Journal of Hydrology 305 (2005) 1–14

www.elsevier.com/locate/jhydrol

Estimating groundwater mixing ratios and their uncertainties using

a statistical multi parameter approach
Joerg Rueedia,b,*, Roland Purtschertb, Urs Beyerleb,c, Carmen Alberichd, Rolf Kipferc
a
Robens Centre for Public and Environmental Health, EIHMS, University of Surrey, Guildford, Surrey GU2 9WA, UK
b
Institute of Climate and Environmental Physics, University of Bern, Sidlerstrasse 5, 3012 Bern, Switzerland
c
Water Resources and Drinking Water, EAWAG, Ueberlandstrasse 133, 8600 Duebendorf, Switzerland
d
Institute of Hydromechanics and Water Resources Management, ETH, 8093 Zuerich Hoenggerberg, Switzerland
Received 29 January 2003; revised 11 June 2004; accepted 15 June 2004

Abstract
The estimation of groundwater mixing ratios is a crucial task in groundwater research and management. The quantity as well
as the quality of groundwater resources are sensible to, e.g. the admixture river water, the interaction between different
groundwater layers and the spatial distribution of such mixing zones. In this paper, we present a procedure to calculate mixing
ratios and their uncertainties using a set of chemical and isotopic parameters. The advantages compared to estimations based on
only few parameters are better-constrained mixing ratios and the limitation of systematic errors due to the parameter choice.
The statistical consistence of the resulting mixing ratios is checked with a c2-test.
In particular in larger aquifers, where sampling resolution is often coarse, the composition of end members may vary
considerably from one borehole to another due to rock water interaction or varying recharge conditions. After selecting
sampling sites where no mixing occurs, the spatial distribution of the end member composition was calculated using Kriging.
This provides the best estimates of end member compositions and their uncertainties at any location of the area of investigation.
The method is, in principle, applicable for any number of end members. In this paper, the spatial distribution of the
interaction of two layers of the Continental Terminal aquifer (Niger, Africa) was investigated. Mixing between the deep CT2
and the shallow CT3 aquifer occurs where the separating layers are thinning out or due to improper sealing of some boreholes.
Radiogenic 4He concentrations, which differ significantly in the two aquifers, were used as independent parameter to
crosscheck the mixing calculations.
q 2004 Elsevier B.V. All rights reserved.

Keywords: Groundwater; Mixing ratio; Uncertainty; End-member; Tracer; Kriging; Niger

1. Introduction

The estimation of groundwater mixing ratios is an

important task in groundwater research and manage-
* Corresponding author. Tel.: C44 1483 682948; fax: C44 1483
689971. ment, e.g. river infiltration (Beyerle et al., 1999;
E-mail address: j.rueedi@surrey.ac.uk (J. Rueedi). Edmunds et al., 1992; Farah et al., 2000) or intrusion
0022-1694/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhydrol.2004.06.044
2 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14
Nomenclature
a correlation distance (m)
C concentration
h distance (m)
m mixing ratio of a parameter i
n total number of parameters
M weighed sum of deviations from the mean
P groundwater parameter
S sample
from leaky aquifers or brines (Balderer et al., 1996;
Cook and Herczeg, 2000). Mixing ratios of different
groundwater components can be calculated if the
mixed waters have distinct signatures, e.g. because of
different chemical and/or isotopic evolution. In the
above studies mixing ratios were calculated mainly
based on estimated end-member concentrations of one
or two parameters only. This approach is based on a
subjective choice of the usefulness of a parameter.
When the a priori information about the groundwater
system is reliable and/or when the chemical and
isotopic signatures of the two end-members are very
well distinguishable this approach leads to reliable
results. However, the consistency with other ground-
water parameters is not guaranteed and uncertainties
are rarely mentioned even though both points are
essential for a further use of the results.
Under the following conditions the above approach
leads to a low accuracy of estimated mixing ratios:
† Sparse information about the groundwater system
(e.g. drilling profiles, bore hole equipment,
groundwater interaction)
† Heterogeneous database of chemical and isotopic
data (e.g. different parameters measured, different
precision of measurement)
† Small differences between the signatures of the two
end-members
† High spatial variations of the end-members used to
estimate mixing ratios
Under these conditions, it would be favourable to
base the calculation of mixing ratios on all available
parameters measured because the error of estimation
can be reduced and the result becomes consistent with
w weight of parameter
x co-ordinate
g half of the covariance (semi variogram)
h nugget effect
s standard deviation
u difference between maximal variance and
nugget effect h
all parameters and can therefore eliminate the possible
bias due to the observer’s choice. To determine the
uncertainty of estimated mixing ratios—even in
simple cases—the uncertainties of the concentrations
of the two end-members and those of the measure-
ments have to be included into the final calculation.
In the first part of the paper a combination of
statistical methods will be presented which involves
all measured parameters in the investigated area to
calculate mixing ratios.
In the second part of the paper these methods will
be applied on a data set obtained from the multi-layer
aquifer system of the Iullemmeden Basin (Niger,
Africa) where the main objective was to correct
observed signatures of environmental tracers (e.g.
dating tracers, noble gases) with respect to mixing and
to detect regions where the groundwaters from two
neighbouring aquifers (CT3 and underlying CT2) mix
together. In our study area, all conditions preventing a
successful application of the conventional approach to
estimate mixing ratios (see above) are fulfilled.
2. Methods
The approach to estimate mixing ratios and their
uncertainties is based on the following procedure:
1. Analysis of available data in terms of data quality,
measurement techniques and precisions
2. Exclusion of non-conservative parameters
3. Selection of samples representing the end-mem-
bers based on all available information (geology,
hydrogeology and spatial distribution of
hydrochemistry)
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14
4. Estimation of end-member parameters and their
uncertainties at each location
5. Correction for other sources influencing the
chemical and/or isotopic groundwater signature
(e.g. local nitrate pollution)
6. Calculation of the overall mixing ratio of a sample
using the calculated mixing ratios of each
groundwater parameter
2.1. Selection of end-members
In the first step, one has to select all unmixed
samples that will be used as the best estimate of the
end-members. This step always involves arbitrariness,
which is why it is the least reproducible step of the
presented approach. Therefore, the selection has to
rely on a well-defined decision basis.
Since the presented method only accounts for
linear mixing of parameters one has to select all
groundwater parameters fulfilling this condition.
When mixing of two groundwaters leads to mineral
dissolution or precipitation the parameters involved in
these reactions are not conservative anymore and
therefore have to be excluded from the following
steps.
2.2. Estimation of spatial end-member concentration
CP and uncertainty sP
When it is considered that the end-member
concentrations of a parameter P are not known at
the sample location x0 where mixing occurs, they have
to be interpolated using unmixed samples. One
possibility to estimate an end-member concentration
at location x0 is the calculation of the mean CP(x0) and
the corresponding standard deviation sP(x0) of all
samples in the study area known to be end-members.
This approach is recommended for small numbers of
end-member samples and leads to the most conserva-
tive error estimation as spatial heterogeneities and
trends result in higher standard deviations of CP(x0).
For large amounts of samples Kriging can be used
to optimally interpolate the unknown end-member
concentration at location x0. As it is described in the
literature (Cressie, 1991; Matheron, 1963;1965;
1970), Kriging enables an estimation of the concen-
tration C(x0) and its standard deviation s(x0) at each
3
arbitrary location (x0) of the area based on the spatial
correlation of the data set. Best-fitting curves are
usually applied to approximate the spatial evolution of
the data co-variances, where different fitting functions
can be found in literature (e.g. de Marsily, 1986). The
spatial behaviour of the co-variances of our data was
found to be closest to a spherical evolution with
increasing distance (Eq. (1)):


 
3 h 1 h 3
gðhÞ Z h C u K h! a (1)
2 a 2 a
gðhÞ Z h C u hR a
where g(h) is the value of the semi-variogram in a
distance h apart of the origin x0Zx(hZ0), h is the
nugget effect, hCu is the maximum variance in far
distance and a is the correlation distance (Fig. 1B).
Note that hCu is equal to half of the overall variance
of the parameter.
2.3. Correction of contamination
When samples S with concentrations CS,P (of
parameter P) are punctually contaminated with
‘unnatural’ substances (e.g. nitrate or organic sub-
stances), which affect the major chemistry or isotopic
groundwater signature, unnatural parameters (e.g.
NOK 3 ) have to be excluded and we applied an
adequate correction for the naturally occurring
parameters affected by contamination (e.g. Ca2C,
NaC) have to be applied. When contamination occurs
over large areas (e.g. nitrate only by precipitation) the
parameter can and should be used to estimate mixing
ratios. However, it does not necessarily improve the
final result.
Correcting contaminated samples can be done by
correlating the concentrations of the contaminating
substance using other groundwater parameters. The
affected parameters can then be corrected based on
the linear regression. The standard deviation of the
residuals (compared to the regression line) has to be
added to the measurement errors sS,P to include the
uncertainties of the regression analysis in the
subsequent calculations.
4 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14

Fig. 1. (A) Principle of point estimation problem. x1,.,x5 denote the co-ordinates where the parameter C is sampled, and x0 is the location where
C has to be estimated. The distance interval from h to hCDh indicates the area in which the mean of all co-variances gi,j between all locations xi
and xj is calculated. (B) Example of semi-variogram using the d18O ratios of CT3 aquifer as database (see Fig. 4 for comparison). The squares
indicate calculated mean variances assuming an averaging distance Dh of 2 km. The best fitting spherical function, indicated with a solid line, is
plotted as a function of distance x.

 s with
2.4. Calculation of the total mixing ratio mG hypothesis) and due to the fact that all mP are
two end-members normally distributed, m can be calculated by aver-
aging the ratios of all n parameters.
Based on the measured parameter P of the sample S Pn
(CS,P GsS,P) taken at the location x 0 and the PZ1 mP wP
m Z P n (4)
estimations of both end-members C1,PGs1,P and PZ1 wP
C2,PGs2,P (at the location x0) we can calculate the
mixing ratios mP and the standard deviation sP 1
wP Z (5)
obtained from each parameter as follows: s2P
CS;P K C2;P As a measure of the usefulness of a parameter the
mP Z (2)
C1;P K C2;P weights wP are chosen to be inversely proportional to
the variance of each single mixing ratio (Eq. (5)). The

1 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
sP Z s2S;P ðC1;P K C2;P Þ2 C s21;P ðCS;P K C2;P Þ2 C s22;P ðCS;P K C1;P Þ2 (3)
ðC1;P K C2;P Þ2
Please note that hydrochemical parameters are inverse of the sum of all weights leads to the
sometimes log-normally, but usually normally dis- uncertainty of the estimated mixing ratio m (e.g.
tributed. With log-normally distributed end-members Brandt, 1992):
the above calculation leads to log-normally distrib-
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uted results (mp) and the following procedure to
1 1
calculate average mixing ratios had to be adapted. s Z Pn Z Pn (6)
PZ1 sP PZ1 wP
K2
When only few data are available a normal distri-
bution is usually the best assumption anyway. For
larger amounts of data, C and s are obtained from To validate whether each parameter represents the
Kriging and therefore are assumed to be normally  s a c2-test can be applied. It
same mixing ratiomG
distributed (Cressie, 1991; Matheron, 1963; 1965; can be shown that for normally distributed mP
1970). X
n
Since each conservative parameter must, by MZ  2
wP ðmP K mÞ (7)
definition, reflect the same mixing ratio m (null PZ1
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14
follows a c2-distribution with nK1 degrees of free-
dom (e.g. Brandt, 1992). Note that the degree of
freedom will be reduced when two (or more)
parameters are well correlated and therefore, not
independent anymore (e.g. often observed good
correlation of NaC and ClK). When the hypothesis
is fulfilled, s in Eq. (6) is the final uncertainty of the
mixing ratio. Otherwise, Rosenfeld et al. (1967)
proposed that all standard deviations sP can be up-
scaled linearly in order to fulfil the condition of the
c2-test. This up-scaling leaves m unchanged but leads
to a larger uncertainty of the total mixing ratio
resulting in a sufficient c2:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
M Pougnet (1967) the aquifers can be interpreted well
s Z P
ðn K 1Þ nPZ1 wP
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi distinguish in detail. In the western part (west of 38E)
Pn
PZ1 wP ðmP K mÞ  2
Z P
ðn K 1Þ nPZ1 wP
It has to be mentioned that this approach is not
founded on a clear mathematical basis (Rosenfeld
et al., 1967). Therefore, it has to be used with care
when systematic errors are possible (e.g. non-linear
mixing) because this would mean that the null
hypothesis is violated.
The described method leads to an estimation of the
mixing ratio mG  s of each sample based on all
conservative parameters, where m and s only depend
on the available data set and not on a subjective choice
of groundwater parameters.
3. Results and discussion
During the first steps of data interpretation and
their comparison with new data measured during our
research project two major problems were encoun-
tered. Firstly, large heterogeneities were observed
when chemical and isotopic signatures were inter-
preted based on available borehole information.
Further, intermediate values were observed in both
chemical and isotopic signatures that did not make
sense in an overall context. However, no information
was available whether or not these samples possibly
contain a mixture of two groundwaters. These two
points lead to the development and application of the
method explained above.
5
3.1. The study area
The Iullemmeden Basin is situated in the South-
West of Niger (Africa) (Fig. 2). The sediment layers
can be divided into the upper continental sediments of
the Continental Terminal (CT) and the lower
continental sediments of the Continental Intercalaire
(CI) separated by massive layers composed of silts
and marls from the last marine transgression (Dodo,
1992; Greigert, 1966). The CT formation can be
divided into three water baring layers, namely the
CT3, CT2 and CT1 aquifer (from top to bottom)
separated by clay and silt layers (Dodo, 1992).
According to Greigert (1966) and Greigert and
within the spatial context but they are difficult to
of the study area, the CT2 and CT1 aquifers contain
(8) water from the up-welling CI aquifer with a different
chemical and isotopic signature (Ousseini et al., 1992;
Le Gal La Salle, 1995). We therefore selected the
eastern part to test our method where no indications
were found of up-welling of CI groundwater (Fig. 2).
We only used the top two water bodies of the CT
formation (CT3, CT2) to show the applicability of the
statistical method because they provide the largest
database. Since the chemical and isotopic signatures
of these two waters are only slightly different and vary
considerably in space no clearly preferable parameter
exists for the calculation of mixing ratios. Therefore, a
combined use of all measured parameters is clearly
preferable to obtain the lowest possible uncertainty of
the final estimation of mixing ratios.
3.2. Selection of end-members
In former studies within the investigated area the
groundwater samples were interpreted based on the
structural information obtained from the drilling
profiles only (Dodo, 1992; Le Gal La Salle et al.,
1995; Ousseini et al., 1992). The resulting picture of
the distribution of chemical and isotopic signatures
was therefore, characterised by very large differences,
sometimes over short distances, and the studies
concluded that the different aquifers could not be
distinguished in terms of hydrochemistry. Since
drilling profiles are difficult to interpret in detail it is
possible that some drilling profiles were wrongly
6 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14

Fig. 2. Map of the study area in the south-west of Niger (Africa). Locations of all CT3 (squares) and CT2 (triangles) wells in the project area
used to the calculate end-members are shown in the right plot. Main cities are indicated with stars.

18 2
interpreted. Therefore, we choose a new approach, and NOK3 ) and the stable isotope ratios d O and d H.
assuming that major differences only exist between NO3 is only used to correct for human contamination.
K

the aquifers whereas each aquifer is more or less
homogeneous in terms of hydrochemical and isotopic
signature. This assumption is justified by the fact that
the basin shows similar geologic features over large
distances. The only geological heterogeneities are
documented in the southwest of the CT2 Aquifer (in
south-western corner of the project area) where
limestone lenses are observed (Dodo, 1992).
The samples used in this paper were partly
measured during this study but older samples from
former projects were introduced to provide a broader
basis. These data are held by the Ministry of Water
Resources (Niamey, Niger) and they are kindly
provided by Abdelkader Dodo. The combined data-
base used in this paper, consisting of more than 300
measurements, is listed in Rueedi (2002). The
estimation of end-members and the subsequent
calculation of mixing ratios are based on pH and
conductivity values measured in the field, the major
ions (NaC, KC, Ca2C, Mg2C, ClK, HCOK 3 , SO4
2K
The determination of end-members, which is
principally based on the drilling profiles, was
performed in the following four steps:
1. As we do not know the accuracy of most older data
we first checked the ion balance and dismissed all
samples with a disagreement bigger that 10%.
Since the statistic method presented takes analyti-
cal errors into account we assumed a fixed relative
measurement error of 5% because we do not know
the analytical error. For the stable isotope
measurements we dismissed measurements that
were far off the local meteoric water line. A
comparison of earlier and newly measured stable
isotope data showed no significant difference
indicating that no bias is introduced due to the
measurement technique or laboratory. A big
advantage of the statistical approach presented is
the fact that different uncertainties of measure-
ments from different years, sources and labs can be
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14 7

introduced into the statistical procedure and
propagated to the uncertainty of the mixing ratio.
2. We had to remove samples that do not show either
CT2 or CT3 groundwater signatures (e.g. mixture
with CI groundwater). Sulphur concentrations
showed to separate CI from CT groundwaters
because increased sulphur contents only appear in
samples from the CI aquifer (at least in the study
area).
3. Contaminated samples containing more than
20 mg/l nitrate were not used as end-member
because they do not represent natural conditions
(57 samples). The choice of the cut-off level is
based on observations made in the western region
where the natural background level of nitrate is
supposed to be about 20 mg/l (Elbaz-Poulichet
et al., 2002).
4. Since the method is used to determine mixing ratios
between CT2 and CT3 groundwater we had to
temporarily remove all supposed mixtures from the
database because they will be analysed using
unmixed samples. The primary selection condition
for the CT2 end-member was, besides the drilling
profiles, that they do not contain 3H or CFCs
(Rueedi, 2002). For CT3 end-members the cation–
cation and the stable isotope plots were found to be
the most useful to distinguish the CT3 groundwater
signature from the other aquifers (Fig. 3). The plots
clearly show a systematic behaviour of the data but
the overlapping of the circles in Fig. 3 indicates that
the distinction is not unique. However, when the
samples are analysed in an overall context (using
hydrogeology and spatial distribution of hydro-
chemistry) it was found that some of the intermedi-
ate samples are mixtures or originate from another
aquifer than proposed by the drilling profiles.
This entire selection and elimination procedure lead to
111 CT3 end-members from the originally 218
supposed CT3 samples. Fifty-seven samples were
eliminated due to a nitrate concentration above
20 mg/l, six samples contained increased sulphur
amounts and all others (44 samples) were temporarily
eliminated and analysed as mixtures. For the CT2
aquifer, 10 from originally 13 samples were selected
as end-members (Fig. 2).

Fig. 3. (A) Mass ratios of single and double charged cations of all available samples from the four aquifers displayed in log-scale. Squares
indicate samples from CT3 aquifer, triangles those from the CT2 aquifer, diamonds those from the CT1 aquifer and circles show samples from
the CI aquifer. The classification of the samples originates from the official documents. Areas where the samples of each of the four aquifers are
preferably found are indicated with ellipses. Open symbols show samples from older projects and full symbols are samples taken during this
project. (B) Stable isotope plot of all samples within the Basin. The straight line indicates the global meteoric water (GMWL) line from (Craig,
1961)).
8 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14

3.3. Estimation of spatial end-member concentration
and uncertainty
The concentrations of the CT3 end-members was
calculated based on Kriging because there are 111
samples available. The advantage of using Kriging is
that the uncertainties of estimation are usually smaller
than the standard deviation of all end-member
samples. The semi-variograms of the CT3 end-
members are displayed in Fig. 4. We used ‘normal’
Kriging because different preferential directions of
Krigging showed no significant anisotropy. Prefer-
ential directions would be expected when chemical
evolution would be present. Therefore, the lack of
preferential directions is an indication for well-
distributed groundwater recharge and confirms the
assumption of homogeneous geologic features (Sec-
tion 3.2) in the study area.
The three fitting parameters of the spherical
function (Eq. (1)) needed for the interpolation
procedure are listed in Table 1. Fig. 4 shows that the
stable isotopes and the pH values underlie a clear

Fig. 4. Semi-variograms of all 11 parameters of CT3 samples selected as end-members. Squares show half of the mean variances g(h) (Eq. (7))
averaged within distance intervals Dh of 2 km. The solid line shows the best-fitting spherical function (Eq. (8)).
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14 9

Table 1
Estimated parameters for spherical fit to variance analysis of CT3 end-members

g0 d18O d2H cond. NaC KC (mg/l) Mg2C Ca2C ClK (mg/l) SO2-
4 (mg/l) alc. (mg/l)
(‰) (‰) (mS/cm) (mg/l) (mg/l) (mg/l)
h 0.05 3.2 800 2 2.4 0.3 11 2.5 1.2 270
u 0.2 6 – 3.5 – 1.3 – 12 – –
A (km) 90 30 – 10 – 10 – 10 – –

spatial correlation. For these parameters Kriging leads
to an improvement of the estimated uncertainty sP at a
given location because Kriging favours samples in the
vicinity of the wanted location x0. The spatial
correlation of d18O and d2H could originate in the
characteristically small-scale rain patterns in this area
(Le Barbe et al., 1997; Lebel et al., 1997). However,
no reason can be named why the spatial behaviour of
the fitted correlation functions are different for these
two parameters even though the original data clouds
look fairly similar. It is possible that only a few points
negatively influence the automated fitting process.
The correlation distances of the chemical par-
ameters are small (NaC, Mg2C and ClK) or even zero
(all others). A negligible correlation distance indicates
that these parameters are spatially independent or
randomly distributed.
In case of the CT2 end-members the calculation of
variograms would be rather questionable, both
because of the small numbers of CT2 end-members
(10 end-members) and because they are all located in
a E–W line (Fig. 2), whereas Kriging is not supposed
to be used for extrapolation. In fact, the small number
of CT2 end-member sites would lead to Kriging
uncertainties that are equal to the overall statistical
variance of all CT2 end-member samples. Therefore,
we assumed a normal distribution and used the
statistical means and standard deviations for the
subsequent mixture calculation. The assumption of a
distribution different to the normal distribution could
not be justified with only 10 samples (Section 2.4).
The result are shown in Table 2.
It has to be mentioned that, in the western part of
the basin, considerable annual fluctuations of con-
ductivity and groundwater chemistry were found
(Elbaz-Poulichet et al., 2002). However, in our
research area, the few repeated measurements taken
in January and May do not show significant
differences in hydrochemistry but there is not enough
information available to dismiss fluctuations due to
quick reaction-times on recharge and evaporation.
However, we expect smaller fluctuations in our area
due to the considerably deeper water tables.
3.4. Correction of contamination
Since nitrate was only detected in young tritiogenic
(TritiumO0) CT3 groundwaters nitrate is a reliable
parameter to detect samples containing CT3 ground-
water (Rueedi, 2002). However, at some sampling
sites (10 samples bigger than 100 mg/l) the nitrate
concentrations are considerably higher than the
observed natural background of maximally 20 mg/l
(Elbaz-Poulichet et al., 2002). Such local contami-
nation sources most probably originate from sewage
outflows near bigger cities and/or from open watering
places. The signature introduced by these sources can
be seen as a third end-member and therefore should be
excluded from the parameters used to calculate binary
mixtures (see Section 2.3).
All chemical parameters were checked for a
correlation with nitrate but only sodium, magnesium,
calcium and consequently the conductivity were
found to be significantly correlated (Fig. 5). A similar

Table 2
Statistical mean and standard deviations for CT2 end-members

d18O (‰) d2H (‰) Cond. NaC KC (mg/l) Mg2C Ca2C ClK (mg/l) SO2K
4 alc. (mg/l)
(mS/cm) (mg/l) (mg/l) (mg/l) (mg/l)
K7.1G0.5 K49.9G4.2 151G14 9.3G4.2 5.3G0.8 8.1G1.8 9.8G3.1 1.3G0.4 3.4G0.9 92G12
10 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14

Fig. 5. Correlation of conductivity, sodium (NaC), magnesium (Mg2C) and calcium (Ca2C) concentrations with nitrate (NOK 3 ) contents in
groundwater samples of the CT3 aquifer. The straight lines indicate the regression lines including the sample containing more than 200 mg/l
nitrate (upper formula in top left of each plot). The dotted straight lines indicate the regressions without this sample (lower formula in top left of
each plot). The dotted lines show the standard deviations of the measurements compared to the regression line of all samples (note that it is not
the standard deviation of the regression line).

observation has been made in the western part of the
basin (Elbaz-Poulichet et al., 2002).
When all samples are included into the linear
regression one point with more than 200 mg/l of nitrate
dominates the result. Therefore, the dotted regression
line in Fig. 5 shows the outcome without this point. The
observed correlation most probably represents the
average chemical composition of the contamination
source. However, the sewage composition might vary
considerably leading to the observed scattering of the
data. As it was proposed in Section 2.3, the correlation
will be used to correct the influenced parameters
leading to a new sample concentration Cs and its
statistical uncertainty ss used in Eqs. (2) and (3).
3.5. Calculation of the total mixing ratio of a sample
All chemical parameters measured in CT2 and CT3
groundwaters are under-saturated with respect to any
mineral phase except quartz. This guarantees the ideal
mixing behaviour of all 9 chemical species and 2
isotopic parameters used to calculate mixing ratios. It
was found that, in this project, the 11 parameters are
quite poorly correlated (low R2 in Table 3). The poor
correlation of the stable isotopes is due to an
evaporation signature. Table 3 shows as well the
results of the t-test applied on the correlations where
(C) indicates a significant correlation and (K)
indicates insignificant correlation. Therefore,
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14 11

Table 3
Correlation coefficients R2 between used parameters and significance of correlation resulting from t-test

Cond. ClK SO2K

4 HCOK
3 KC NaC Mg2C Ca2C d18O d2H
Cond. 1 0.109 0.001 0.185 0.062 0.355 0.303 0.483 0.087 0.023
ClK C 1 0.033 0.004 0.127 0.121 0.028 0.038 0.000 0.006
SO2K
4 – – 1 0.007 0.118 0.001 0.033 0.002 0.059 0.050
HCOK 3 C K K 1 0.079 0.015 0.370 0.619 0.001 0.000
K C
C K K K 1 0.004 0.063 0.094 0.012 0.018
NaC C K K K K 1 0.058 0.083 0.320 0.145
Mg2C C K K C K K 1 0.424 0.002 0.013
Ca2C C K K C K K C 1 0.002 0.000
d18O K K K K K K K K 1 0.343
d2H K K K K K K K K C 1

(C) indicates significant correlation and (K) indicates that there is no correlation between the two parameters.

the degree of freedom for the c2-test is equal to 5

when all parameters were measured.
The statistical procedure was applied on all
samples, which were not selected as end-members
(107 CT3 samples and 3 CT2 samples with and without
nitrate). Fig. 6 shows, as an example, the mixing ratios
of two samples calculated with each parameter
compared with the calculated total mixing ratio
including all parameters. The top plot shows a case
where the c2-test was fulfilled. The much smaller error
of the total mixing ratio clearly supports the argument
that the applied procedure leads to a smaller uncer-
tainty of estimation than the use of one parameter only.
The lower plot, on the other hand, shows the total ratio
(and uncertainty) before and after the c2-test failed.
It can be seen that the final uncertainty is actually

Fig. 6. Two examples of mixed samples and the corresponding

mixing ratios. Calculated mixing ratios mP and uncertainty sP of
each parameter are indicated with squares and error bars. The plots
show the final mixing ratios ðmG sÞ indicated with the hatched areas
(calculated based on all single ratios). The top plot shows a case Fig. 7. Amounts of radiogenic 4He (4Herad) in groundwater samples
where the c2 was fulfilled. The bottom plot shows a case where the plotted against the calculated mixing ratios of CT2 in CT3
test failed and the initially calculated ratio (inner hatched area) had groundwater. Typical amounts of 4Herad measured in the two end-
to be corrected to obtain the final mixing ratio (outer hatched area). members are indicated with hatched areas.
12 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14

bigger than the ones of the stable isotopes but it is
based on all parameters and therefore, independent of
the users choice of a parameter.
To show the applicability of the method on the data
presented, Fig. 7 displays the comparison of the
calculated ratios with the radiogenic 4He (4Herad)
contents of the few samples measured on pumped
boreholes. The 4Herad is defined as the difference
between the measured 4He concentration (4Hemeas)
and the atmospheric 4He component given by the
equilibrium concentration (4Heeq) plus the excess air
component (4Heexc). The calculation of 4Herad was
done using the approach of Aeschbach-Hertig et al.
(2000). Data can be found in Beyerle et al. (2003) and
Rueedi (2002). 4Herad was chosen to check the
results because the two groundwaters contain clearly
distinguishable amounts of 4Herad (see grey bars in
Fig. 7). Although the estimated mixing ratio seems to
be too large in case of one sample, the overall good
agreement between 4Herad and the calculated mixing
ratio shows that the presented method is applicable
even for an unfavourable database.
The relative errors of mixing ratio estimations are
between 8 and 20% when all 11 parameters are used.
However, at sites where only few parameters were
measured the relative errors can reach up to 100%.
Depending on the location of mixing ratio estimation
the results mainly depend on stable isotope ratios,
ClK, KC, Mg2C and HCOK concentrations, whereas
the other parameters (Na C, Ca 2C , SO 2K 4 and
conductivity) do hardly constrain the calculations
because the variations of their end-members are large

Fig. 8. The map shows a contour plot of calculated mixing ratios (CT2 in CT3 groundwater) of all samples within the project area which were
taken from open wells. Diamonds indicate CT3 end-members and dots indicate CT2 end-members. The solid lines delineate the boundaries of
the CT2 and CT3 aquifers after Greigert and Pougnet (1967).
 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14
(Fig. 6). However, which parameter dominates the
mixing ratio calculation is determined by the
statistical method applied and not by the researcher.
Fig. 8 shows all calculated mixing ratios of wells in
the project area. The reason is that wells only capture
the top few meters of the CT3 aquifer whereas
boreholes may reach down to the CT2 layer. There
were a few supposed CT3 boreholes detected between
Dogon Doutchi and Nassarawa where mixing ratios
were between 0.5 and 0.9. These boreholes most
likely withdraw water from both aquifers. The depths
of these holes support this observation. The calculated
mixing ratios of these boreholes can and will be used
to correct other measurements such as dating
tracers. The map in Fig. 8 shows that mixtures
can be observed mainly near the northern boundary
of the CT3 aquifer (thick full lines), where the CT3 is
only thin, and near the southern boundary of the area
where CT3 and CT2 are supposed to be well separated
(thick dashed line) (Greigert and Pougnet, 1967).
However, mixtures are detected further up-stream
(NNE) of this area indicating that interaction between
the two aquifers occurs further up-stream than
expected. Whether this boundary is the real limit of
the confining layer or developed due to the increasing
use of CT2 or CT3 groundwater for drinking water
supply remains open. Additional consultation of the
hydraulic records of both aquifers unfortunately did
not help because in the observed regions the gradients
between the two aquifers are of the same order of
magnitude as the uncertainties of the levels (Dodo,
1992; Ousseini et al., 1992). However, the results
enable the selection of regions where further, more
detailed investigations should focus on to determine
anthropogenic consequences on the local groundwater
resources.
4. Conclusions
The presented approach to estimate groundwater
mixing ratios proved to be useful and allowed to
calculate mixing ratios and their uncertainties.
The major improvements to former methods are that
the results are consistent with all groundwater
parameters and that the errors of estimation can be
drastically reduced in some cases. In the less optimal
cases uncertainties are slightly higher than the ones
13
of the ‘best’ parameter but the result is independent of
the choice of the ‘best’ parameter. It is to be noted
that, even though the statistical procedure is clearly
defined and consistent with all data, the results still
depend on the initial choice of the end-members. This
first step always involves arbitrariness and therefore it
is clearly the limiting factor for the reproducibility of
the entire approach. However, if the geologic
information is scarce, as in our study area, the
presented approach clearly helps to understand and
interpret the measurements better.
The interpretation of calculated mixing ratios has
to be undertaken with great care. For example,
mixtures possibly originating from improper sealing
of the borehole do not allow conclusions about the
groundwater system but they are essential to interpret
additional parameters (e.g. groundwater dating tracer)
that are possibly only measured at a few selected
wells. For the interpretation of non-linear parameters
(e.g. radioactive tracer, chemical reactions) it is
essential to know if the groundwater sample is
unmixed or a mixture of two groundwaters with
different signatures and it is important to know the
uncertainties of estimation.
Furthermore, the results have shown to provide
more information about the groundwater system. The
spatial distribution of calculated mixing ratios indi-
cates that the two groundwaters from the CT2 and the
CT3 aquifer are hydraulically connected slightly
further up-stream than assumed by former studies.
This information is essential for hydrodynamic
groundwater models and it reveals regions where
further investigations should focus on.
In general, the knowledge of the uncertainty of a
mixture is essential for any further use of the mixing
ratios, e.g. correction of other measurements like
hydraulic heads and conclusions on water resources.
Acknowledgements
This study was supported by the Swiss National
Science Foundation (project no. 20-53629.98).
We would like to thank Abdelkader Dodo of the
Ministry of Groundwater Resources for his support
with additional groundwater data of the study area.
14 J. Rueedi et al. / Journal of Hydrology 305 (2005) 1–14
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