The Science of the Total Environment 310 (2003) 25–35

The natural (baseline) quality of groundwater: a UK pilot study

W.M. Edmundsa,*, P. Shanda, P. Hartb, R.S. Wardc
a
British Geological Survey, Crowmarsh Gifford, Wallingford, Oxon, OX10 8BB, UK
b
Environment Agency, Kingfisher House, Goldhay Way, Orton Goldhay, Peterborough, PE2 5ZR, UK
c
National Groundwater and Contaminated Land Centre, Olton Court, Solihull, B92 7HX, UK

Received 28 January 2002; accepted 1 November 2002

Abstract

Knowledge of the natural baseline quality of groundwaters is an essential prerequisite for understanding pollution
and for imposing regulatory limits. The natural baseline of groundwaters may show a range of concentrations
depending on aquifer mineralogy, facies changes, flow paths and residence time. The geochemical controls on natural
concentrations are discussed and an approach to defining baseline concentrations using geochemical and statistical
tools is proposed. The approach is illustrated using a flowline from the Chalk aquifer in Berkshire, UK where aerobic
and anaerobic sections of the aquifer are separately considered. The baseline concentrations for some elements are
close to atmospheric values whereas others evolve through time-dependent water–rock interaction. Certain solutes
(K, NHq 4 ), often considered contaminants, reach naturally high concentrations due to geochemical controls; transition
metal concentrations are generally low, although their concentrations may be modified by redox controls. It is
recommended that the baseline approach be incorporated into future management strategies, notably monitoring.
䊚 2003 Elsevier Science B.V. All rights reserved.

Keywords: Groundwater; Baseline quality; Hydrogeochemistry; Monitoring; Water Policy

1. Introduction ment. This may be reflected in the increasing

Natural reactions between water and rock give
rise to a wide diversity in the mineral character of
groundwater, imparting intrinsic properties such as
hardness and softness, salinity and even bitterness
and sweetness, recognisable by humans since the
earliest times. There is growing public awareness
of the natural properties of groundwater, as well
as the perception that changing water taste and
properties are linked to pollution and water treat-
*Corresponding author.
E-mail address: wme@bgs.ac.uk (W.M. Edmunds).
demand for bottled mineral waters.
There is, therefore, a need for better understand-
ing of the intrinsic quality of natural waters,
especially groundwaters, and how their character-
istics are acquired. For the purposes of ground-
water management, there is a requirement for
improved understanding of the controlling pro-
cesses and, where possible, the natural, geologi-
cally controlled baseline chemistry. This is
especially important if the impacts of contaminants
on groundwaters are to be assessed. In order to
understand the pollution trends and impacts on an
aquifer, it is essential to have knowledge of the

0048-9697/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 8 - 9 6 9 7 Ž 0 2 . 0 0 6 2 0 - 4
26 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
natural baseline quality so that imposed environ-
mental change can be measured with an acceptable
degree of confidence. EU standards for drinking
water quality impose rigorous controls on water
quality management issues but the limits may be
breached due to entirely natural processes
(Edmunds et al., 1987; Banks et al., 1995; Frengs-
tad et al., 2000). Under certain geochemical con-
ditions several potentially harmful elements or
their complexes (e.g. Al, As, Be, Cr, F, Ni, Rn,
Se, Tl) in addition to common species such as
NOy 3 may be mobile (Edmunds and Trafford,
1992; Shand et al., 1998) and understanding how
and where these occur is necessary for effective
aquifer management.
Although drinking water quality standards exist,
no guidelines are currently published or widely
available for use by regulators or developers of
groundwater, or indeed the general public, for
defining the baseline quality of groundwater in
England and Wales, nor indeed in other countries.
Such guidelines are needed in particular to be able
to assess the extent to which present UK Drinking
Water Standards may be breached, and how policy
and legislation with respect to the European Direc-
tives on water quality may be formulated. Deteri-
orating groundwater quality due to pollution may
lead to an overall depletion in the available
resource base. The use of simple indicators to
characterise the pristine or polluted status of
groundwaters has been proposed (Edmunds,
1994), but detailed information on specific ele-
ments and species is also required for detailed
legislation. Groundwater is seen as a high purity
commodity, which helps to maintain the quality of
rivers through the sustaining contribution that
groundwater makes to baseflow and any deterio-
ration in these inputs must be carefully monitored.
Other pressures such as climate change and the
consideration of waste water re-use also require
that we know the initial water quality conditions.
The objective of this paper is to provide a
working definition of the baseline concept and
how in practice it may be determined. The con-
cepts are illustrated using results from part of the
Chalk aquifer of the UK. Finally, the implications
for groundwater management and UK policy areas
are considered.
2. Controls on the natural quality of
groundwater
Groundwater quality evolves rapidly as it passes
through the subsurface pathways within the soil
and the unsaturated zone and thence to the satu-
rated zone of the aquifer. Atmospheric inputs have
an important influence and in many shallow
groundwaters may represent a major proportion of
the solutes, these also acting as tracers of origin.
Thus, chloride, which may be regarded as effec-
tively inert, with the other halogen elements, can
be used to follow the input composition; in coastal
regions the maritime influence of Na and Mg as
well as Cl, may be easily recognised. At the
present day, atmospheric pollution may also con-
tribute to groundwater loading for species such as
2y
NOy 3 , SO4 and NHq 4 (as well as some Cl)
compared with the pre-industrial era.
Two factors, the PCO produced in the soil and
the aquifer mineralogy are predominant in deter-
mining the mineralisation of the groundwater.
Acid–base reactions, nitrogen transformations and
microbiological activity lead to production of
CO2, and are of over-riding importance in deter-
mining the reactivity of waters during infiltration.
Thick organic soils produce high PCO , whereas in
areas with thin soils, low PCO may result in little
water–rock reaction. However, it is the geological
diversity that provides the main influence on water
quality. The mineral assemblage of the host rock,
the relative abundance of individual minerals, sol-
ubility, crystallinity and purity are primary con-
trols. The geological map provides a starting point
for indicating areas of hard and soft water, corre-
sponding to areas underlain by carbonate and non-
carbonate rocks. However, minor amounts of
minerals which dissolve rapidly, such as calcite
(in veins or as a cement), may dominate the water
quality even in some silicate-dominated lithologies
such as granites (Cook et al., 1991).
Compared with the near surface, the water
chemistry at depth evolves more slowly by a series
of geochemical reactions including mineral disso-
lution and precipitation, redox reactions, cation
exchange, sorption and mixing. A distinct
sequence of compositions caused by geochemical
changes with time as water moves downgradient
 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
is commonly observed, as in the UK Chalk or
Triassic sandstones (Edmunds et al., 1987; Smed-
ley and Edmunds, 2002). Spatial variability in
groundwater baseline values is expected to be the
norm since aquifers are rarely homogeneous in
physical, lithological or geochemical properties.
3. Definition of baseline groundwater quality
The baseline concentration of a substance in
groundwater is defined here as ‘the concentration
of a given element, species or chemical substance
present in solution, which is derived from natural
geological, biological, or atmospheric sources’.
Additional definitions may be required for regula-
tion purposes, for example, when the present day
status of groundwater may represent the starting
point of monitoring. This may be defined as
background and such an initial condition may
include some anthropogenic component in the
water quality.
In order to interpret the water quality variations
in terms of the baseline, some knowledge of
residence times of groundwater is required. Meas-
urement of the absolute age of groundwater pres-
ents many difficulties and carbon-14 is the most
widely used technique (Clark and Fritz, 1997).
The interpretation of radiocarbon, however, pres-
ents various problems, including the fact that it is
a reactive tracer, intimately involved with reactions
with minerals, especially carbonates. By investi-
gating the evolution of water quality along flow
lines it may be possible to establish relative times-
cales using a combination of geochemical and
isotopic methods (Edmunds and Smedley, 2000).
The identification (or absence) of marker species
related to activities of the industrial era, tritium
w3Hx, ozone-depleting gases—chlorofluorocarbons
(CFCs)—and certain other micro-organic pollut-
ants may provide evidence of a recent component
in the groundwater. Enhanced total organic carbon
(TOC) concentrations in most aquifers also acts
as a good indicator of pollution (Edmunds, 1994).
It is therefore convenient using various tracers to
be able to distinguish categories of water of dif-
ferent ‘age’:
i. Palaeowater—recharge originating during or
before the last glacial era, clearly recognisable
27
from isotopic indicators and demonstrably free
of any contaminants.
ii. Pre-Industrial Era Water; water of Holocene
age, also with no traces of human impact.
iii. Pre-1960s recharge; free of radioactive sub-
stances but some traces (e.g. NOy 3 ) of human
impact.
iv. Water from the Modern era (post-1960) con-
taining tritium and organic micro-pollutants.
Thus, an ideal starting point is to locate waters
where there are no traces of human impact, essen-
tially those from the pre-industrial era, although
this is not so easy for several reasons. Boreholes
penetrate water of different ages or qualities with
increasing depth, since stratification invariably
develops under undisturbed natural conditions.
This is the result of different flow rates in turn
being due to hydraulic gradients, the natural vari-
ation in aquifer physical properties, and natural
variations in the geochemical and geological prop-
erties of aquifers. In aquifers showing strong dual
porosity, such as the Chalk, the water contained in
fractures may be considerably different chemically
from the older water contained in the matrix.
4. Determination of baseline quality
Baseline studies must take account of geological
complexity and trends in chemistry taking place
over recent geological timescales as well as the
much shorter duration of human impacts. A deduc-
tive (geochemically-based) approach aided by sim-
ple statistical tools is recommended. Thus, it is
necessary to understand the chemical evolution of
groundwaters along flow lines in aquifers enabling
facies changes to be identified. Statistical tools
may help indicate the degree of complexity within
the system but will never substitute for a concep-
tual approach based on a sound understanding of
the geochemistry of the water–rock interactions
taking place within the hydrogeological
framework.
For practical purposes it may be necessary to
provide ranges in baseline values and not simply
a single average concentration, although some
normative value may be helpful as a guideline.
This range can be described in many ways, e.g.
28 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
Fig. 1. Use of cumulative probability diagrams to indicate baseline characteristics in groundwaters.
by giving a mean and standard deviation, the total
range in values, or by describing minimum and
maximum baseline concentrations after removing
outliers. The value of commonly used statistical
parameters, such as median or mode, are of use
when comparing the baseline chemistry of aquifers
from different areas or within the same aquifer
from different regions. Use of the median value
instead of the mean is preferred for comparing
different datasets because it is more robust and
much less affected by outlying values. It is also
useful to define an upper baseline, for example the
95th percentile (Edmunds et al., 1987), or 97.7%
(meanq2-sigma) (Langmuir, 1997).
Traditionally, the use of statistical techniques
has assumed that geochemical distributions are
either normal, or more generally, lognormal
(Ahrens, 1954). In most natural systems, including
groundwater, geochemical distributions may be
polymodal and are usually heavily skewed. (Shand
and Frengstad, 2001). Non-parametric statistical
methods are also advocated for geochemical dis-
tributions, which may be non-standard (Reimann
and Filimoser, 2000). The approach adopted in
this paper is to consider groundwater data sets for
single aquifers (or sections of aquifers). Internal
variations then need to be interpreted in terms of
the hydrogeology andyor hydrogeochemical
processes.
Probability plots have been extensively used in
the mining industry and are particularly useful in
highlighting different populations of data. Runnells
et al. (1998) used such diagrams to identify
background and anthropogenic populations of ele-
ments in surface and groundwater samples adjacent
to a mining and smelting area in Utah, USA. They
are favoured in baseline studies as a means to
discriminate natural baseline chemistry from that
due to pollution, (although outliers due to natural
phenomena may also occur). However, there are
several types of geochemical reaction which will
alter distributions by removing or limiting concen-
trations in solution including redox processes,
adsorption onto solid mineral phases and saturation
with respect to minerals which will limit the
solubility of one or more elements. This is illus-
trated in Fig. 1 for the main situations encountered
in groundwater environments where the inferences
that may be drawn from probability plots are also
given.
 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
Fig. 2. Location of samples used in the Chalk baseline study in the London Basin. The line of section across the west of the basin
is indicated.
Other techniques which have been used to illus-
trate hydrogeochemical datasets include box plots
which display the median, mean, specified percen-
tiles and outliers. Histograms may also be used,
but these can show different distributions depend-
ing on the ranges in concentration used in plots.
Piper (tri-linear) diagrams, X–Y plots and maps of
data showing the areal variation in concentration
may also be effectively used. Box plots and prob-
ability plots are the preferred method of represen-
tation since these show unbiased statistical data,
although analytical and sampling errors may still
exist.
5. The Chalk of Berkshire as a case study
5.1. Background and baseline controls
The Chalk of Berkshire has been extensively
developed for public supply for over a century and
has been well studied from a resources viewpoint
29
in connection with river augmentation schemes
(Owen and Robinson, 1978). Detailed investiga-
tion of the hydrogeochemical processes in this
aquifer have also been carried out (Edmunds et
al., 1987). The area considered here covers the
unconfined Chalk outcrop of the Chilterns and
Berkshire Downs as well as the confined Chalk
aquifer lying in the Berkshire syncline, the western
extension of the London Basin; locations of the
sites are shown in Fig. 2 and for further details of
the western section the reader is referred to
Edmunds et al. (1987).
The Chalk is a dual porosity aquifer and whilst
fracture flow predominates, the intergranular
(matrix) porosity contains older water which may
have a strong effect on the chemistry. The matrix
of the chalk, having a permeability several orders
of magnitude lower than the fractures, acts as a
potential reservoir for older water which has
evolved on a geological timescale and which may
affect the groundwater quality by slow exchange
30 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
with water in the fractures and fissures. The Chalk
is a marine limestone and continues to undergo
diagenetic changes as freshwater moves through.
This will influence the natural chemistry both in
terms of salinity and through water–rock interac-
tions which adjust the hydrochemistry with time.
Despite the purity of the chalk, the small amount
of other elements substituting in the calcite may
also have a disproportionate effect on determining
the natural water chemistry.
The chemistry of rainfall has a major impact on
the initial groundwater composition for several
elements, of which Cl can be regarded as a
conservative reference element (Edmunds et al.,
1987). The present-day Cl concentration in the
rainfall is approximately 5 mg ly1 and following
evapotranspiration under grassland, the lowest bas-
eline concentrations of approximately 10 mg ly1
might be expected, with higher concentrations
under woodland or forest.
5.2. Groundwater residence time
The waters are predominantly of Holocene age,
less than 10 000 years old. Their residence time
has been determined using 14C, 3H and 4He
(Edmunds et al., 1987). In the unconfined zone,
moderately high tritium values indicate that most
groundwaters are recent, but some low tritium
waters may also be found at outcrop, where the
bulk of the water must be at least 30 years old;
this demonstrates that considerable heterogeneity
of age and therefore chemistry must exist in the
Chalk, reflecting physical characteristics of the
aquifer. Oxygen, on the basis of tritium content in
the groundwaters, is consumed within a few dec-
ades of residence in the aquifer.
5.3. Sources and handling of data
Chemical data from 65 boreholes in Berkshire
and the Chilterns area were sampled at different
times over the past decade from studies carried
out by the British Geological Survey and the
Environment Agency; all samples were filtered
(0.45 mm) and acidified with 1% nitric acid. The
minima, maxima and median values for the select-
ed parameters have been calculated (Table 1) and
the data subdivided into two sets, those represent-
ing the confined and the unconfined aquifer. This
has been done since there are a priori reasons
based on geochemistry (reducing vs. oxidising
conditions) why the two populations should be
different. Where median values are below a given
detection limit, the ‘less than’ values are substitut-
ed. Cumulative–frequency diagrams (Fig. 3a–d)
provide information on the relative abundance of
the major and minorytrace elements in the ground-
water and are used to provide the basis for consid-
ering both the natural processes as well as human
influences. The 95th percentile for each determi-
nand has been taken as an estimate of the upper
limit of the baseline concentration range (Table
1).
5.4. The influence of pollution
The impact of pollution is restricted to the
unconfined groundwaters. Median concentrations,
given in Table 1 for most elements, may be
regarded as representative of the average unpollut-
ed groundwater composition for the region; any
non-natural effects are likely to be found in the
upper 50%. An exception is nitrate and it is
estimated that some 80% of the groundwaters in
the unconfined aquifer have significant contribu-
tions (above 5 mg l y1 NO3 –N) from agricultural
sources. The impacts from agriculture (in the
unconfined Chalk) may also be seen in some other
elements such as Cl (above say, 20 mg ly1, being
double the rainfall inputs) and SO2y4 , also above
20 mg ly1. A few samples having Cl above 100
mg ly1, in the confined Chalk contain a ‘natural’
contribution from residual formation water.
5.5. Natural baseline chemistry
2y
Selected data (Cl, Na, Mg, Ca, K, NOy 3 , SO4 ,
q
NH4 , F,) illustrate the geochemical evolution of
groundwaters as they move along the flow lines
(Fig. 4) and across the redox boundary; Table 1
provides summaries for other elements. The dom-
inant baseline chemical characteristics are rapidly
determined during percolation particularly at the
soil–chalk interface. Congruent dissolution of the
chalk occurs and saturation with calcite is typically
 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35 31

Table 1

Determinand Units Unconfined aquifer Confined aquifer

Min Max Median Upper baseline n Min Max Median Upper baseline n
T Temperature 8C 10.0 13.0 10.9 11.6 20 10.9 18.0 12.6 15.1 32
pH (Field measured) 6.80 8.43 7.16 7.36 20 7.00 8.24 7.40 7.79 33
Eh Redox potential mV 130 417 371 416 16 -50 445 80 381 30
DO Dissolved oxygen mg ly1 0.1 10.5 9 10.5 17 -0.1 10 0.2 9.18 32
SEC Conductivity mS cmy1 555 1100 683 887 12 636 1500 785 1410 21
Ca Calcium mg ly1 86 169 110 150 21 36 118 57 114 33
Mg Magnesium mg ly1 0.9 8.9 2.07 8.2 21 1.5 30 19 29.2 33
Na Sodium mg ly1 5.6 24 8.9 21.9 21 8.1 219 36 122 33
K Potassium mg ly1 0.6 5.3 1.5 4.3 21 1.1 10.2 6.8 9.88 33
Cl Chloride mg ly1 9 41 17 41 21 14.5 204 30 151 33
HCO3 Bicarbonate mg ly1 221 341 289 330 18 267 349 303 324 24
SO4 Sulfate mg ly1 2.5 197 13 125 21 13.5 68 33 55.8 33
NO3yN Nitrate (N) mg ly1 0.09 11.1 5.2 7.5 21 -0.02 7 -0.02 6.7 33
NH4yN Ammonium (N) mg ly1 -8 70 -8 69 13 -8 893 198 750 32
Al Aluminium mg ly1 -7 18 -7 2.8 20 -7 -7 -7 -7 33
As Arsenic mg ly1 -1 4 2 3.5 12 -1 5 3 4 22
B Boron mg ly1 -2 120 18 86.9 23 -2 1430 185 1180 36
Ba Barium mg ly1 1.5 100 60 100 21 18 146 90 124 33
C Cobalt mg ly1 -1.33 3.6 -1.33 1.87 8 -1.33 -1.33 -1.33 -1.33 11
Cd Cadmium mg ly1 -2 -2 -2 -2 8 -2 2.4 -2 -0.02 12
Cr Chromium mg ly1 -1 -1 -1 -1 2 -1 -2 -1 -1 4
Cu Copper mg ly1 -1.33 23 2.45 5.98 22 -1.33 29 1 13.1 35
F Fluoride mg ly1 60 350 150 326 17 -100 4800 1300 2360 33
Fe Total iron mg ly1 -1 4380 7 834 28 -1 2560 217 719 47
Fe(II) Ferrous iron mg ly1 -10 1900 -10 849 12 -10 1380 130 635 22
I Iodine mg ly1 3 10 5 9.5 11 4 54 18.5 49.3 26
Li Lithium mg ly1 -0.5 9 5 9 19 1.4 220 13.5 25 32
Mn Manganese mg ly1 -0.2 282 -10 81.6 28 -0.2 60 8 34.7 48
Mo Molybdenum mg ly1 -7 -7 -7 -7 4 -7 -7 -7 -7 2
Ni Nickel mg ly1 -2 11 -3 7.5 22 -3 7 -3 -3 37
P Orthophosphorus mg ly1 -3 6.5 -3 6.5 11 -3 278 3.2 12.7 22
Pb Lead mg ly1 -10 2 -10 -2.8 9 -2 -10 -10 -6.4 12
Rb Rubidium mg ly1 -50 -50 -50 -50 3 -50 -50 -50 -50 9
Si Silicon mg ly1 4100 10800 6500 10700 21 4700 10700 8200 10500 33
Sr Strontium mg ly1 40 1500 250 1400 21 180 6300 3600 6190 33
U Uranium mg ly1 0.24 1.7 0.28 1.37 6 0.01 0.6 0.03 0.23 19
Y Yttrium mg ly1 -0.2 -0.2 -0.2 -0.2 7 -0.2 -0.2 -0.2 -0.2 11
Zn Zinc mg ly1 -1.3 34 9.9 30 10 -1.3 414 21.3 207 15
Atrazine mg ly1 1 1 1 1
TCE Trichloroethene mg ly1 4 4 4 1
d18O Oxygeny18 ‰ y6.2 y7.9 y7.3 y6.7 14 y6.6 y7.9 y7.2 y6.7 29
d2H Deuterium ‰ y44 y49 y46 y45 14 y41 y47 y42 30
Unfiltered
Fe Total iron mgyl -0.01 0.53 -0.01 0.12 100 -0.01 2.41 0.11 1.74 50
Mn Manganese mgyl -0.01 0.04 -0.01 0.02 101 -0.01 0.21 0.01 0.08 49

attained within a few metres of the surface. Below
this depth the rate of chalk dissolution is greatly
reduced and very little further increase in total
mineralisation takes place. Initially the groundwa-
ter acquires a Ca-rich composition with MgyCa
ratio close to that of the rock. However, as ground-
water moves down-gradient, its composition is
modified by several processes, especially the
incongruent reaction of the chalk calcite which
releases Mg2q (as well as Sr2q, Fe2q and other
trace elements characteristic of the marine environ-
ment in which it was formed) to the groundwater
giving rise to an increase in the MgyCa ratio.
Dissolved-oxygen concentrations remain rela-
tively high (median 9 mg ly1) throughout the
unconfined aquifer indicating the virtual absence
32 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35

Fig. 3. Cumulative frequency diagrams for major, minor and trace element distributions in the confined and unconfined Chalk of
Berkshire. (a) major and minor elements in the unconfined section and (b) major and trace elements in the unconfined section.

of pyrite or other minerals, maintaining the aerobic
environment at least to the confinedyunconfined
boundary. Total Fe2q occurs in solution at or below
10 mg ly1 in the aerobic groundwaters. At the
redox boundary, major geochemical changes occur
which influence baseline concentrations. Reducing
conditions allow Fe2q concentrations to increase
by up to three orders of magnitude and NO3 –N is
rapidly reduced to N2 gas; however, NHq 4 is found
as a stable form of nitrogen. Reduced sulfur (H2S)
may be detected but sulfate concentrations are
observed to increase across the redox boundary;
this is due to slow rate of sulfate reduction under
the in situ conditions of the Chalk aquifer.
Cation-exchange reactions are relatively unim-
portant in the Chalk and at maximum amount to
the equivalent of 30 mg ly1 Na in the confined
aquifer, the remaining increase in Na being
accounted for by addition of saline water. Several
cations increase in concentration along the flow
gradient as a result of the reaction of the small
amounts of marine clay minerals. This is well
illustrated by Kq and NHq 4 , elevated concentra-
tions of which are often associated with pollution;
in the confined groundwaters this increase is an
entirely natural phenomenon.
Fluoride is initially derived from rainfall. The
mean value for F in rainfall at a local meteorolog-
 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35 33

ical station, Chilton, is 0.10 mg ly1, which is

similar to the unconfined aquifer median value of
0.15 mg ly1 (Edmunds et al., 1987). Fluoride
shows an increase down-gradient in the confined
aquifer (Fig. 4) indicating a progressive reaction
with the phosphatic horizons in the Chalk matrix
leading to a median value of 1.3 mg ly1, which is
still lower than might be attained at saturation with
the controlling mineral, fluorite.
Iodide concentrations in the unconfined ground-
waters are similar to or slightly higher than that in
rainfall, but increases in the deeper confined aqui-
fer mainly in line with residence time, indicating
an internal source. Boron concentrations in ground-
water from the unconfined aquifer are in the range
2–120 mg ly1, with a median value of 18 mg ly1.
The increase of B in the confined aquifer parallels
that of Cl and is likely to be derived from residual
salinity sources.
The baseline concentrations of most metals
remain low. Manganese concentrations at outcrop
are usually below the detection limit of 0.03 mg
ly1. Detectable Mn is found only beyond the redox
boundary where concentrations are typically
between 3 and 20 mg ly1. Manganese is liberated
during the dissolution of carbonate but then is
rapidly removed by oxidation under most of the
in situ conditions. Copper is redox-sensitive and
is present at concentrations up to 7 mg ly1 in most
aerobic groundwaters but Cu is at or below the
detection limit of 0.3 mg ly1 in nearly all of the
reducing groundwaters. Cadmium was not found
above the detection limit of 0.3 mg ly1. The
median value for arsenic in groundwaters in the
unconfined aquifer was found to be 2 mg ly1 as
compared with 3 mg ly1 in the confined anaerobic
aquifer section. The higher total As in the anaer-
obic groundwater is consistent with the greater
solubility of AsIII species under the lower Eh
conditions.

6. Conclusions and implications for manage-

ment of groundwaters

Several issues emerge which need to be incor-

Fig. 4. Downgradient evolution of selected major and minor
elements in the Berkshire Chalk relative to the redox boundary; porated into future strategies for groundwater man-
the line of cross section is shown in Fig. 2. Cl and Mg are agement. Definitions of baseline are given here
indicated by solid symbols; Na and Ca by open symbols.. which can form the basis for distinguishing pristine
34 W.M. Edmunds et al. / The Science of the Total Environment 310 (2003) 25–35
from polluted waters as well as criteria for identi-
fying modern waters with only traces of human
impact from more polluted waters. A single value
for baseline in an aquifer may be difficult to define
because of spatial geological factors as well as
groundwater residence time.
The need for defining baseline quality arises for
statutory and legal purposes as well as for surveil-
lance and monitoring. There are currently no legal
requirements to determine the natural baseline
quality. However, there are situations where knowl-
edge of the baseline quality forms a useful stan-
dard, which may be compared with contemporary
groundwater quality in order to ascertain existing
impacts andyor risks of groundwater contamina-
tion or pollution. In certain regulatory licensing
situations, for example, where pristine quality
groundwater is at risk of deterioration from land
use activities, it may be warranted to establish
target or trigger level concentrations with reference
to natural baseline conditions. In such situations
where the natural baseline is referred to in a
licence, this standard may have legal standing.
For member states of the European Union, the
proposed Water Framework Directive requires that
an integrated approach to catchment management
is developed, based on distinct water bodies and
implemented with the aim of protecting, and where
necessary, improving the ecological status of the
catchment. The importance of high quality ground-
water in helping to provide good status for surface
waters becomes important, requiring improved
characterisation of its quality. The need to maintain
the status of ecosystems also has implications both
for groundwater quality as well as quantity.
Groundwaters may, however, have properties
resulting from geochemical processes which give
cause for concern in terms of human health—
either in the excess of certain substances (e.g. high
Fe, As, F) or in the deficiency of others (e.g. I
and Se). This emphasises the need for an improved
understanding of groundwater quality variations
and the processes controlling the release and atten-
uation of different elements. Once the baseline
characteristics are well defined, taking account of
geological and geochemical anomalies, then a basis
is formed for defining pollution. This becomes
increasingly important as evidence is found of the
deterioration of pristine groundwaters.
The concept of baseline is needed as a founda-
tion for groundwater monitoring. This is important
both retrospectively by analysing trends data to
see how far systems have been affected since
groundwaters started to be developed. It is also
urgently needed as a yardstick for detecting dete-
rioration of groundwater quality and as a basis for
stabilising or restoring water quality to required
standards. Further development of the ideas in this
paper are being undertaken at the European level
in a 12-country study (BaSeLiNe) due to report
in mid-2003. It is anticipated that recommenda-
tions from this study will be incorporated in policy
guidelines in the Water Framework Directive (and
its daughter Directive dealing specifically with
groundwater).
Acknowledgments
Discussion with colleagues in the BGS as well
as the Environment Agency is acknowledged in
developing the ideas expressed in this paper. We
would also like to acknowledge the exchange of
ideas on the concept of baseline undertaken during
exchange visits (PS) with the Norwegian Geolog-
ical Survey, funded by the British Council and
Norwegian Research Council. Some of the ideas
in this paper have formed the background for the
EC funded BaSeLiNe (EVK1-CT1999-00006)
study due for completion in 2003. This paper is
published with the permission of the Director,
British Geological Survey, Natural Environment
Research Council.
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