Applied Geochemistry 24 (2009) 10581073

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Geochemistrys vital contribution to solving water resource problems

W.M. Edmunds
Oxford University Centre for Water Research, School of Geography and the Environment, Oxford University, South Parks Road, Oxford OX1 3QY, UK

a r t i c l e

i n f o

Article history:
Available online 25 February 2009

a b s t r a c t
As part of the events celebrating 40 a of IAGC, it is tting to trace the modern evolution and development
of hydrogeochemistry. However, fascination with water quality can be traced back more than 2 ka. In the
post-war years, hydrogeochemistry was inuenced heavily by the advances in other disciplines including
physical chemistry, metallurgy and oceanography. Hydrological applications of isotope science also
developed rapidly at this time, and important advances in analytical chemistry allowed multi-element
and trace element applications to be made. Experimental studies on equilibrium processes and reaction
kinetics allowed bench-scale insight into waterrock interaction. Consolidation of knowledge on processes in groundwaters and the current awareness of hydrogeochemistry by water professionals owe
much to the work of Robert Garrels, John Hem, and co-workers in the early 1960s. Studies of down-gradient evolution enabled a eld-scale understanding of groundwater quality and geochemical processes as
a function of residence time (dissolution and precipitation processes in carbonate and non-carbonate
aquifers; redox processes; cation exchange and salinity origins).
Emerging water resource and water quality issues in the 1960s and 70s permitted the application of
hydrogeochemistry to contaminant and related problems and this trend continues. The impacts of diffuse
pollution from intensive agriculture, waste disposal and point source pollution from urban and industrial
sources relied on geochemistry to solve questions of origin and attenuation. In semi-arid regions facing
water scarcity, geochemical approaches have been vital in the assessment of renewability and characterising palaeowaters. The protection and new incoming regulation of water resources will rely increasingly
on a sound geochemical basis for management.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
This is a good opportunity for a 40-a retrospective on hydrogeochemistry and how it has shaped some of the thinking and practice
in the management of water resources. It is now apparent that we
can no longer engage in purely reductionist approaches or stay
within narrow disciplines to resolve pressing environmental problems. Geochemistry has always had a global, if not a planetary,
dimension that has enabled research to be directed at problems
at different scales. In hydrogeochemistry, therefore, the evolution
of large water bodies with residence times of up to a million years
may require research at the molecular level to allow understanding
of age distributions and processes controlling quality. Earth system
science and consideration of global geochemical cycles (Garrels
et al., 1975; Berner and Berner, 1996) are now most appropriate
for setting the context for the resolution of water scarcity and quality issues. Glynn and Plummer (2005) have recently traced the
development of geochemical principles over the past 50 a that
have played a role in improving understanding and conceptualization of chemical and hydrologic processes in groundwater systems.
The present paper now takes the subject further into the area of
water resources, looking back also at the distant origins.
E-mail address: wme@btinternet.com
0883-2927/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2009.02.021

Groundwater represents about 96% of the worlds reserves of

unfrozen fresh waters (Shiklomanov and Rodda, 2003). The developing global water crisis (Postel, 1996; UNESCO, 2006) has evolved
in little over half a century and affects most severely the arid and
semi-arid regions of the world where groundwater is relied upon
for water supply. This is a crisis of both quantity and quality. It
has emerged mainly as a result of bold supply-led engineering
solutions, which have resulted in the creation of large dams and
large well-elds. Drilling for water has often been unregulated
and the situation exacerbated by government subsidies for agriculture (the main user of water with up to 90% of the total use in some
countries) and the low price of electricity for pumping. Much of the
progress in food production has taken place unsustainably at the
expense of groundwater. The green revolution in India and other
countries, producing miracle rice has relied upon groundwater
leading to severe drawdown of water tables.
The objective of the present paper is to consider the evolution in
understanding of water quality, of groundwater in particular, and
the role that geochemistry has played especially over the past 40
a. Not only has geochemistry addressed questions of water quality,
but it has also played a signicant role in dening certain physical
properties of aquifers (for example, recharge rates, residence times
and ow pathways). Finally, the role of geochemistry in helping to
solve the pressing current and future issues of water scarcity and

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

1059

quality deterioration will be considered and how the large body of

geochemical knowledge can feed in to water policy and
management.

properties to water. The chronology of water quality events leading to the birth of modern hydrogeochemical science is summarised in Table 1.

2. Historical perspectives

2.2. Towards an understanding of water quality the age of

enlightenment

2.1. Early stirrings

Fascination with water quality originates early in written records. Springs, symbolic of the sustainability of life on Earth, are
venerated in Babylonian tablets and in the creation stories of many
civilisations, and also in the Bible and other religious texts. The
narrow interface between fresh and (bitter) salt water in arid regions is celebrated in the story of Moses nding water in Sinai
(Exodus 15). Hard and soft water were dened in a discourse on
water quality by Hippocrates (460377 BC) and mentioned by
Hem (1985). This was translated by Baker (1949):
Consider the waters which the inhabitants use, whether they be
marshy and soft, or hard and running from elevated or rocky
situations. . .
Pliny the Elder, who was killed in the AD 79 eruption of Vesuvius, may however be regarded as the rst hydrogeochemist with his
pertinent observations on water quality which may be translated
as:
All water is sweeter in winter, in summer less so, in autumn least
and less during droughts. The taste of rivers is usually variable
owing to the great difference in river beds. For waters vary with
the land over which they ow and with the juices of the plants they
wash.
From this may
Hydrogeochemistry:

be

formulated

the

rst

law

of

Waters take on the properties of the rocks through which they

pass.
Waterrock interaction has been an important focus of IAGC
during the past 40 a but it is interesting to note how it has fascinated scientists and philosophers over 2 ka or more. Importantly,
Pliny also recognised the relevance of organic matter in imparting

Modern scientic theory and understanding of the water cycle

date from the seventeenth century. The earliest explanations of
the hydrological cycle, often termed the reversed hydrological cycle,
probably stem from biblical sources (Ecclesiastes 1:7). The unexplained constancy of the ocean volume was accounted for by the
return of seawater through the rocks, which then puried them
and returned the water to the surface as freshwater rivers and
springs. This interpretation of the hydrological cycle persisted
through the writings of ancient Greece and Rome as in Senecas
Quaestiones Naturales and into the Middle Ages (Tuan, 1968) until
correctly explained by Jorden (1631), then by Sir Edmund Halley
(Halley, 1691).
The evolution of thought regarding natural water quality can be
followed through the observations of many famous scientists who
studied renowned thermal waters such as the Roman springs at
Bath, England and which have been summarised by Edmunds
(2004). Edward Jorden, who studied medicine and chemistry at
Padua at the time of Galileo and who moved to Bath, was the rst
to explain the modern hydrological cycle (Jorden, 1631). The distinguished scientist Joseph Glanvill, who worked with Sir Isaac
Newton and was one of the rst Fellows of the Royal Society,
was also Rector of the Abbey Church in Bath. This was a characteristic of many scientists of the time who combined rigorous scientic study with holy orders, medicine, or philosophy. He was one
of the rst to promote the experimental approach in scientic
investigation (see Smith, 1972). Glanvill (1669) proposed a hypothesis for the heat of the waters, being an exothermic chemical reaction caused by the mixing of uids. He had probably observed the
oxidation of sulphide minerals and seen the process of travertine
cementation around springs this is therefore one of the earliest
accounts of waterrock interaction:
The baths are of great antiquity. . . which if so, would give occasion
to enquire how consistent with it that hypothesis (concerning the

Table 1
Chronology of important hydrogeochemistry events.
460377 BC
2379 AD
1669
1691
1800
18001820
1849, 1853
1887
1893
1925
1935
1950
1953
1959
1964
1970
1970
1973
1986
1998
2000
2006
2007

Hippocrates introduces the concept of hard and soft water

Pliny the Elder introduces the differences between surface and groundwater quality, the importance of organic matter, and waterrock interaction (water
takes on the properties of rocks through which it has passed)
Joseph Glanvill explains exothermic processes as a source of heat of thermal waters
Sir Edmund Halley correctly presents the explanation of the hydrological cycle
George Gibbes describes silica solubility and the rst reference to geothermometry
Discovery of a number of chemical elements and their occurrence in groundwaters
London cholera outbreak start of the science of potable water analysis
Arrhenius develops his dissociation theory: Introduction of ionic constituents
Marie Curie discovers radium in Paris
Vernadsky publishes The Biosphere
Dole is the rst to apply environmental isotopes (oxygen) on Lake Michigan
First issue of Geochimica et Cosmochimica Acta
Libby recognizes the potential applications of tritium in hydrology
John Hem publishes rst edition of Study and Interpretation of the Chemical Characteristics of Natural Waters
Garrels and Christ publish Solutions, Minerals and Equilibria
Establishment of US Environment Protection Agency
Publication of key paper on natural remediation Selbstreinigungsvorgange im aeroben und anaeroben grundwasserbereich (Golwer et al.)
First published geochemical model for groundwater (SOLMINEQ) by Kharaka and Barnes
First issue of Applied Geochemistry
Translation into English of Vernadskys The Biosphere by Langmuir
Publication of EU Water Framework Directive
Publication of EU Groundwater Directive
IAGC celebrates 40th anniversary

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

The springs at Bath were also the test bed for many scientic
theories, for example on the volcanic versus the exothermic origins
of heat and the origins of salinity. William Smith, the founder of
geological science who also worked and lived near Bath, correctly
explained the deep source of the spring and the concept of geothermal gradient. With the quest for the structure of matter and the
recognition of the elements leading to the foundation of chemistry
as a science (by Antoine Lavoisier) around 1750, the Bath waters
became important as a laboratory for the discovery of new elements and a rush of publications ensued. Gibbes (1800) rst discovered large amounts of silica in the springs and also provides
what may be the rst reference to geothermometry:
A still more convincing argument to prove that their heat is
intense at a certain depth is their containing so large a proportion
of siliceous earth. I believe that siliceous earth is capable of being
diffused in water when that water has been subjected to an intense
heat . . . and pressure.
The springs were a test bed for studies of dissolved gases by Joseph Priestley and others, and in the early 20th century for discoveries relating to radioactive elements. The discovery of radium in
1893 by the Curies in Paris immediately led to research in Britain
into natural radioactivity. Sir William Ramsay discovered Rn in the
thermal waters at Bath in 1898, and in the same year Lord Rayleigh
discovered He in the springs. Sir William Ramsay (Ramsay, 1912a)
conrmed the Ra content of the springs and also radium emanation, the last undiscovered noble gas (Rn) as well as Ne, in the
springs (Ramsay, 1912b).
2.3. The post-war era
There had been little fascination for scientic study of natural
waters by geochemists in the early twentieth century. The physical
and chemical properties of natural waters were often considered
separately and water quality was the domain of the chemist. Most
of the rationale for water quality studies in the rst half of the
twentieth century was to derive drinking water standards and
standards for agriculture. A landmark was the publication by
Clarke (1924) who rst compiled an inventory of water quality
across USA. Mainstream geochemists (e.g., Goldschmidt, 1954)
were mostly concerned with the abundance of the elements in
crustal rocks with little or no reference to their aqueous
geochemistry.
One barometer of the emerging post-war interest in the scientic discipline of hydrogeochemistry is the breakdown of papers
in Geochimica et Cosmochimica Acta (GCA) which rst appeared in
1953 (Fig. 1). The steady growth of the discipline until 1970 can
be seen followed by a more rapid growth after 1970, in line with
the growth of interest in environmental issues. The GCA proportion
of water related papers has remained high through the past two
decades. The high percentage of articles in Applied Geochemistry
since its launch in 1986 is also matched by the growth in water related articles. The early papers in GCA mark the emerging science
of isotope hydrology (e.g., Friedman, 1953; Epstein and Mayeda,
1953). Out in front in the rst issue of GCA, however, is the classic
paper by Margaret Foster (Foster, 1953) on the origin of high sodium bicarbonate groundwaters of the US Atlantic coastal plain.
A further classic in the early GCA was the series of three papers
by Chebotarev (1955) on the metamorphism of natural waters, fol-

400

300

total water articles

heat of these waters) would be which makes it to be the fermentation of minerals; and whether it be likely that the minerals through
which these waters should pass, should be in that state of imperfection so many hundred years, and that the whole disposed matter in
those places should not be perfectly concreted in so great a tract of
time.

Geochimica et Cosmochimica Acta

Applied Geochemistry

200

100

1940

1950

1960

1970

1950

1960

1970

1980

1990

2000

2010

1980

1990

2000

2010

1.1
1.0

fraction of water articles published

1060

0.9
0.8
0.7
0.6
0.5
0.4
0.3
1940

Year
Fig. 1. Classication of papers published in Geochimica et Cosmochimica Acta and
Applied Geochemistry: (a) total water articles since rst issue in 1951. The score has
been compiled using the keywords water AND (ground OR natural OR hydrogeochemi OR hydrogeolog OR hydrochemi OR isotop OR (aqueous AND (solution
OR solute OR ion)) OR spring OR stream OR dissolut OR brine OR saline OR salt); (b)
same data shown as the fraction of total articles dealing with water. The arrow
corresponds to the rst appearance of Applied Geochemistry.

lowed by two papers on silica hydrochemistry (White et al., 1956;

Krauskopf, 1956).
Hydrogeochemistry was also inuenced by other disciplines.
The work by chemists and metallurgists on thermodynamics set
the scene for a strong physical chemistry inuence on water
chemistry. Thus Pourbaix (1949) introduced the concept of stability eld diagrams from his work in metallurgy and this was
adopted by hydrochemists as a critical tool for describing the redox properties of natural waters (Hem and Cropper, 1959). Similar pioneering work had also been conducted pre-World War 2 by
oceanographers (Cooper, 1937) and in the early days of hydrogeochemistry much was gained from comparison with processes
across different elds of science. The post-war texts on chemical
thermodynamics (Prigogine and Defay, 1954; Lewis and Randall,
1961) were inuential in forming a groundwork on the transition
from studies in a mainly laboratory environment to eld based
studies and experimental work on natural systems. The work on
natural redox environments across the disciplines of oceanography, sedimentary petrography, soil science, and limnology was
summarised by Baas-Becking et al. (1960). At the same time, there
was great interest in element budgets of the worlds major rivers,
mainly driven by the work of oceanographers, with work conducted mainly by American and Russian scientists (Konovalov,
1959; Gibbs, 1967; Kharkar et al., 1968).

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

Hydrogeochemistry was also strongly inuenced by the developments in analytical methods as seen with the advances in mass
spectrometry allowing isotope hydrology to emerge as a key discipline. The advent of multi-element techniques, such as AAS, allowed improved detection limits and rapid analysis over and
above the rather laborious colorimetric analysis employed until
that time. One further example that had and continues to have a
profound effect on environmental studies was the invention of
gas chromatography and the electron capture detector in particular
(Lovelock, 1963).
The birth of hydrogeochemistry as a modern scientic discipline took place in the early 1960s with the publication of the classic text Solutions Minerals and Equilibria by Garrels and Christ
(1964), the single most important book in the past 40 a. It introduced the thermodynamic concepts required for study of water
rock interaction where impure minerals, rather than laboratory
pure chemicals, are the norm. In simple language, and with worked
examples, this book introduced low temperature geochemistry to a
whole new generation not least the author of this paper, who was
aided in the transition from high temperature metamorphic geochemistry to low temperature environments by this life-changing
text. The life and inuence of Bob Garrels has been documented
by Berner (1992). Further advances were made in the USA spearheaded by students of Garrels including many who in turn have
made their own notable mark on the science (including Langmuir,
Bricker, Hanshaw, Helgeson, Runnells, Sato, Wollast, Kump and
Berner).
The inuence of Russian scientists on the evolution of the new
science was also highly signicant. Vladimir Vernadsky (1863
1945) published his seminal work The Biosphere (Vernadsky,
1926), which only appeared in English in 1998, translated by Langmuir (Vernadsky, 1998). Vernadsky was trained as a geologist but
was drawn into other elds under the inuence of many renowned
scientists at St. Petersburg University, among whom was Mendeleev. Vernadsky was the rst to realise the importance of biology
and human impacts in earth processes. His essays on geochemistry
and the biosphere represented a synthesis of knowledge at that
time and indicate the importance of early Russian scientists on
the formulation of hydrogeochemical concepts.
Following the formation of IAGC in 1967, an international meeting was organised on Hydrogeochemistry and Biogeochemistry in
Tokyo. A number of interest groups across the P-T range of interest
to geoscientists working in all disciplines were proposed at this
meeting by Vladimir Valyashko and Earl Ingerson. Of these, the
Working Group on Water Rock Interaction has proved the most
enduring and has provided a stimulus to scientists working in
water resources and related elds for a generation (Hitchon,
1989). Twelve triennial symposia have now been held and low
temperature waterrock interaction formed a major part of the
most recent symposium held in Kunming, China (Bullen and Wang,
2007).
2.4. Evolution of analytical and investigative tools
2.4.1. Nineteenth century
Geochemists and hydrogeochemists remain fascinated by mineral waters. As we have seen, some of the earliest theories about
groundwater and water quality emerged from studies by natural
philosophers on mineral and thermal waters. It is also of interest
that most of the early development of analytical chemistry was
spurred in Europe by investigations of the spas (Hamlin, 1990).
In America, a historical perspective of early quantitative chemical
analyses of groundwater is also given by Davis and Davis (1997).
Medicinal powers were claimed for thousands of springs throughout Europe, and their waters possessed a great range of compositions and properties. This was the domain of the chemist and

1061

especially of individual academics that made claims and counterclaims for the properties of their springs and those of rival balnaeological establishments. In this way patronage of the spas developed and a few very successful establishments emerged; in
England towns such as Bath, Harrogate and Cheltenham owe their
prominence to the successful promotion of their unique mineral
water properties. Similar famous spa resorts such as Baden Baden
in Germany attracted many of Europe and Russias most famous
literary names thereby forming important cultural centres of European philosophy and literature.
One event, the 1848-9 cholera outbreak in London, and the later
outbreak in 1853, drew attention to the transmission of disease by
drinking polluted potable shallow groundwater and the investigation of the Broad Street outbreak by the physician John Snow
(Price, 2004) was instrumental in transforming attitudes to potable
water analysis.
Water analyses in the 19th and early 20th centuries were reported either in terms of constituent acids and bases or more
widely as the salts in which the dissolved substances combined
on evaporation as dry residues. Amazingly, the legacy of this practice still lives on, since the modern water industry in many countries still refers to nitrates and chlorides, rather than
recognizing the modern convention. However, this controversial
practice was questioned as early as 1815 by John Murray who proposed that the salts obtained in analysis were not necessarily the
salts that existed in solution (Hamlin, 1990). From the beginning
of the 19th century to its end, water analysts were wrestling with
the great issues of the philosophy of science. But at the same time
they had to make their results useful to clients, whether these were
proprietors of mineral water establishments or, increasingly after
1850, municipal authorities, public health ofcials, or emergent
water companies.
2.4.2. Modern conventions, modern analysis
The modern practice of expressing water analyses in terms of
ionic constituents derives from Svante Arrhenius (Arrhenius,
1884). His dissociation theory proposed that acids are substances
that dissociate in water to yield electrically charged atoms or molecules. From that time it became more common to report all constituents in natural waters in terms of ionic constituents. Many of
the subsequent advances in analytical science were derived from
marine science, rather than fresh waters, for much of the rst half
of the 20th century. The geochemical interpretation of natural
waters has its origins in the mining industry (Palmer, 1911;
Hem, 1985).
It was not until the 1950s and 1960s that geochemical analysis
became more diverse with the advent of colorimetric analysis, pioneered mainly by oceanographers (for example, Riley and Skirrow,
1965). Colorimetric analysis allowed development of a range of
sensitive techniques for the analysis of trace constituents in natural waters which hitherto had been virtually impossible to analyze
with any precision or accuracy.
The discipline of modern hydrogeochemistry also owes much to
the work of the US Geological Survey (USGS) scientists in the early
1960s, especially the basic procedures for eld study and geologically-based interpretation of water analyses (Back and Freeze,
1983). Until this time most water quality measurements were laboratory based, but the need for in situ measurements of redox-related parameters and above all pH for the characterisation of
properties of surface and groundwaters was documented in a series of water supply papers (Rainwater and Thatcher, 1960) and
summarised in the classic work by John Hem (1959; updated
1985). The latter work by Hem has undoubtedly been the single
most important inuence promoting hydrogeochemistry among a
generation of hydrogeologists. However, at the same time the
zonation of processes in aquifers, pioneered by Foster in the

1062

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

1950s, was formalized by Back (1966) as hydrochemical facies The

USGS also initiated a series of standards for water analysis, as it
had done for rock analysis, which helped focus on accuracy in
water analysis, especially for trace elements. All this work was consolidated in USGS (1998). IAGC, through its Working Group on the
Geochemistry of Natural Waters, also conducted an international
comparison programme which highlighted the difculties at the
time in particular of trace analysis (Ellis, 1976).
The huge expansion in output and knowledge from the 1970s
(Fig. 1) owes much to the breakthroughs in instrumental analysis,
rst with AAS and then with ICP-AES and ICP-MS methods. Multielement analysis using the latter techniques has now become routine in research on waters and has also enabled investigation of
many elements at sub-lg L 1 concentrations. In addition, ion chromatography allowed multi-element analysis of microlitre volumes
of water (Small and Miller, 1982) opening the door to extensive anion investigations for example in the study of acid rain (Saether
and Andreassen, 1995). With this has come the inevitable need
for optimal attention to sampling, cleanliness, and standardization
procedures. These analytical advances have also allowed breakthroughs in microanalysis, for example of pore waters (Kinniburgh
and Miles, 1983; Moss and Edmunds, 1992).
2.4.3. Isotope analysis
The application of environmental isotopes in hydrology dates
back to 1935, when O isotope ratios were rst measured on Lake
Michigan water by Dole (1935). The rst systematic application
to natural waters was spurred by the classic paper of Craig
(1961) who showed systematic global differences in the isotopic
composition of precipitation. The rst paper on radiocarbon application to groundwater dating was by Munnich (1957). The injection of 3H (and other radioisotopes) into the global water cycle
from thermonuclear weapons testing in the 1950s and early
1960s, provided an ideal universal conservative tracer and a decade or more of ground-breaking work, initially by nuclear physicists and subsequently by hydrogeologists and geochemists
(Libby, 1953; Kaufman and Libby, 1954; von Buttlar and Libby,
1955; von Buttlar and Wendt, 1958).
After 40 a of research, stable and radio-isotope techniques have
become embedded in hydrogeological curricula and applications,
where they are essential in dening conceptual models, establishing groundwater circulation processes, understanding the evolution of water quality, tracing the origins of both water and
solutes, in groundwater residence time studies, and palaeohydrology. There are several excellent texts on this topic (Fritz and Fontes, 1980; Clark and Fritz, 1997; Mook, 2001) which summarise
the systematics as well as the applications of isotope hydrology
to groundwaters, and introduce the very wide range of isotope
tools now available (Cook and Herczeg, 1999; Aggarwal et al.,
2005). The future of isotope applications in hydrogeochemistry
continues to look promising with the advent of multi-collector
ICP-MS instruments, leading to the possibility of extending stable
isotope studies to most of the periodic table.

groundwater systems in the 1960s, where it was recognised that

large irreversible non-equilibrium changes often accompanied
changes in the oxidation states of the elements (Glynn and Plummer, 2005). Thorstenson (1984) provided a critical review of redox
concepts pointing out for example that a thermodynamically
meaningful value of redox potential cannot be assigned to disequilibrium systems and that the most useful approach to the study of
redox characteristics is the analysis and study of multiple redox
couples in the system; for all practical purposes, thermodynamically dened redox potentials do not exist (and thus cannot be
measured) in natural waters. Nevertheless, the measurement of
Eh and determination of the redox boundary remain of immense
signicance as a practical tool for hydrogeologists.
3.1. Carbonate systems
Equilibrium studies of natural systems evolved from the work
of laboratory chemists in the previous two decades, especially on
the carbonate system (e.g., Harned and Scholes, 1941) and with
parallel work on modern carbonates by sedimentary geochemists.
In the 1960s, several denitive works on carbonate aquifers in the
USA appeared including the Floridan limestones (Hsu, 1963; Back
and Hanshaw, 1970) and karstic systems.
One of the most important and instructive papers at this time
was the study of Appalachian groundwaters by Langmuir (1971).
Investigations were completed without the aid of fast computers,
thereby forcing a critical evaluation of the thermodynamic input
data (e.g., carbonate mineral solubility constants and ion pair formation required for equilibrium calculations and for comparison
with eld measurements. This resulted in a clear demonstration
of the critical importance of precise and accurate measurement
of eld pH, as well as the relative importance of other parameters
in determining carbonate mineral saturation. The studies on this

3. Consolidation of knowledge on processes in aquifer systems

Scientic studies on groundwaters and hydrogeochemical processes in the 1960s and 1970s developed rapidly as a result of work
by physical chemists, eld based studies, and application of experimental data. Following the benchmark publication by Garrels and
Christ (1964), which consolidated the theoretical background, the
groundwork was clear for application to understanding groundwater processes in terms of waterrock interaction.
Silln (1967) introduced the concept of the master variables (pH
and pE). The concept of redox boundaries or barriers already used
to describe roll-front ore deposits for example, was applied to

Fig. 2. Open and closed system behaviour. Possible approaches to equilibrium of

groundwater in contact with CO2 and calcite and dolomite. Classic paper on the
Appalachian springs (Langmuir, 1971).

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

mixed sequence of limestones and dolomites (Fig. 2) also demonstrated the open and closed system behaviour of carbonate reactions as well as the importance of diffuse and conduit ow. This
work was followed by pioneering studies by Deines et al. (1974)
who treated the C isotopic evolution in the formation of the Pennsylvania waters.
Many of the problems associated with groundwater development that relate to salinity, especially in carbonate sediments,
originate from the displacement of formation waters from marine
sediments. The nature of saline waters in sedimentary rocks was
summarised in the classic paper by White et al. (1963) who proposed that residual formation (connate) water was likely to be locally preserved as a source of salinity. This was demonstrated by
Bath and Edmunds (1981) in an isotopic and chemical study of a
500 m pore water sequence for the Chalk aquifer of the UK. Fresh
groundwater in the upper aquifer grades with depth into saline
water, which at 500 m depth can be shown to be little-modied
Cretaceous sea water.
3.2. Non-carbonate systems
The understanding of silica in groundwaters stems from work in
the 1950s by Krauskopf (1956) and then extended and summarised
for low temperatures by Davis (1964). Further understanding of
the solubility of quartz and silica polymorphs derives from the
work of Morey et al. (1962, 1964) and great interest in the subject
received a boost with development of silica as a geothermometer
(Fournier and Rowe, 1966). Explaining the controls on silica in
groundwaters, however, still remains a challenge for low temperature geochemists.
An outstanding example of treatment of water chemistry in
non-carbonate systems was the Sierra Nevada study of stream
and shallow groundwaters (Garrels and Mackenzie, 1967). Water
chemistry was used to construct stoichiometric compositions of
original minerals in geologically simple catchments. Helgeson
(1968) developed a theoretical approach to the behaviour of silicate mineral reactions with stability eld diagrams showing the
pathways of weathering reactions in natural waters, as well as
emphasising the irreversibility of silicate reactions.
In contrast to the well buffered carbonate aquifers, many earlier
denitive hydrogeochemical studies were carried out on sandstones and other non-carbonate aquifers, where mineral undersaturation, redox processes, and ion exchange could be better
investigated. These aquifers also attracted the attention of isotope
specialists, because many of the problems of radiocarbon interpretation were simplied in the absence of carbonate minerals (Pearson and White, 1967). A number of investigations were conducted
on the aquifers of the Atlantic and Gulf coastal plains of the USA
and followed the work of Cederstrom (1946) and Foster (1953) in
which the role of organic matter in CO2 production and base-exchange in the generation of high bicarbonate waters was recognised. Nevertheless, traces of residual carbonate in some clastic
aquifers, as well as granitic rocks, often dominate the overall
hydrochemistry.
Improved understanding of the solubility of Fe was achieved by
studies in the Cretaceous and Tertiary aquifer sequence of Maryland, USA (Barnes and Back, 1964; Back and Barnes, 1965) and
New Jersey (Langmuir, 1969). These studies showed that eld concentrations closely followed the redox boundaries and that predicted theoretical concentrations matched closely with the
observed data. Further studies of the Coastal Plain aquifers have
led to the modern understanding of Fe behaviour, time-dependent
processes, and cation exchange, often where interdependent controls by waterrock interaction on both water composition and
mineralogy may be followed (Schluger and Roberson, 1975). The
Aquia aquifer in Maryland also serves as a classic eld laboratory

1063

for the understanding of cation exchange in relation to freshening

of groundwaters by chromatographic processes, as marine waters
are displaced by down-gradient migration of fresh water recharge
(Chapelle and Knobel, 1983; Appelo, 1994).
3.3. Classic studies of groundwater ow systems
Understanding of hydrogeochemical processes has been greatly
enhanced by those studies which have looked at sequential
changes in temperature, timescales, and chemistry. Water management has to take into account the continuous nature of
waterrock interaction with time whether inherited from natural
past evolution or processes taking place in real time. These studies
are numerous and have been conducted over the past 40 a in Europe and North America as well as in some of the large sedimentary
basins of North Africa, Australia and China.
One of the most comprehensive of these is the study by Pearson
et al. (1991) of the Molasse Basin, lying between Switzerland and
Germany, in which a complex sequence of faulted sedimentary
rocks forming part of the Alpine foreland was investigated. Its focus was squarely on the testing of isotopic tools, yet it also interprets these in full conjunction with supporting chemical
(including dissolved gas), mineralogical, and hydrogeological data.
The range of tools is impressive. Isotopes that were studied to
investigate ow rates included 3H, 3He, 4He, 14C, 36Cl, 36Ar, 39Ar,
40
Ar, 85Kr, 234U and 238U. Investigation of recharge conditions were
studied using the dissolved noble gases (Ne, Ar, Kr, Xe) as well as
d18O and d2H. A wide range of isotopes was also included to investigate the geochemical evolution of groundwaters, including d13C,
d34S, 87Sr/86Sr, 36Cl/Cl, 37Ar/Ar, 40Ar/36Ar, as well as the concentrations and ratios of a range of U and Th isotopes and their daughter
products. Overall, this is an honest and very detailed state-of-theart study, which is at the same time a classic showpiece for isotope
applications, yet a warning on the limitations of obtaining simple
answers from complex aquifer systems.
The Cretaceous Milk River Sandstone aquifer, which is recharged mainly from Montana, USA but ows northwards into Alberta, Canada, was studied by an international consortium
(Ivanovich et al., 1991). It is a relatively thin (3060 m) sandstone
unit but with a ow path of 80100 km, with hydraulic estimates
of ow times in excess of 500 ka (Hendry et al., 1991). The Milk
River study covers a similar range of isotopic tools as the Molasse
Basin, but also highlights problems with the applications of individual isotope systems. It also shows the value of the previously
established hydrochemistry in determining the ow patterns and
the zones of higher transmissivity.
The East Midlands Triassic sandstone aquifer UK () has also
been the subject of many papers looking at time-dependent Edmunds et al., 1982; Smedley and Edmunds, 2002geochemical processes. It has the advantage of being virtually unaffected by
salinity increases down-gradient and has well dened redox properties. It contains an inert tracer record of pre-industrial conditions, as well as allowing the charting of the impact of pollution.
Changes in the hydrochemistry can also be well correlated with
changes in the mineralogy (Fig. 3).
3.4. Development of geochemical modelling
In the early 1970s, increasing computing power led to the
rst comprehensive geochemical models for groundwater, e.g.,
SOLMINEQ (Kharaka and Barnes, 1973) and WATEQ (Truesdell
and Jones, 1974). This rst family were equilibrium/speciation
models but led the way to more powerful versions WATEQF
(Plummer et al., 1984), WATEQ4F (Ball and Nordstrom, 1991),
SOLMINEQ.88 (Kharaka et al., 1988) and related programmes
that were also able to simulate mass transfer changes resulting

1064

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

conceptual modelling of the hydrogeology). To a large extent,

these earlier models have now been combined and extended into
the powerful PHREEQC model (Parkhurst and Appelo, 1999) with
applications in most problem areas of hydrogeochemistry (Appelo and Postma, 2005).

4. Water resources towards problem-orientated geochemistry

2KAlSi3O8 + 2H+ +9H2O Al2Si2O5(OH)4 + 2K+ + 4H4SiO4

mMg/Ca

4.1. More food, more water, less quality

The drive towards self sufciency in food following the Second

World War led to an intensication of agriculture in Europe and
elsewhere with ploughing of grassland and the application of
chemical fertilisers and agrichemicals. Similarly, the green revolution in developing countries led to a dramatic increase in water demand (mainly met by uncontrolled groundwater development)
coupled with new strains of crops that relied on fertiliser application. Combined 3H and solute studies demonstrated that rates of
movement of water and contaminants towards the water table
took place only slowly (Smith et al., 1970; Parker et al., 1991). Geochemical research on redox processes and the N cycle, by analogy
with soils, focused mainly on the role of organic C as the electron
donor for NO3 reduction (Korom, 1992). However, it was also
shown that rates of NO3 removal by organic matter were limited
by its reactivity and concentration much of the organic C present
in aquifers is rather inert and not readily available. Moreover,
microbiological catalysis is of limited extent in most groundwaters
because the conditions for metabolism are not met with at depth.
Nitrate reduction is also thermodynamically favoured by other
electron donors, especially Fe(II) which occurs widely in young
clastic sediments (Postma et al., 1991) and impure limestones (Ottley et al., 1997) and may be the dominant active process in denitrication in timescales of signicance in water management.

mNa/Cl

0
1.0
0.8

mK/Na

At the same time that geochemists were assembling the toolkits

for the study of natural processes of waterrock interaction, water
resource and water quality problems emerged which forced an
integrated and applied focus in hydrogeochemistry, often following sources of funding related to contemporary environmental issues. These problems arose at the same time as groundwater, in
particular, was being used proigately with the introduction of
electric pumps and contamination of supplies without appearance
of the consequences in aquifers. Three main environmental problems led to focused research by geochemists and hydrogeologists
related to diffuse pollution from agriculture, industrial wastes,
and waste disposal activities.

0.6
0.4
0.2
0.0

4.2. From pristine waters to human impacts

10

15
Groundwater Temperature (C)

20

Fig. 3. East Midlands aquifer UK: waterrock interaction. Dissolution of K-feldspar

as a result of groundwater circulation in the recent geological past and accounting
for present day composition of groundwater. New formed illite/kaolinite grows
tangentially on the skeleton of the K-feldspar. Concomitant changes are seen in the
water chemistry moving down-gradient. The changes in Mg/Ca ratio reect the
dissolution of late calcite followed by the reaction of interstitial dolomite (see
Edmunds et al., 1982). Increase in Na/Cl ratio reects initial plagioclase dissolution
with some cation exchange. Then, the sharp K/Na ratio increase is due to the
predominant reaction of K-feldspar.

from hydrogeochemical processes. A new generation of mass

balance models was initiated including BALANCE (Parkhurst
et al., 1982) and NETPATH (Plummer et al., 1994) which were
able to dene the amounts of minerals dissolved along a ow
path (although requiring sound mineralogical knowledge and

The impacts of human activities on water quality were only

recognised in the past half century before which time pristine conditions reecting natural processes controlled the hydrochemistry
(Fig. 4). The rst studies on pollution in the 1960s and 1970s were
focused on dening the scale of problems resulting from the haphazard disposal of wastes. Recognising the scale of groundwater
pollution was assisted by the lower detection limits for many substances and by the ability to analyse for new compounds at the
microgram level, including organic substances. Detectable contamination of groundwaters is now widespread, although this may not
mean that supplies need to be abandoned because concentrations
of most contaminating substances are well below accepted limits
for drinking waters.
Much of the research effort and related policy formulation in
the UK arose from a series of dramatic pollution incidents. The hazardous nature of waste disposal from landll leachates was only

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

1065

Fig. 4. Evolution of groundwater quality and progressive impacts of human inuences.

realised in the UK as a result of accidents such as the explosions

from gas migration and the discovery of drums of cyanide (Department of the Environment, 1978; Williams et al., 1991). In another
landmark example, the public water supply at Sawston, Cambridgeshire, UK was taken out of commission as a result of pollution by trichloroethylene (Misstear et al., 1998). This was the
rst example in which common law principles were applied to
groundwater pollution in the UK. The water company failed in its
case against the polluters, a leather tannery company, on grounds
that the pollution occurred prior to introduction of water quality
legislation in the 1980s. This case helped to dene the nature of
groundwater pollution and had a lasting impact on the disposal
of hazardous chemicals.

disposed of there since the 1960s. The most polluted soils were
mechanically disposed of but a residual contamination still
remains.
The current practice at many such sites is to identify and isolate
the contaminants and to rely on natural (bio)geochemical processes for remediation over long timescales of decades or more.
It is now recognised that breakdown occurs via microbiologically
mediated oxidation with dissolved O2, NO3 and SO24 , with Fe-oxyhydroxides as electron acceptors (Appelo and Postma, 2005;
Chappelle et al., 1996; Cozarelli et al., 2001). Stringent legislation
now prevents the damaging practices of the post-war era.

4.3. Natural remediation

Acid rain has been recognised as a local pollutant since the mid19th century (Smith, 1852) and its industrial inuence recognised
in the 1950s (Gorham, 1955). However, the impacts of transboundary pollution from fossil fuel combustion on lakes and river
quality only became an important issue in the 1970s, leading to a
signicant growth in geochemical studies. Long-term impacts of
rainfall and industrial emissions on ecosystems were monitored
in the classic studies at Hubbard Brook, USA (Likens and Bormann,
1995). The increases in catchment acidication encouraged studies
by soil scientists and geochemists of individual elements mobile
under acidic conditions; this included studies of Al (Paces, 1978;
Nordstrom and Ball, 1986), Be (Edmunds and Trafford, 1992) and
other metals. Focus on acid lithologies, including sandstones and
granitic rocks, demonstrated that not only surface waters but also
shallow groundwaters were at risk; soil and unsaturated zone
studies showed that base cation removal was accelerated with
consequent mobilisation of Al and other metals. Acid rain impacts
also accelerated studies of remediation (Cook et al., 1991) and the
development of predictive models for scenarios of changing emission patterns (Whitehead, 1992). Geochemical modelling also
advanced at this time with the need for prediction and management; the ability to model the chemical weathering induced by
acidication (Sverdrup and Warfvinge, 1993) led to development

The ability of geological materials, and groundwaters in particular, to attenuate a wide range of contaminants to varying extents
was rst thoroughly studied in Germany as a result of careful monitoring during the 1960s (Golwer et al., 1970) and in Canada with
detailed studies on the Borden landll, Ontario (MacKay et al.,
1986). These eld studies demonstrated that the theoretical redox
sequences (Stumm and Morgan, 1996) also operated in contaminated systems, progressing from anaerobic to aerobic conditions.
The ability for hydrocarbons to become degraded by natural biogeochemical processes was also highlighted in the 1990s (Baedecker et al., 1993).
The early incidences of pollution often led to costly interventions with varying degrees of success. Cleaning up of polluted aquifers was seen as a challenge from engineering, hydrogeological,
and chemical viewpoints. The water supply in the authors home
village also became polluted during the 1990s with trihalomethane. The source remained a puzzle until it was traced back to a disused aireld about 6 km away at Harwell where it had been used
for cleaning aircraft parts 50 a earlier during the Second World
War. This site also hosted the rst experimental nuclear reactor
in the UK and chemical wastes including solvents had also been

4.4. Acid rain impacts

1066

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

of the critical loads concept, where the carrying capacity of the

landscape for individual contaminants can be modelled (Langan
et al., 2001; Skefngton, 1999).
5. Water scarcity water quantity vs. water quality
Over the past two centuries, society has moved from its traditional dependence on water availability within the natural
uctuating water cycle to an era of engineering-led development
impounding rivers, altering river courses, and developing wellelds (Fig. 4). This demand-led change has been dramatic only
within the last half century and has had lasting and often irreversible impacts on groundwaters. Many areas, such as the Great Plains
in semi-arid USA, were soon developed beyond their capacity for
renewal. Large artesian basins, generally containing high quality
water, are found in Australia (Radke et al., 2000), North Africa
and the Middle East (Edmunds, 2003; Barber, 1965). Communities
in these basins, often nomadic and reliant for centuries on traditional resources, were now offered a bonanza of low-salinity artesian water and the opportunity for development. Geochemical
studies have proved dramatically that these groundwaters represent exhaustible palaeowater reserves and that the resources are
being mined unsustainably. The prospect looms for a return to an
improved management of traditional rain-fed resources, especially
in areas where alternative sources are impractical, unaffordable, or
where poor management exists.
This pattern is repeated in many areas of the world where
groundwater development has run ahead of proper management
and regulation, leading to the current water crises. Rapid development also brought a synergy of water quality issues. Most well drilling was based on achieving favourable yields by penetrating tens
or hundreds of metres of the saturated aquifer, thereby pumping
mixtures of water of different ages and quality. Unintended salinity
caused by drawdown is evident in arid regions as well as pollution
in shallow aquifers. Geochemistry has played an important role in
identifying many of the key issues.
5.1. Groundwater renewability
The identication of renewability of groundwaters has been
achieved by the combination of isotopic and geochemical techniques, notably 3H proles and Cl mass balances, especially in
areas with low rainfall. Tritium was widely used in the late

1960s and 70s to advance knowledge of recharge processes, especially using unsaturated zone proles in temperate regions (Andersen and Sevel, 1974). This and similar studies in deep sandy
unsaturated zone proles showed that piston displacement of
moisture generally occurred, although in dual-porosity media,
such as chalk, some by-pass ow was observed (Smith et al.,
1970). The position of the 3H peak could be used to measure recharge rates, although using 3H for mass balance studies proved
problematic. Tritium was also tested as a tracer under semi-arid
to arid conditions in Saudi Arabia (Diner et al., 1974), but it was
under much drier climates that isotope methods combined with
other tracers were subsequently proved to be important tools for
investigating recharge processes (Allison and Hughes, 1978; Edmunds and Walton, 1980).
In Senegal, the 3H peak in the early 1990s was still preserved at
a depth of between 1220 m (Aranyossy and Gaye, 1992) with no
by-pass ow. In this region, the combined use of 3H, stable isotopes
and Cl (Fig. 5) provided conrmation of recharge rates over decadal scales in sands with low moisture content (24 wt.%), an
impossible task using physical methods (Gaye and Edmunds,
1996). In some areas dominated by indurated surface layers, deep
vegetation, or very low rates of recharge, the 3H peak is less well
dened (Phillips, 1994), indicating some moisture recycling to
greater depths (up to 10 m), although overall penetration of modern water could still be estimated.
Under arid conditions with low rainfall and high rates of evapotranspiration, classical physical water balance techniques break
down. This problem, at least in the case of permeable terrains,
was overcome using Cl mass balance in conjunction with the 3H
peak method and also with studies of stable isotope movement.
Studies by Eriksson and Khunakasem (1969) pioneered the use of
the Cl mass balance in studies of aquifers at a regional scale, work
that has not been followed since then as actively as it deserves for
the study of the spatial variability of recharge. Chloride, unlike 3H,
is conserved in the soil prole and providing the rainfall Cl inputs
are known then a Cl mass balance may be determined. This approach was developed in the late 1970s in Australia and Cyprus
(Allison and Hughes, 1978; Edmunds and Walton, 1980). These
studies were then extended to many other areas, including North
Africa (Gaye and Edmunds, 1996) and North America (Phillips,1994). They were also widely developed in Botswana (De Vries
et al., 2000) and here the Cl mass balance is used nationally as a
tool for water balance.

Fig. 5. Use of multiple tracers in unsaturated zone moisture in unconsolidated sands from Louga, Senegal, to determine recharge and recharge history. An absolute age
indicator, tritium, indicates the position (in 1991) of the 1963 thermonuclear weapons testing peak and also that piston ow takes place in these sediments. Chloride is used
to determine recharge rate of 34.4 mm a 1 based on the ratio of mean soil moisture (Cp = 23.8) and rainfall Cl (Cs = 2.8 mg L 1) and precipitation P = 290 mm a 1. In this case a
record of recharge history over ca. 80 a is preserved higher Cl showing the period of the 19691980s drought. Periods with higher evaporation are conrmed by more
positive values of stable isotope indicators.

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

5.2. Non-renewable water

The most important contribution by the isotope community to
hydrogeology has been the concerted effort to determine the absolute age of groundwater, most particularly using radiocarbon. The
principles of radiocarbon dating of groundwaters were rst set out
by Vogel and Ehhalt (1963), although one of the rst eld applications was to conrm the Late Pleistocene age of the very fresh
waters beneath the Egyptian Sahara (Degens, 1962). During the
1970s it was realized that a geochemical approach to radiocarbon
interpretation was required (Pearson and Hanshaw, 1970). Thus,
knowledge of the behaviour of total dissolved inorganic C (TDIC)
was needed, assisted by measurement of 13C in soils and host
rocks. A series of groundwater geochemical models was developed
to handle the ranges in input functions as well as the extent of possible waterrock reactions (e.g., Pearson and Hanshaw, 1970; Reardon and Fritz, 1978; Fontes and Garnier, 1979; Wigley et al., 1978;
Kalin, 2000). These models have been used with varying degrees of
success since that time. It has been shown, for example, that reliable model interpretation may be achieved for non-carbonate
aquifers but that the effects of incongruent reactions and other
processes that affect the radiocarbon content of dissolved inorganic C in some carbonate groundwater systems can be difcult
to quantify, leaving relatively large uncertainties in adjusted radiocarbon ages (Darling et al., 1997).
Partly because of the problems inherent in 14C dating, much effort and isotopic ingenuity has been expended in nding other
tools for dating groundwaters. The main contenders for this purpose have been the inert noble gas radioisotopes 37Ar, 39Ar,
81
Kr, (Lehmann et al., 1993; Loosli et al., 2001). These have often
been used in parallel with 14C and, despite the relative effort and
expense of collection for relatively few samples, have provided a
major contribution to understanding groundwater age distributions, insight into the limitations of other tools, as well as a better
understanding of groundwater ow systems. Recently, the use of
81
Kr has enabled groundwaters in the Great Artesian Basin (Australia) and the Western Desert of Egypt to be dated at between 200
400 ka and up to 1 Ma, respectively, the oldest conrmed ages for
groundwater residence to date (Lehmann et al., 2003; Sturchio
et al., 2004). The other major contribution of the noble gas isotope
85
Kr has been in conrming (with other tracers such as CFCs and
3
H) the extent of mixing of old and modern groundwaters and
improving the understanding of age stratication in aquifers
(Ekwurzel et al., 1994). A relatively large number of environmental
isotopes and tracers have been developed over the past 40 a for
groundwater dating on the 060 a timescale, notably 3H/3He dating and CFC measurements (Plummer, 2005; International Atomic
Energy Agency (IAEA), 2006). Some of these examples are considered below in the context of multi-tracer studies of key reference
aquifers. These studies have also allowed reinterpretation of 4He
and 36Cl as dating tools, at least for relative age measurement of
very old waters.
The resolution of radiocarbon dating of groundwaters remains
rather low, perhaps not better than 1 ka, despite the ability to resolve 14C activities well below this. There remains the problem of
determining the initial 14C activity in radiocarbon dating. The
range typically is 50 pMC (closed system evolution) to 100 pMC
(open system evolution) one whole half-life. Dating is also constrained by sampling, because (a) groundwaters are almost inevitably mixtures, and (b) by the errors inherent in modelling
approaches, most notably in carbonate rocks. Multitracer studies
help to conrm age relationship and stable isotopes (d18O, d2H)
in particular can be used to resolve the presence of palaeo- or modern waters.
Geochemical investigations also show the usually high purity of
groundwaters in some large sedimentary basins. Yet, water quality

1067

problems may arise in arid and semi-arid continental regions (and

elsewhere) due to the widespread aerobic conditions (Winograd
and Robertson, 1982). Oxygen persists in many deep groundwaters
with radiocarbon ages in excess of 20 ka (Edmunds, 2003). Nitrate
remains inert under these conditions and commonly reaches concentrations above drinking water limits in studies recorded across
many semi-arid regions (Barnes et al., 1992; Edmunds and Gaye,
1997; Hartsough et al., 2001). The origin of the high NO3 is attributed mainly to N-xation by leguminous plants, although cyanobacteria have also been proposed. A further water quality problem in
the aerobic environment is the build-up of some elements (Cr, U,
and other metals forming oxyanions) as found in the Algerian Continental Intercalaire aquifer for example (Edmunds et al., 2003).
5.3. Salinity issues
Geochemists have always been attracted by questions of salinity, which are most apparent in semi-arid and arid regions where
small increases in salinity have an immediate impact on water
resources. Identication of origins can be determined using multi-tracer techniques (Edmunds and Droubi, 1998). Near-surface
accumulations of salinity in Africa have occurred since the shift
to modern climate regimes approximately 4.5 ka BP, and saline
zones may lie in close proximity to fresh palaeowaters. In Australia, the stability of the past climate over tens of thousands of years
and the efcient water use by vegetation led to highly saline soils
and water in the unsaturated zone. Human intervention over less
than 200 a cleared native vegetation, increased recharge rates,
and allowed percolation of salts to the shallow groundwater, and
ultimately to the increase in river salinity (Allison et al., 1990).
The impacts of the clearance of native vegetation are clearly
demonstrated by unsaturated zone proles of Cl, 36Cl and 3H (Cook
et al., 1994), where fresh water from the increased recharge has
displaced the saline water within decades.
The ratio Br/Cl is one of the most effective indicators of salinity
origin, allowing distinction between marine aerosol, evaporite, and
formation water origins (Herczeg and Edmunds, 1999). The relation between Cl and d18O is also a classical indicator of the degree
of evaporative enrichment in groundwaters and has been a reliable
indicator of salinisation caused by irrigation return waters. The relative concentrations of reactive tracers, notably the major inorganic ions, have also been widely used because they provide
clues to the waterrock interactions that gave rise to the overall
groundwater mineralisation. Isotopic tracers have increasingly
been applied to the investigation of saline water origins, such as
different generations of sea water and formation waters, including
d37Cl (Weaver, 1999), 87Sr/86Sr (Yechieli et al., 1992) and d11B
(Vengosh and Spivack, 1999).

6. Water policy and regulation

The worlds water resources have been dened and roughly
quantied, although large uncertainties still remain for groundwater (Shiklomanov and Rodda, 2003), and the extent of pollution is
also now well recognised. Geochemistry has been important in
understanding the substrate within which waters move, in dening timescales of water movement through the hydrological cycle,
and in quantifying the capacity of the natural system for handling
the random abuses made on it by mankind. In order to convey the
message of geochemistry, it now also becomes important to work
with other disciplines ecologists, economists, social scientists,
politicians and others, and to respond to questions concerning
water from society.
The looming water crisis and a framework for 21st century
water management have been debated and recommendations

1068

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

made at numerous conferences under UN auspices since the mid1970s, but especially since the early 1990s (Rodda, 1995). In
1992, the Dublin principles (subsequently incorporated in UN
Agenda 21) were enunciated as a basis for action (1) to reverse
the trends toward water shortages and rising levels of pollution,
(2) to enhance the role of women, (3) to increase public participation, and (4) to encourage the recognition of water as an economic
good. The synergy between water quality and quantity in diminishing the worlds potable resources (Fig. 6) is widely recognised
in various conference reports. One of the major problems is how
to achieve the balance between water security and food security,
because agricultural water demand typically uses 8090% of the
fresh water resource in many countries. The Millennium Development Goals (MDGs) now form the policy basis for improving water
and sanitation globally, very optimistically by 2015, and water
quality challenges are implicit in these goals. The most comprehensive summary of the state of the worlds water is given in the
excellent nal report of the UN World Water Assessment Programme published at the 2006 Mexico 4th World Water Forum
(UNESCO, 2006).
6.1. The European Water Framework Directive
In Europe, the Water Framework Directive (WFD) 2000/60/EC
(EC, 2000), sets out criteria for the assessment of groundwater
chemical status on the basis of existing Community quality standards (for NO3, pesticides and biocides) and on the requirement
for Member States to identify pollutants (dened as substances that
may occur from both natural and anthropogenic sources, and synthetic pollutants) and related threshold values that are representative of all groundwater bodies found as being at risk. The WFD seeks
common denitions of the status of groundwater (and surface
water) quality. Environmental objectives are sought to ensure that
good water status is achieved throughout the Community. Where
good water status already exists, it should be maintained and any
signicant and sustained upward trend in the concentration of
any pollutant should be identied and reversed.
A separate directive, the Groundwater Directive (GD) was formulated (EC, 2006) to address the special problems of groundwater, which is recognised as the most sensitive and the largest
body of freshwater in the European Union. The GD lays emphasis
on the needs to protect the environment as a whole and human
health in particular, avoiding detrimental concentrations of harmful pollutants and providing adequate measures towards protection of groundwater and, where pollution is recognised, to
develop criteria for trend reversals.

The corresponding practice in the USA is for the EPA to regulate

pollution-generating activities and also to set drinking water standards that water utilities must meet. At the same time, the USGS
assesses regional aquifers and water quality though the National
Water Quality Assessment (NAWQA) programme.
The implementation of the European WFD requires scientically defendable and achievable objectives in order to recognise,
stabilise and reverse upward trends and to evaluate the efciency
of remediation measures. Lack of recognition of causes of water
quality problems and well intentioned but ill thought-out restoration efforts result in expensive failures that may even cause harm.
As part of the implementation process all Member States are required to carry out an initial characterisation of all groundwater
bodies to assess their uses and the degree to which they are at risk
of failing to meet the objectives for each groundwater body. There
is plenty of work here for geochemists!
6.2. Natural baseline water quality
One of the main targets for geochemists in the foundation for
new water policy is to determine natural baseline quality of
groundwaters, because without this it is impossible to recognise
whether elevated concentrations of various substances are geological in origin or anthropogenic (Shand et al., 2007). The importance
of dening natural background quality was emphasised by Langmuir (1997) and has been highlighted in several individual aquifer
studies (Edmunds et al., 1987; Banks et al., 1995; Lee and Helsel,
2005). In many ways this is the culmination of much of the detailed hydrogeochemical work over the past 40 a. It is now recognised that groundwaters are heterogeneous bodies of water in
which gradients are developed by time-dependent geochemical
reactions and in which lateral changes take place due to changes
in lithology. The natural baseline is therefore a range of values
and cannot be dened using a purely statistical approach a geochemical conceptual model based on the hydrogeology is required
and the processes controlling the water quality must be understood (Fig. 7).
Geochemical investigations at a global scale have now largely
identied the extent of excess and deciency of those elements
that are harmful for health in drinking water. This has often involved working closely with the medical community and the state
of the art has recently been summarised by Selinus et al. (2005).
Deciencies in I (causing problems of thyroid function, particularly
in continental regions), in F (causing dental caries in non-carbonate
(soft-water) terrains) and Se in many regions are now recognised.
99.99
99.9

60000

Ba (g l-1)

99

Range of estimates of total world water

90

40000

30000

Probability

Cubic kilometers/annum

50000

Range of estimates of available world water

50
30
10

Losses due to pollution

20000

70

1
10000

0.1

Global demand for water

0
1880

0.01
1900

1920

1940

1960

1980

2000

2020

2040

2060

Year
Fig. 6. Scenarios for world water resources and demands. After Rodda (1995).

10

100

1000

10000

Fig. 7. Baseline composition of Ba in groundwaters from 25 reference aquifers in 12

European countries demonstrating the fact that natural groundwater quality is a
range of values related to geochemical evolution.

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

Remediation is possible using dietary supplements, and the origins

of I and F deciencies are well understood. For Se, however, little is
still known globally in part due to the difculties of analysis and
also because bioavailability is an important consideration.
Much more is now known on the health problems caused by
high natural backgrounds of F of geological origin (Edmunds and
Smedley, 2005) and especially As which has proved to be one of
the largest global health problems related to natural groundwaters.
The extent of the natural abundance of As in Recent alluvial and
deltaic sediments and in other specic geochemical environments
has been well established (Smedley and Kinniburgh, 2002; Welch
and Stollenwerk, 2003). There is now a wealth of geochemical literature relating to the issue of As occurrence and the mechanisms
involved in uptake and deposition. Continuing interest in this topic
relates to the complexity of the geochemical processes involved
and the intimate nature of the interactions as well as the search
for other endemic areas.
6.3. Reversing pollution trends
Evidence of pollution is well seen in many shallow groundwaters. Current policy requires the reversal of increasing pollution
trends once the natural quality is known. Controversy still surrounds the levels to which quality should be restored because
attaining the natural baseline is commonly unrealistic and compromise targets are being sought by most countries. This is explored in relation to the EU Groundwater Directive by
Quevauvallier (2008).
Diffuse pollution by NO3 and agrichemicals, a legacy of several
decades of EU policy favouring intensive agriculture, now presents
the water industry and its customers with expensive clean up procedures, including installation of NO3-removal plants at pumping
stations. In addition to design of effective source protection, it is
important that geochemists are involved in exploring alternative
options for lowering NO3 based on natural attenuation. One
scheme (Fig. 6) adopted for the Lincolnshire Limestone (UK) uses
the natural redox boundary as a basis for re-siting supply wells
down-gradient where natural attenuation reduces the concentrations of incoming rising NO3 (Parker et al., 1991).
In most temperate regions covered by forest or grassland the
natural baseline for NO3 is less than 2 mg L 1 NO3N (Shand and
Edmunds, 2008). In many semi-arid regions, as discussed earlier,
the natural baseline may be in excess of 10 mg L 1 NO3N. Drinking water with this quality has formed the basis for many societies
in the semi-arid tropics for thousands of years. It raises the intriguing question of the present water quality standards for NO3 and the
basis on which these are set, when there is little or no evidence
(apart from impact on infants) of harmful effects of higher NO3 levels. Humans have probably adapted slowly to certain levels of mineral constituents in surface and groundwater over long periods
(Garrels et al., 1975).
The policy of dilute and disperse when handling pollution in
surface and groundwaters has now been discredited partly because high-value treated water has often been used for this purpose. In addition, in most countries sinks for disposal of wastes
through landlls are being exhausted and containment at source
is now being required. A geochemical approach is needed to develop improved understanding of environmental vulnerabilities, as
well as engaging in innovative solutions to prevent pollution and
decrease demand for high quality treated water.
6.4. Groundwatersurface water interactions
In many parts of the world, rivers have been seriously degraded,
often acting as open sewers and with severe loss of ows due to
unregulated groundwater abstraction. Apart from initial storm

1069

peaks, surface water can usually be regarded as an outcrop of

groundwater, as evident from the stream hydrograph. The importance of groundwater in maintaining the good status of surface
waters has often been taken for granted and requires more probing
studies. Groundwater residence times in shallow alluvium, for
example, may be considerable and, using isotopic signatures, it
has been shown that the water entering streams during storms
may be displaced from earlier rainfall events (Sklash et al., 1976).
The widespread practice of siting water supply boreholes in ood
plains to induce recharge from surface waters has often been at
the expense of sustaining river ows sufcient to maintain the ecological status and of impacts on wetlands. This is an important consideration in the WFD (EC, 2000). Similarly, upward trends in
harmful nutrients (P, NO3 and organic chemicals) in streams and
rivers causing eutrophication may sometimes be related to baseow contamination from groundwaters that once maintained high
quality of surface waters. The hyporheic zone, where groundwater
and surface water interact, is a zone of high geochemical and biological reactivity, the understanding and management of which
needs further work by geochemists.

7. Future challenges
Forty years and more of geochemical endeavour have now provided the toolkit to address and solve the current range of water
and other environmental problems. But, how successful have we
been in using the vast array of knowledge to alleviate some of
the urgent water quality problems and how successful have we
been in inltrating this knowledge into water policy? The problems of water scarcity and degradation are urgent and the main
challenge for today and the future is to apply the knowledge already available. Scientic research often has an applied value
which is not fully exploited once it has been published. Challenges
in water resources related to water quality, where geochemical
application is needed, include: improved groundwater protection,
stabilising and reversing pollution trends, improved estimates of
residence times, predicting climate change impacts relating to
quality, restoration of clean rivers and wetlands, management of
salinity, better water storage strategies, treating surface waters
and groundwaters holistically as one connected asset, and linking
land management with water quality at a landscape scale.
It is also evident from many studies where water table decline
is continuous that we do not well-understand the groundwater
balance and further application of geochemistry to look at components of the water cycle is still needed. The concept of landscape
geochemistry, developed and used widely in Russia, should be
reintroduced as a means of integrating some of the themes that
have become disconnected over recent decades.
As hinted above, the array of analytical tools now provide
unlimited scope for understanding geochemical and biogeochemical processes at the molecular scale reductionist geochemistry
will have a role, especially in observing mineralogical changes effected as part of waterrock interaction. Among these is the use
of more powerful energy sources, such as the synchrotron, to analyse smaller amounts of more elements on mineral surfaces, for
example. Advances in geomicrobiology are also of growing importance, for example, the use of DNA testing to determine microbial
activity.
However, it is also important to consider that huge challenges
exist in water quality improvements in developing countries. The
primary target is likely to meet the challenge of providing pathogen-free water as part of the MDG targets. In parallel, it is important
to consider other water quality issues such as salinity management
in semi-arid areas and the screening for harmful elements not
only F and As, but possibly other as yet unknown hazards.

1070

W.M. Edmunds / Applied Geochemistry 24 (2009) 10581073

The stress on water resources is particularly problematic in

areas of high population density such as coastal regions. Apart
from avoiding migration of saline water, the use of aquifer storage
and recovery offers an interesting alternative to surface water storage, where seasonal excess water can be injected underground for
later use during times of peak demand (Pyne, 1995). This technology offers some added benets, such as in situ denitrication of
high-N water by injection in anaerobic zones, as well as other
interesting challenges for geochemists.
Increasingly, it becomes necessary to work across scientic disciplines and many of the challenges for water resources lie at the
interfaces between them. One example of this comes from the
study of palaeowaters. Geochemical studies are able to provide recharge sequences and timescales for groundwater emplacement
but results need to be coupled with palaeoclimatic studies to fully
understand the nature of the long- and short-term sustainability of
the most precious natural resource. Modelling of the water resource has to consider the climate changes over thousands of years
because current hydraulic head distributions will not reect initial
recharge conditions. In a complimentary way, groundwater geochemical studies can also be used as an archive of past climatic
events and contribute to understanding of past global changes
(Edmunds, 2005).
Despite decades of technology devoted to water treatment, the
purity of municipal and piped drinking waters is under some
scrutiny by the public at the present time, not least in advanced
societies. These concerns are mainly unjustied, yet this has driven
an unprecedented market growth in bottled mineral waters. The
properties of pure natural waters (spring and well waters) command a disproportionate market value and the bottled water
image-makers seek evidence of the purity, longevity, and healthgiving properties of their water with a zeal reminiscent of the early
philosophers. It is rather anomalous that so much marketing effort
is devoted to describe the mineral properties and geological origins
of these products, yet their regulation is often less stringent than
for water supplied to the taps. Geochemists have more work to
do in this direction, to work with the water industry to explain
the high quality, properties and geological characteristics of natural waters and of the minerals and rocks through which they have
passed.
Acknowledgments
The paper draws on work carried out in collaboration with
many colleagues in the British Geological Survey over the past
two decades whose help and advice is gratefully acknowledged.
Tony Milodowski is thanked for help with SEM studies. Lisa Geijtenbeek-Colledge of Elsevier is thanked for her biblometric work
which led to the production of Fig. 1. The author would like to apologise to friends and colleagues for any omissions to important papers in such a wide ranging review. Paul Shand and Brian Hitchon
provided early reviews of the manuscript and their comments are
gratefully acknowledged. Finally the author wishes to pay special
thanks to Neil Plummer who provided a review of the paper and
has helped to place the important contribution of the USGS in its
proper context.
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