161, 177
monoxide 62, 8 3 , 84, 87 , 97, 99, 151, Chlorinated organic
153, 159 compounds 233–41, 246–7
occurrence 2, 61 dioxin form ation 236
in organic molecules 33–7 Chlorine 2, 127, 188, 192, 197, 236,
reducing agent 152– 3, 159 239
respiration 18– 19, 22, 70 and ozone depletion 24– 30
in soils 136–9 incineration 237
Carbonate monoxide 25, 28–9
ion pairs 166– 7 nitrate 27– 8
minerals 17, 61, 116, 133, 164– 7 Chlorofluorocarbons
solutions 61–5, 138, 143–5, 147–8, greenhouse effect 80– 1, 83, 85,
166, 168 87
see also Calcium carbonate; ozone depletion 29–30
Carbon dioxide–bicarbonate– use 29, 233
carbonate system Chlorophenols 236
Carboxylic acid 35, 137
Chlorophyll 23–4 , 65–6, 68
Carnivores 63, 103
Chromium 99– 100, 125, 154, 156, 175,
C arnot efficiency 76– 7
188, 204
Catalyst 33, 37, 71–2, 99, 113, G
Chronic poisoning 194
see also Enzymes
Chrysene 242
Catalytic convertor 99, 190
Cigarettes see Smoking
Cation
Cinnabar 196
in body fluids 177– 8
Citric acid 139
in minerals 130, 1 3 2 ^ , 164, 173– 5
Clay minerals
reactions 58, 178
in sea water 45–7, 173 occurrence 139, 150, 159, 165
simple 247, 252–3, G properties 115– 16, 138, 162, 172–6,
C ation–exchange capacity 115– 17, 205, 221, 224
175–6, 188–9, 204, G structure 159, 173– 5
Cells Clean Air Acts 115, 118, 241
composition 33, 37, 52, 65, 125, Clinical effects 194
177–8 Clouds greenhouse effect 86
oxygen uptake 150–2 Coal 218
and radioactivity 43, 220– 1, 231–2 formation 77–9
types 6–9, 65–6, G sulfur content 120
Cellulase 70, 72 tar oil 233
Cellulose 34, 70, 72, 104, 118 Cobalt 188
C FC –11 see Chlorofluorocarbons Complexes 124– 5, 138–9, 146, 151,
C F C –12 see Chlorofluorocarbons 166, 188–9, 198, 205, G
Chalcopyrite 184– 5 Complexing agent 138–9, 189, 220
Chernobyl Condensation reactions 33^4
accident 210, 213, 222–6 Configuration 71–2
fall out 215, 224– 6 Consumers 69, G
reactor 223–4 Continents 4–6, 12, 130– 1
Chitin 166 Control rods 212– 13, 223
Copper Dibrom oethane 192

copper–64 40 l ,l–D ichloro–2,2–di–(/?–chlorophenyl)–
essential 188 ethene 238–9, 246
mobilization 118 2.4–D see 2,4–Dichlorophenoxyacetic
occurrence 120, 132, 139, 184, 204 acid
re–cycling 185 2.4–Dichlorophenoxyacetic acid
Corrosion (2,4–D) 237
causes 119–20, 155–7, 161 D ichlorodiphenyltrichloroethane or
protection 156–7, 161 1, 1, l –trichloro–2,2–di–(4–
Cosmic rays 22, 42, 227, 232 chlorophenyl)ethane 238–9, 243,
Coumestrol 245 246
Covalent bonds 48– 51, 70–2, 132, 134, D ichloroethane 192
136, 249– 52, G Dicofol 243, 246
Crust D iethylstilbestrol 243–^
composition 2, 5, 12– 13, 129– 33, Dihydrogen see Hydrogen
135–6 Dimethylstilbestrol 243–4
structure 3–6, 12– 16, 129–33, 135–6 Dimethylsulfide 107–8, 111
Crystal lattice 140, 188, 252– 3, G Dinitrogen oxide
Cycles greenhouse gas 80– 1, 83 , 87
geochemical 12– 16, 181, 184– 5 ozone destruction 30
see also Individual elements Dinitrogen see Nitrogen
Cytochromes 66 Dioxin 233–7, 239, 246– 7
Dioxygen see Oxygen
D aughter element 209, 230 D ipolar 48, 50, 51, 53, 54– 5
D D D see l , l –Dichloro–2,2–di–(p– Disaccharide 34
chlorophenyl)ethane D istribution of results
D D E see l ,l–Dichloro–2,2–di–(/?– lognormal 10– 12
chlorophenyl)ethene normal 10– 12
D D T see D N A see Deoxyribonucleic acid
Dichlorodiphenyltrichloroethane D obson units 26– 7, G
Decommissioning Dolomite 116, 164– 5
nuclear power plants 215, 217– 18 D onnan membranes 162– 3, 178, G
weapons 217 D ust 14, 45, 123–4 , 140, 225
Deficiency, nutrient 103– 5, 150, 152, Dynamic equilibrium 54
185–9, 206– 7
Demethylation 199 Earthquakes 6
Denitrification 90, 95 Eh see Redox potential
Density of water 48– 51 Electric arc furnace 154
Deoxyribonucleic acid 34, 36–7, 124, Electrode potential 21, 159
193 Electromagnetic radiation see
Deposition Electromagnetic spectrum
dry 113– 14, 221, G Electromagnetic spectrum 22– 5, 39,
wet 113– 14, 221, G 41, 79–82
Depression of freezing point 119, G see also Radiation
Desulfurization 120– 1 Electron
Detergents 124– 5, 168–9 acceptor 20– 1, 24, 70, 94, 110, 155,
Deuterium 38, 41–2 161
Dialysis 162– 3 in atoms 1, 164, 202, 248– 53
INDEX 269
capture, K 40, 41, 179 Errors

in covalent bonds 48– 51, 78, 251– 1 random 10– 12, G
delocalization 78 systematic 10– 12, G
donor 20– 1, 24, 67 Essential elements
lone pairs 48– 51 deficiency 117– 18, 161, 185– 8
in radioactivity 39–43, 219–20, 222, major 125– 7, 150, 176–7, 185–8
230–2 minor 94, 185– 8, 201, 206
transfer 92, 94, 151, 155–7 see also Deficiency, nutrient
Electronegative 48, 251 Estuary 45
Electronegativity 251– 3, G Ethanoic acid 57
order of 251 Ethanol 54, 70, 233– 4
Electropositive 253 carcinogenesis 233–4
Electrostatic interaction 39, 48, 252– 3, Ethinyloestradiol 243–4 , 246
G Eukaryotes 6–9
Electrovalent bonds see Ionic bonding Eutrophication 126– 7, 181
Element 248–9 Evaporites 17, 133, 164– 5, 173
Endocrine
disruption 243–7
Fat
glands 259
composition 34–6
Endosulfan–a 243, 245
as energy store 69, 72–3, 103–4
Energy
organic chemicals in 235, 237,
activation 71–2, 93^1
239–40
conversion 22, 51–3, 73–7, 209,
see also Lipids
213– 15
Fatty acid 34–6, 168
forms 73
grade 77 Fault 4, G
industrial uses 101, 153, 160, 185 Feldspar 132– 3, 135, 158–9, 172–3,
nuclear 38, 41– 3, 180, 209– 15 188
and organisms 6– 9, 18– 19, 22– 4, Feralitic soil 137
34–5, 63–73, 110– 11 Ferm entation 7, 9, 70, 110– 11, G
solar 22–6, 77–82, 95–9 Ferric see Iron(III)
see also Free energy; Ferromagnesian minerals 142–3, G
Photosynthesis Ferrous see Iron(II)
Enrichment factor 191 First order reaction 42–3
Enthalpy 75, G Fish
Entropy 74– 5, G evolution 9
Enzymes food chain 62– 3, 198–9
action 2, 67–8, 70–4, 93–4, 151, G health factors 1, 118– 19, 240, 243,
composition 37, 91, 93, 115, 206 246– 7
poisoning 193, 199 kills 15, 65, 119
see also Catalysts skeletons 166
Epilimnion 50– 52 Fissile nuclides 213– 14
Equilibrium Flue gas desulphurization 120– 1
constant 55–6, 64, G Fluorine 188, 251
reaction 55–9, 63–5, 73–5, 100– 1, Flux, geochemical 14, 184– 5
198–9, G Food chain 62–3, 69, G
state of 54, 57, 73– 5 Formaldehyde 59
Erosion 15, 123, 184 Fossil 6
Free energy 75–6, 89–92, 108, 110, examples 243–4

156, 169–70, G sexual development 243, 246
Free radicals 26, 59–60, 84– 5, 98, 100, see also Oestrogens
113, G Humus 138–9, 175, 192
Frequency 22 H ydration 54– 5, 148–9, 188, 198, 201,
Fuel 205
desulfurization 121 H ydrocarbons 77–9, 96–9
fossil Hydrochloric acid 57
combustion 19, 31, 76– 7, 99, 113, H ydrochlorofluorocarbons 29, 83, 85,
218 87
composition 78, 120 Hydrogen
form ation 61, 77–9 activity 56–7
nuclear 38, 41–2, 209– 15 bomb 41, 222
reserves 41, 88 bonds 48– 51, 168–9, 173– 5
G am m a radiation 22, 40– 1, 179– 80, cyanide 185
212– 13, 218, 224, 232 dihydrogen 7– 10
GCM see General Circulation Model donors 9, 22
General Circulation Model 85–7 essential 185, 188
Geochemical cycle 13– 17, 94, 184– 5 ions 55–9, 63– 5, 92–3, 110, 115, 136,
see also Individual elements 144– 5
Geothermal energy 77, 122 isotopes 38–9, 42–3, 218
Gleying 145–7, 149 occurrence 2 , 38
G lobal warming potential 85, 87 sulfide 7–9, 18– 19, 107– 8, 110– 12
Glucose 7, 9, 22, 34, 70, 94 see also pH
Glycerol 35–6 Hydrolysis 34, 58
Glycogen 70 Hydroperoxyl radical 60, 84
Goethite 148, 152, 159 Hydroxide 55–8, 63, 173– 5
Granite 5, 12, 116, 131, 208 Hydroxyl radical 25–6, 59–60, 84– 5
Green light 24 Hypolimnion 50, 52
Greenhouse effect 79–88
G row th response curve 186–7 Ice 48–9, 51
Gypsum 120– 1, 164 Igneous rocks
acid 5, 116, 130– 1
Haematite 147– 8, 152 basic 5, 116, 130– 1
Haemoglobin 66, 102, 150–2, 193^4 form ation 129– 30
H alf life 42–3, 179–80, 208–9, 218–21, intermediate 116, 130
228, 230 ultra basic 116, 130
Halons 29 weathering 16, 131–2, 135–7
H ard water 167–70, 192 Illite 174, 175, 177
H CFCs see Hydrochlorofluorocarbons Incinerators 236, 240
H eart disease 170– 1, 194 Indole carbinol 234
Helium 2, 38–42 Inert gas 227, 249
Herbivores 103 Infrared 22, 25, 79–85
Heterogeneous oxidation see Oxidation Inorganic molecules 6, G
Hexacyanoferrate 222 Interatom ic 20
Horizons see Soil Intermolecular 20, 48, 107, 109
Hormones Intram olecular 107, 109
activity 243– 5, G Invertebrates 166
INDEX 271
Iodine Isomorphous substitution 123, 132,

fall out 220 136, 172, 175, G
half–life 218, 220 Isotope 38– 43, 179, 208–9, 228, 248, G
uptake 220
Iodine–129 218 Kaolinite 138, 173– 5
Iodine–131 220, 226 Kinetic energy 43, 49, 51, G
Ion Kinetics 2, 21, G
in crystals 129, 132, 188, 252– 3
formation 43, 251–2
Lactic acid 70
pairs 166–7, G
Land erosion 15, 184
properties 252– 3
Land–fill nuclear waste 218
solubility 54– 5, 126, 139, 155, 166,
Laterite 137, 147, 150
175, 188–9
L D 50 187, 232
see also Anions; Cations
Lead
Ionic bonding 136, 252–3
abundance 725, 185, 190, 194, 204
see also Electrovalent bonding
alkyl compounds 190, 192
Ionic product 56–7
cycle 190–2, 196
Iron
health effects 118, 187, 192^4, 230
abundance 2, 12, 141, 185, 204
isotopes 39, 209, 228– 30
catalyst 100
minerals 120, 133, 185, 190– 1
corrosion 155–7
oxidation/reduction 21
cycle 141–2
recycling 185, 190
deficiency 150, 152
Eh–pH diagrams 143– 50 in petrol 99, 190, 236
essential 150, 188 solubility 191–2
haemoglobin 66, 150–2 in water pipes 118, 167, 192
isotope 38–39 Light see Visible light
nitrogenase 9 3 ^ plane polarized 71
occurrence 5, 19–20, 141–50, 159 Lime see Calcium oxide
oxidation/reduction 17–20, 111– 12, Limestone
141–2, 155–7 buffering capacity 116– 17, 122
pan 147, 150 composition 62, 133, 165
phosphate 123, 125, 156, 177 in crust 12, 17, 133
production 152– 4 formation 166–7
pyrites 20, 111– 12, 121, 147–8 solubility 47, 119, 166–7
recycling 154, 185 uses 119, 121, 153
Lipids 34– 6, 69–73, 177, 239
(II)
minerals 131–2, 137–8, 141–2, 185 see also Fats
occurrence 18, 137–8, 141–2, Lithium 133, 175
145–9, 151–2 Lognormal distribution 11– 12
in solution 19, 138, 145–9 Lone pairs 48– 51
(no Lysine 103–4
ions 137–8
minerals 18, 185 M agma 16, 129– 32
occurrence 137–8, 145– 50 Magnesium
oxide 18, 19, 137–8, 148– 50, abundance 2, 164
152–3, 155–7 adenosine–S'–diphosphate 94
in solution 138–9, 145–9 adenosme–S'–triphosphate 94
Magnesium (contd) M gADP see Magnesium adenosine–5'–

carbonate 115– 16, 119, 133, 166–7, diphosphate
192 M gATP see Magnesium adenosine–5'–
chlorophyll 65, 68 triphosphate
cycle 164–5 Mica 131, 134, 172
essential 118, 161, 188 Microbes see M icroorganisms
isotope 38 Microorganisms
in organisms 178 nitrogen cycle 19, 89–95
silicates 130–2, 138, 165, 174–5 mercury cycle 197–9
in solution 118, 127, 156–7, 161, soap 169
164– 8 sulfur cycle 106– 12
weathering 137– 8, 140 M ilk, souring 70
Magnetite 148, 152 Mine waste 112, 185, 215
M alaria 238 Mineral 17, 129– 32, 134– 5
Manganese 18, 113, 141, 188 M irror images 70–2
M antle 3–6, 13, 129– 30, 141 M oderator, nuclear reactors 210– 13,
Marble 119 223–4
M ean 11– 12, G M olar concentration 56– 7, G
Melting point 35, 48, 252 M olarity 56, G
M ercury Mole 56
abundance 125 , 196, 204 Molecule 17, 19–20, 33, 56, 70– 1,
chloride 187, 198 79– 80, G
cycle 196–9 M olybdenum 93, 188
in diet 199–200 M onom er 33, G
methylation 197– 8 M onosaccharide 33–4, 69–70
sulfide 191, 196– 8 M ontm orillonite 174– 5
toxicity 199–200 M ountains 4– 5, 130
Mesothelioma 182– 3 Myoglobin 150–2
Metabolic process 66–9, 231
Metallothionein 206–7 N A T see N itric acid trihydrate
M etam orphic rock 16, 124, 129, 133 N atural gas see M ethane
M ethaemoglobin 151 N ekton 62
M ethaemoglobinaemia 102, 151 N eon 2, 38, 227, 249
M ethane N ernst equation 144– 5
abundance 10, 61, 62, 83 N eutral solution 56– 7
atmospheric removal 98–99 N eutrinos 39
greenhouse gas 80–7 N eutron 39–4 1 , 208– 14, 223, 248
natural gas 41, 78–9, 100– 1, 118, N eutron:proton ratio 39, 208
120– 1, 233 Nickel
and ozone 30– 1, 84, 98 abundance 2
primitive atmosphere 9– 10 –cadmium batteries 201
reserves 41 catalyst 101
tundra 86 essential 188
M ethionine 1 0 3 ^ – isotope 39^40
Methyl bromide 30 radius 132
M ethylation 197–99 stainless steel 154, 156
M ethylmercury 197–200 N itrate
M etmyoglobin 151 atmosphere 19
INDEX 273
fertilizer 94, 101–2 Nucleic acid 6–7, 33–4 , 36–7

nitrogen cycle 89–91, 94– 5 Nucleons 39, 208
plant growth 186 Nucleus
reduction 92, 95, 110– 11 atom 38–43, 208– 12, 248
in water 102 cell 6–7, 9
Nitric acid 18, 59, 96, 100– 1
trihydrate (NAT) 27– 8 Ocean
Nitric oxide 18, 25– 8, 30– 1, 59–60, 90, basin 4–6
95– 101 composition 2, 7, 46–7, 166, 172
Nitrification 94 in cycles 13– 16, 43–6
Nitrites 89–90
life in 6–9, 41– 3
Nitrogen
pH 63– 5
abundance 2, 9, 89
productivity 51–2, 126– 7
cycle 89–95, 106
ridge 5–6
dinitrogen 9, 45, 89–96, 99– 100
sediments 110
essential 33–4 , 61, 103– 5, 117,
see also Individual elements
125–7, 185–6, 188
Oestrogen
fertilizers 30, 100–2, 118, 176–7, 203
activity 243–5
fixation 90–4
disruption 243– 7
oxides
receptor proteins 243– 5
formation 18, 30– 1, 59–60, 79,
Oil
89–91
Hydrocarbon 35, 41, 77–9, 120– 1,
greenhouse gas 80– 5, 87
182–3, 233
ozone destruction 24– 8, 30– 1
in rain 45, 59 Lipid 33–6
tropospheric pollution 31, 95– 100, Olivine 130–2
117, 120 Omnivores 103
Nitrogenase 93–4, 151 Optical isomerism 70– 1
Nitrosam ine 102 Organic
Nitrous oxide see Dinitrogen oxide acid 137–8, 146, 188
Noble gas see Inert gas m atter in soil
N on–methane hydrocarbons 78, 80, cation exchange capacity 115– 17,
83–4, 87 , 97– 100 125
N onylphenol 243, 245–6 and lead 192
N orm al distribution 10– 12 weathering 136–4 0 , 146– 7,
Nuclear 149–50, 161
accidents 213, 219 molecules 7–9, 33–7, 65–73
energy 209– 15 see also Chapter 18; Specific
fall out 220 compounds
fuel 213– 14, 217 Orthoclase feldspar 131, 134, 172
fuel, reprocessing 214, 216– 17 Orthophosphate see Phosphate
power 212– 13, 217, 220 Osmosis 178
weapons, testing 215, 220, 222 Osmotic pressure 178
Nuclear Oxalic acid 139
fission 41, 210– 15 Oxidation G
fusion 38, 41, 222 half reaction 21, 92, 110
radiation dose 222, 224, 226, 227, heterogenous 113
232 homogeneous 113
Oxidation (contd) and redox potential 142– 50

by oxygen 17– 19, 20– 1, 93, 110, weathering 17, 1 3 6 ^ 0 , 161–2
136–7, 161, 225 Phenylalanine 103–4
potential 21, G Phosphate
see also Iron fertilizer 118, 123–4 , 177, 202–3
Oxide ions 134 iron (III) 125, 156
Oxidizing agent 21 organic 33–7, 66– 7, 94
Oxyanion 17 photosynthesis 66–77, 69, 125
Oxygen rock 17, 123–4 , 165–6
abundance 2, 17 solution 65, 124– 5, 208
atomic 18, 24–6, 31, 59, 96– 8, 113 Phospholipid 35, 177
cycle 17– 18 Phosphorus
dioxygen abundance 2, 123–4
abundance 10, 17 cycle 94, 123– 5
atmosphere 1, 17–25, 31, 59–60, essential 34, 94, 118, 123–7, 188
69, 95–9, 141, 161, 236 in oceans 65, 126–7
in blood 102, 150–2 Phosphorylation 66–7
form ation 9, 18, 22^4, 249– 51 Photochemical reaction 9, 18, 22– 34,
electronegativity 48, 251 96–9
electronic structure 249 Photochemical smog 59–60, 95 100
essential 33, 188 Photodissociation 18, G
furnace 154 Photolysis 18, 96, 113
in incinerators 236 Photosynthesis G
ionic radius 17 algae 24, 125
isotope 38 energy storage 68, 73
in minerals 17, 130– 1, 134– 5, 173– 5 nitrogen fixation 94
Ozone reactions 22–4 , 65–9
abundance 26–8 Photosynthetic bacteria 9
layer 26 Photosynthetic reactions 9, 22–4,
stratospheric 24– 30 65–9, 77, 125
tropospheric 31, 81–5, 97– 100, 113 Phthalate esters 247
Physical weathering 51, 135– 7
PAHs see Polynuclear aromatic Phytoestrogens 245– 7
hydrocarbons Phytoplankton 34, 62–3
Pathfinder 196 Pica 194
Peat 138, 175 pK w 57
Pentachlorodibenzofurans 234– 5 Plagioclase feldspar 131, 132, 134, 136,
Pentachlorodibenzo–/?–dioxins 234– 5 138
Peptide 36– 7 Plane polarized light 71, G
Periodic table 201, 249– 50, 253 Plates, crustal 4–6, 12, 130– 1
Perspiration 52 Platinum 99– 100
Pesticide resistance 238–9 Plutonium
Petrol 31, 38, 98, 120, 190, 194 form ation 209, 213– 14
pH isotopes 214, 222, 225
definition 57 reprocessing 217
and metal uptake 117, 204 see also breeder reactors
and mercury 198 Podzols 146–9
natural waters 63– 5, 115, 117, 119 pOH 57
INDEX 275
Poisoning Pyruvic acid 7, 70

acute 194
chronic 194 Quartz 119, 130– 1, 134
cumulative 193
Polar stratospheric clouds 27–8 Radiation
Polar substances 36, 54, G electromagnetic 22–4
Pollution 181–2, 187–8 infrared 22, 25, 79–88
see also Individual elements solar 9 , 22–4, 65–9, 71
Polychlorinated biphenyls 231, 236–7, ultraviolet 18, 22, 24–31, 59, 95–8
239– 41, 247 visible 22–4, 65–9, 125
Polychlorinated dibenzofurans Radioactive waste 220–6
(PCDFs) 234–7 high level 215– 17, 219
Polychlorinated dibenzo–/?–dioxins intermediate level 216– 19
(PCDDs) 234– 7 low level 216, 218– 19
Polymer 33, G Radioactivity 39^13, 179–80, 208–9,
Polynuclear aromatic 212, 214– 34
hydrocarbons 241–3 Radio–isotope see Radioactivity
Polypeptide 36–7 Radiometric dating see Radioactivity
Polysaccharide 33–4, 70–2 Radium 228– 30
Polyvinyl chlorides 236 Radius ratio 252
Porphyrin 65–6, 68, 150 Radon
Positron 40 half–life 228– 30
Potassium properties 227– 32
abundance 2, 47, 172, 178 R adon–219: 228– 9
argon dating 179 R adon–220: 228– 32
clays 173–7 R adon–222: 228– 9
cycle 174 Rain out 114, G
essential 127, 176– 8, 188, 220 Redox reactions 20– 1, 112, 138,
fertilizer 176–7, 203 142– 50, G
ionic radius 17 see also Oxidation; Reduction
primary minerals 130–2 Reduced species 19
Potassium–40 179–80, 209 Reduction G
Power station 55, 76–7, 115, 121–2, half reaction 92, 110
160, 209– 15 iron 20. 139, 141– 50, 152–3
Precision 10– 13, G potential 21, 142– 5, G
Producers 62, 69, 125, G sulfur 106– 12
Prokaryotes 6–9 see also Oxidation; Redox reactions
Proteins Reservoirs, geochemical 13– 17, 184
in body fluids 162– 3, 177 Residence time 14– 15, 29, 83, 85, 113,
cellular material 37, 69 165, 172
food 103– 5 Respiration G
structure 36, 37, 106–9 aerobic 9, 18– 19, 22, 67–9, 92, 110
Protons 24, 38^13, 57, 67, 208–9, 248 anaerobic 67–9, 110– 11
PSCs see Polar stratospheric clouds RNA see Ribonucleic acid
PVC Ribonucleic acid 36–7, 123, 193
see Polyvinyl chloride Ruthenium 225
Pyrites 20– 1, 121, 147–8
Pyrrole ring 66, 68 , 150 Salt 58
Sandstone 12, 47, 116 , 119 solution 44– 7, 166– 7

Saturated acid 34– 5 Soft water 169–71
Saturated lipid 34– 5 Soil
Sea spray 14, 45 erosion 14– 16, 184
Sedimentary rocks 5, 16, 129, 132– 3, form ation 135–40, 145– 50, 158–9,
164– 7 161
Semipermeable membrane 178 horizon 139– 40, 147, 149–50
Sensitivity 10– 11, G metals in 725, 145– 50, 189, 202, 204,
Seveso 234– 5 220– 2
Sewage sludge minerals 123^4, 173–6
disposal 126, 202– 5 pore water 139
metals in 204– 5 sulfur in 106– 12
m ethane form ation 111 see also Individual elements
treatm ent 125, 203 Solar radiation see Radiation
Shales 112, 184, 191 Solute 53–9
Shells, electron 248–9 Solution
Siderite 147– 8, 152 acidic 57–9, 65, 116– 17, 119, 137–9
Sievert 218, 226– 7, 231, G
alkaline 57–9, 65, 137–8
Significant figures 13, G
aqueous 53–9, 63– 5
Silicates G
neutral 55– 8, 137– 8
buffer 65
saturated 54
crystal structure 130–6, 173– 5
Solvent 53–9, 119, 177– 8, 216
structural unit 17, 130, 134– 5
Soot 241
weathering 135–4 0 , 158–9
Standard deviation 10– 12, 42, G
Silicon
Starch 33–4, 70, 72
abundance 2, 47, 134
Stearic acid 168
aluminium alloys 160
Steel 153–6, 185
essential 166, 188
isotope 38 Stereochemistry 70–2
natural waters 45, 47, 137 Stereoisomerism 70– 1
slag 153 Stratosphere 5, 9, 24– 30, 85, 95
see also Silicates Subclinical effects 194
Slag 153 Subduction 4, 6, 130
Smog 95– 100, 117, 182 Substrate 71, 73
Smoke 97, 117– 18, 241 Sucrose 34
Smoking 182, 193, 206, 232, 242 Sulfate 17–20, 30, 58, 107– 13, 118–21,
Soap 168–9 168
Sodium see also Sulfur
abundance 2, 46–7, 172– 3, 178 Sulfide 20, 108– 14, 120, 133, 144, 191,
carbonate 124 196, 201
chloride 54, 161, 173 see also Pyrites; Sulfur
cycle 172– 3 Sulfur
essential 119, 127, 177– 8, 188 abundance 2, 106, 120
hydroxide 58, 161, 196 acid rain 1, 113–22, 136, 161–2
ionic radius 17, 132, 164 cycle 105– 12
minerals 130– 3, 136, 172 dioxide 18, 79, 107–8, 110, 113–22,
nitrilotriacetate 124– 5 185
pump 178–9 essential 33, 93, 117– 18, 127, 188
INDEX 277
metal sulfides 108, 112, 146, 184– 5, U ranium

188 half–life 208–9
oxidation 17–20, 107– 14, 120 hexafluoride 215
reduction 106– 12, 156– 7 ores 208, 215, 217
trioxide 18, 107, 108, 110, 113 oxide 125, 208, 213, 215, 223, 225
see also Desulfurization; Proteins properties 208
Sulfuric acid 18, 59, 108, 112– 13, U ranium –234: 209
119–21, 185 U ranium –235: 42, 208– 15, 217, 228–9
Superphosphate 118 U ranium –238: 41, 180, 208, 213, 218,
228–9
TCD D see Tetrachlorodibenzo–/?–dioxin Urea 95, 101
Terpene 31 UV–A 24, 31, 97
Testosterone 243–4 UV–B 24–6, 30– 1, 59
T etrachlorodibenzo–/?–dioxin 233–7, UY–C 24– 6, 29, 95
246
Thermal capacity 53 Valence 249
Thermodynamics Valency 249
laws of 2, 73–7 Vanadium 188, 208
stability 2–3, 73–7, 89–90, 91–4 Vertebrates 166
Thorium 41, 180, 209, 218, 228–9 Visible light see Radiation
Three Mile Island, nuclear
Vitamins 66, 104– 5
accident 222– 3
Vitellogenin 247
Threshold limit value 196
Thyroid
W a sh o u t 114, G
endocrine G
W ater
iodine uptake 220– 1, 226
Tin 39, 188 abundance 43–4, 81
Tobacco 206 in atmosphere 18, 27, 79– 82, 86
Toxic elements 118, 161, 185–9 cycle 43– 5
see also Lead; Mercury; Cadmium; development of life 6– 10
Zinc greenhouse gas 79–82, 86
T oxic equivalent’ (TEQ) value 236–7 hard 167–71, 192
T oxic equivalent factor’ (TEF) 237 hydrogen donor 9, 22, 67
Toxicity 105, 185–9 oxidation/reduction 142– 5
see also Poisoning soft 118, 167–71
Transpiration 52, 118, G solvent 53–9
Triglyceride 24–6, 72 structure 48– 53
Tritium 39, 41–3, 218 see also Individual elements
Troilite 112 Wavelength 22–3
Troposphere 5, 26, 29, 31, 83– 5, Weathering
96– 100 chemical 4 ^ 6 , 112, 135– 40, 158–9,
Tungsten 154 191–2
physical 51, 135–6
Ultraviolet see Radiation see also Individual elements
see also UV–A; UV–B; UV–C
U nsaturated acid 35 X rays 23, 41, 227, 232
U nsaturated fat 35 Xenon 210, 222, 227, 249
278 ENVIRONM ENTAL CHEMISTRY
Zinc metal 160, 214

abundance 201–2 sulfide 120, 196, 201
cycle 201–2 toxic 118, 205
essential 188, 201, 206 Zirconium alloy 223–4
galvanization 156–7 Zooplankton 62–3

Enviromental Chemistry Peter O&#39;Neill

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London • Weinheim • New York ♦ Tokyo • Melbourne • Madras

T hom son Science, 2-6 Boundary Row, London SE1 8HN, U K

Thom son Science, Pappelallee 3, 69469 Weinheim, Germ any

First edition 1985

Second edition 1993

Third edition 1998

© 1998 Thom son Science

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ISBN 0 7514 0483 7

PART ONE THE OXYGEN-RICH PLANET 1

PART TWO M A JO R ELEM ENTS FO U N D IN LIVING

PART THREE M A JO R ELEM ENTS IN THE EARTH’S CRUST 129

11 Calcium and magnesium 164

12 Sodium and potassium 172

PART FO UR M INOR ELEM ENTS A N D ENVIRONM ENTAL

18 Hazardous organic compounds 233

Appendix Chemical compound formation 248

Pbsolid ^ ^ s o lu tio n + (P l-1 )

The consequence o f this simple change could be the poisoning o f people

Universe Earth Crust Ocean Atmosphere Biosphere

Figure 1.1 Structure.

Continental crust Atmosphere - - stratosphere

Percentage of Earth’s surface occupied

Sector Major elements in order of decreasing concentration

ocean O, H (Cl, Na, Mg, S)

sedimentary rocks O, Si, Al, Fe, Ca, K, Mg, C, Na

2 ] f(r“i;i,ic igneHUS O, Si. Al, K. Na . Ca. Fe. Mg

mantle O, Si, Mg, Fe

mountain building mid-ocean

------► <------ <«----- ------►

1.1 Development of life

cell wall nucleoid mitochondrion

(a) Prokaryotic cell (b) Eukaryotic cell

atom s. Because m any o f them are essential to life, carbon-containing

Figure 1.5 A possible pattern for the development of life on Earth.

The release o f dioxygen b ro u g h t ab o u t m ajor changes to the E a rth ’s surface

1.2 Distribution of the elements

average, o f all the results. In practice it is found th at the elemental

(a) Normal distribution (b) Lognormal distribution

Proportion of results that are within Positively skewed results - if the

Figure 1.7 Normal and lognormal distributions o f results.

hom ogeneous as m ight a t first be thought. T he concentrations o f the m ajor

surface? It is n o t surprising th a t different estim ates o f crustal abundances

1.3 Geochemical cycles

Tables such as Table P l . l , showing the distribution o f the elements, ignore

tra n sp o rt pathw ay in a fixed period o f tim e, usually 1 year (Figure 1.8). If

am o u n t o f elem ent in reservoir .

F o r example, if the am o un t o f sodium dissolved in the ocean is 15 x 1018 kg,

1 precipitation (rain, snow) 5 gas evolution

Figure 1.8 A general model of the geochemical cycle.

Figure 1.9 Geological processes involved in geochemical cycles.

Oxygen A bundance by weight (the relative abundance is given in

causing increased solubility

Figure 2.1 Chemical species found in the oxygen cycle.

p roduced by photosynthesis. In addition, a sm all am o u n t is produced by the

U V rad iatio n is also involved in the conversion o f dioxygen into the

0 2 u Xi!fht O + O (atom ic oxygen) (2 .2)

This ab so rp tio n prevents the m ajority o f the energetic UV rad iation th a t is

S2~ + 2 0 2 — > SO2- (2.6)

A t present there seems to be a state o f equilibrium between the rate o f

2.1 Molecular oxygen in the atmosphere

L ooking at Figure 2.1, we see th a t carbon dioxide ( C 0 2), sulfur dioxide

Enviromental Chemistry Peter O'Neill

Enviromental Chemistry Peter O'Neill

w here N is A v ag ad ro ’s num ber = 6.023 x 1023 m o l-1 ; h is P lanck’s con

£ _ I_ i_ I_ i___ L

J I I L J I1