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Development and testing of three hybrid

methods for the assessment of aquifer
vulnerability to nitrates, based on the drastic
model, an example from NE Korinthia, Greece

Article in Journal of Hydrology February 2007

Impact Factor: 3.05 DOI: 10.1016/j.jhydrol.2006.08.014

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Development and testing of three hybrid methods

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for the assessment of aquifer vulnerability
to nitrates, based on the drastic model, an
example from NE Korinthia, Greece

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A.K. Antonakos *, N.J. Lambrakis on
University of Patras, Geology Department, 26500 Rio, Greece

Received 22 February 2006; received in revised form 30 August 2006; accepted 31 August 2006
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KEYWORDS Summary The assessment of groundwater vulnerability to pollution has proved to be an effec-
Aquifer vulnerability; tive tool for the delineation of protection zones in areas affected by groundwater contamina-
Drastic; tion due to the intensive fertilizer applications. The main objective of this study has been to
Korinthia; develop and check the results of three hybrid methods for specific aquifer vulnerability assess-
Greece; ment based upon the parameters, classification and rating principles of the well known DRASTIC
Logistic regression; model. The first method, proposed by [Panagopoulos, G., Antonakos, A., Lambrakis, N., 2006.
Weights of evidence Optimization of DRASTIC model for groundwater vulnerability assessment, by the use of simple
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statistical methods and GIS. Hydrogeology Journal (published online).], has proved to be an
effective way to modify the DRASTIC model in order to achieve better correlation with actual
nitrates occurrence. Descriptive statistics and simple statistical tests on a hydrochemical data-
set are used by the method in order to change the initial factor ratings and factor weights par-
o

ticipating in the vulnerability assessment equation. The other two methods were developed by
the use of logistic regression and weights of evidence statistical procedures and the use of the
same hydrochemical dataset, and attain relatively high correlation factors when referring to
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sample points while correlation was significantly lower for the entire distributions of vulnera-
bility estimation and actual nitrates occurrence.
2006 Elsevier B.V. All rights reserved.
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Introduction

Intrinsic vulnerability of an aquifer can be defined as the

* Corresponding author. Tel.: +3210 9414210; fax: +32610 997782. ease with which a contaminant introduced into the ground
E-mail address: anton_a@hol.gr (A.K. Antonakos). surface can reach and diffuse in groundwater (Margat,

0022-1694/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhydrol.2006.08.014
Development and testing of three hybrid methods for the assessment of aquifer vulnerability
1968; Vrba and Zaporozec, 1994). It is a relative, dimension-
less and non-measurable property, which depends on the
aquifer characteristics, but also the characteristics of the
wider geological and hydrological environment (unsaturated
zone, soil horizon, relief, recharge, etc.).
Specific vulnerability may be expressed as the likelihood
that an aquifer be polluted by contaminants, which are
introduced into the ground surface. This is determined by
the aquifer intrinsic vulnerability and the contaminant load-
ing that is applied to the specific point of the hydrogeolog-
ical basin or even in a region around this point. The
contaminant loading is determined by the quantity, the
physico-chemical properties, and the way in which the var-
ious contaminants are released into the environment.
The assessment of groundwater vulnerability to pollution
has been subject to intensive research during the past years
and a variety of methods have been developed. The sim-
plest to apply and for that reason the most widely used
are the Rating Models. These methods classify each
parameter, which potentially influences the probability of
pollution of the aquifer, in a scale and lead to a score, which
designates the vulnerability of the groundwater (LeGrand,
1964; Foster, 1987; US Environmental Protection Agency,
1993).
An evolution of these methods is the Point Count Sys-
tem Models (PCSM) or Parameter Weighting and Rating
Methods, which apart from classifying the various
parameters also introduce relative weight coefficients
for each factor.
The most widespread PCSM method of evaluation of the
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intrinsic vulnerability is the DRASTIC method (Aller et al.,
1987). This method, taking into account seven parameters
of the geological and hydrological environment, was devel-
pe
oped in the USA, where it has been applied several times
(Durnford et al., 1990; Evans and Myers, 1990; Halliday
and Wolfe, 1991; Rundquist et al., 1991; Fritch et al.,
2000; Shukla et al., 2000), but also in many other regions
of the world (Lobo-Ferreira and Oliveira, 1997; Lynch
et al., 1997; Melloul and Collin, 1998; Johansson et al.,
1999; Kim and Hamm, 1999; Zabet, 2002).
Two other groups of methods for the assessment of aqui-
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fer specific vulnerability (pollution potential) are the statis-
tical and process-based methods.
Statistical methods range from simple descriptive statis-
tics of concentrations of targeted contaminants to more
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complex regression analyses that incorporate the effects
of several predictor variables. When a dataset of water-
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quality and potential explanatory variables is available, sta-
tistical models, mainly in the form of regression equations,
can be used to predict probabilities of contamination.
Hypothesis tests allow elimination of insignificant variables
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that offer little to the assessment process. The procedure
produces weighting factors that optimize the use of impor-
tant variables thereby removing the need for subjective
influences of best professional judgment in determining
the importance of each variable. Logistic regression is a sta-
tistical method that predicts the probability of occurrence
of a binary pattern. (Helsel and Hirsch, 1992). Concentra-
tions of pollutants are continuous parameters but can be
transformed to binary form using a threshold concentration.
Concentrations above this threshold can be denoted as pres-
ence and concentrations below this threshold as absence.
289
Parameters used as predictor variables can be continuous
or discrete variables.
A method similar to logistic regression, based on the
probability of occurrence of a binary pattern and Bayes
rules for probability, is the weights of evidence method
originally developed for mineral potential mapping.
The end product of these two methods is a distribution of
probability that a pollutant will exceed a certain value,
showing statistically derived indications of vulnerability as
opposed to the more subjective categorical rating methods.
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Process-based methods refer to approaches that either
simulate or otherwise take into account physical processes
of water movement and the associated fate and transport
of contaminants in the environment. These approaches usu-
ally include the use of process simulating models that calcu-
co
late the distribution of vulnerable or intrinsically
susceptible areas based on the movement of water and sol-
utes. Because of data needs and complexity, these methods
are suitable mainly for large scale studies.
Combinations of the above methods also known as hybrid
methods are defined in general as any methods that com-
bine components of statistical, process-based, and (or) in-
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dex methods. Objective hybrid methods include
combinations of statistical, process-based, or other objec-
tive components in the determination of explanatory vari-
on
ables or processes. Objective hybrid methods commonly
rely on preconceived scoring systems such as DRASTIC or
other index methods.
In this study, three hybrid methods combining the DRAS-
TIC methods categorization and rating principles, with sta-
tistical procedures such as descriptive statistics, logistic
regression and weights of evidence are developed and their
results are compared. Comparison is based on the correla-
tion of their results to actual pollution occurrence (ex-
pressed as nitrate concentration or probability of
exceeding a certain nitrate concentration), their complex-
ity and their data needs. The selection of nitrates as a pol-
lution index was based not only on the fact that it
constitutes the main contaminant that human activities
introduce into the environment of the study area, but also
because it has been proposed as a representative indicator
of groundwater quality degradation (US Environmental Pro-
tection Agency, 1996).
Geological and hydrogeological setting
The study area is located in the northeastern part of Pelo-
ponnesus Greece, in the central part of Korinthia prefecture
area and it is approximately 902 km2 in area (Fig. 1).
The geological bedrock consists of the carbonate sedi-
ments of the Trapezona sequence (a transition zone between
Pindos and Pelagonian geotectonic zones) in the southeast-
ern part of the study area and the carbonate sediments
and flysch of the Pindos and Tripolis zones in the southwest-
ern part of the study area (Katsikatsos, 1992) (Fig. 2a).
The Trapezona carbonate sequence consists of plated
limestones of Triassic to Upper Jurassic age with nodules
and thin bands of chert. In Middle Jurassic, this sequence
was interfered by the shalescherts formation made up of
bedded sandstone clay and marl with ophiolithic bodies in
theme.
290
Figure 1 Shaded relief and geographic orientation map of the study area.
The Tripolis zone consists of a dolomitic limestone to
limestone series of Upper Jurassic to Eocene age, which
are uncomformably overlaid by the Tripolis zone flysch
formation.
The Pindos zone formation in the study area consists of
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Upper Cretaceous platy limestones, which are uncomform-
ably overlaid by the Pindos zone flysch formation. Pindos
zone is geotectonically overthrusted on the Tripolis zone
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with a general NESW thrust direction.
The main part of the study area is covered by post oro-
genic sediments of Pliocene to Holocene age, which uncom-
formably overlay the bedrock formations. They consist of
Pliocene lacustrine marls interbedded by thin layers of con-
glomerates and sandstones, cemented fluvial (proximal and
distal) conglomerates of Calabrian age, sea terraces of Tyr-
rhenian age, eluvial deposits consisting of alterations of red
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sand, clay, sandy loam and loose conglomerates of Pleisto-
cene age and finally recent alluvial deposits and talus cones
(Fig. 2a).
From the hydrogeological point of view six major hydro-
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geological units (aquifers) can be distinguished:
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The carbonate aquifers of the bedrock which are fully
karstic for the Trapezona sequence and Tripolis zone
and partly karstic for the Pindos zone. They are highly
productive aquifers with an average thickness of 100
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400 m and hydraulic conductivity values varying from
0.34775.6 m/day (Mastoris et al., 1971; Morfis and
Zojer, 1986).
The flysch formations of Tripolis and Pindos zones as well
as the shalescherts formations of the Trapezona
sequence can be distinguished as impermeable units.
The Pliocene marl aquifer that develops in the thin beds
of sandstones and conglomerates interbedded within the
marl formation. It is a confined aquifer with an average
thickness of 210 m and low hydraulic conductivity val-
ues (0.086 m/day) (Mastoris et al., 1971).
A.K. Antonakos, N.J. Lambrakis
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The Calabrian conglomerates aquifer with an average
thickness of 50100 m and high values of hydraulic con-
ductivity (129.6 m/day) (Zervogiannis, 1991).
The aquifer that develops within the eluvial and sea ter-
races formations, with an average thickness of 3050 m
and medium to high hydraulic conductivity values
(1.72 m/day) (Mastoris et al., 1971).
The aquifer that develops within recent alluvial and talus
cone deposits with an average thickness of 4060 m and
hydraulic conductivity values varying from 8.64 to
69.12 m/day (Koumantakis et al., 1999). This aquifer is
in most cases in hydraulic contact with the underlying
aquifer of eluvial and sea terraces formations from which
it is laterally recharged.
The impermeable layer underlying all the aquifers of the
post orogenic sediments is the lacustine marls of the Plio-
cene marl formation as it can be seen in the geological cross
section of Fig. 2a.
The mean annual precipitation in the study area for the
period 19752004 is 594 mm, which corresponds to the
mean annual rainfall water volume of 535.8 106 m3. Pre-
cipitation is directly related to altitude by the relationship
P = 0.34 h + 468. The water balance parameters have been
computed based on the procedures described by Thorn-
thwaite et al. (1955). A big part of the annual precipitation
namely 360.9 106 m3 (67.5%) is lost via evapotranspiration,
while 102.6 106 m3 (19.1%) infiltrates and recharges
groundwater. The rest 71.8 106 m3 (13.4%) discharges to
the sea as surface runoff.
A major part of the study area, namely 49.9%, is covered
with intensive cultivations (vineyards, fruit trees, olive
groves) which are widely spread in the whole extent of
the study area. The use of inorganic fertilizers in these cul-
tivations has a great polluting effect on groundwater. The
composition of these fertilizers is mainly ammonium sul-
phate and ammonium nitrate, so the major expected pollu-
Development and testing of three hybrid methods for the assessment of aquifer vulnerability 291

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Figure 2 Base maps of the study area: (a) geological map and geological cross-section of the study area; (b) land use map of the
study area; (c) soil type map of the study area.
292
tant in the study area is nitrogen mainly in the form of ni-
trates. A big part of the coastal zone of the study area is
covered by urban and suburban areas, which add an extra
environmental pressure to the groundwater of the coastal
alluvial aquifer.
Materials and methods
For the determination of actual pollution occurrence in the
study area, an extensive sampling and analysis program of
groundwater was conducted. Groundwater samples were
collected in the dry period of the 2003 hydrological year
at a more or less uniform sampling network, which includes
124 sampling points, covering the whole extent of the study
area. Bores were flashed by turning on the bore pump and
allowing it to run for approximately 30 min, until it was
freshly drawn from the aquifer. Plastic 500 ml bottles were
filled with the groundwater sample, filtered through a Milli-
pore filter paper (0.45 lm), and stored in an insulated
cooler until frozen later in the day. Samples were analyzed
for NO3 by the cadmium reduction method, using a DR/4000
Hach spectrophotometer.
In addition, to the results of this study, results from
three other studies conducted earlier in parts of the study
area (Daskalaki et al., 1998; Voudouris et al., 2000; Stamatis
and Voudouris, 2003) were used in order to support the sta-
tistical significance of the database used for spatial interpo-
lation and statistical analysis. In order to verify that no
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statistically significant difference exists between those
datasets, individual MannWhitney U test (Mann and Whit-
ney, 1947) was conducted between all possible pairs of
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datasets as well as an overall KruskalWallis dependency
test (Kruskal and Wallis, 1952). These tests prove that no
statistically significant difference exists among the data
sets used for analysis.
Depth to groundwater distribution was produced based
on water level measurements contacted in 165 wells uni-
formly spread in the whole extent of the study area interpo-
lated by the use of ordinary kriging method.
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The determination of the aquifers hydraulic parame-
ters was based on 14 pumping tests conducted in previ-
ous studies (Mastoris et al., 1971; Voudouris et al.,
2000).
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Due to lack of a soil type map for the study area, a map
was constructed for the needs of the present study, with the
combined use of the Land Resource Map (scale 1:50,000)
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published by the Institute of Forestry of the National Agri-
cultural Research Foundation and 202 soil core samples
and textural analysis performed by the Institute of Forestry
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and the Institute of Soil Research of the National Agricul-
tural Research Foundation. Unit separations of Land Re-
source Map are based on characteristics like landforms,
soil depth, slope, aspect, erosion, surficial geology and
state of natural vegetation. Soil type map (Fig. 2c) was con-
structed after assigning soil texture classes to every unit of
Land Resource Map according to the soil core sample(s)
every unit map contained.
Finally for the determination of the land use types of the
study area, the Corine Land Cover (Bossard et al., 2000)
data and classification were used.
A.K. Antonakos, N.J. Lambrakis
Methodology of determination of aquifer
specific vulnerability (pollution risk)
The modified DRASTIC method
As it was mentioned before, the DRASTIC method considers
seven parameters, making up the acronym: Depth to
groundwater, Recharge, Aquifer type, Soil type, Topogra-
phy, Impact of the vadose zone, hydraulic Conductivity.
These parameters are imported in a simple linear equa-
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tion, after they have been reduced from the physical range
scale to a ten-grade relative scale. Each parameter is mul-
tiplied by a weighting coefficient, which has been deter-
mined subjectively, based on the professional judgment of
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the authors of this method. The reduction of the physical
range scale to the relative ten-grade scale is conducted with
the same philosophy. The linear equation of determination
has the following form:
V intrinsic D  kD R  kR A  kA S  kS T  kT I  kI
C  kC 1
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Where V(intrinsic) is the intrinsic vulnerability, D the depth
to groundwater, R the recharge, A the aquifer type, S the
soil type, T the topography (surface slope), I the impact
on
of the vadose zone type, C the hydraulic conductivity and
k the weighting coefficient for each factor.
The major drawback of this method is the subjectivity of
the determination of the rating scale and the weighting
coefficients. Doubts have also been expressed for the selec-
tion of the specific parameters and the exclusion of others
(Garrett et al., 1989; Vrba and Zaporozec, 1994; Merchant,
1994; Rosen, 1994).
Improvements of the DRASTIC model have been proposed
by several researchers. Most of them propose the subtrac-
tion of factors included in the model (Evans and Myers,
1990; Rupert, 1999) or the inclusion of additional factors
like land use or irrigation type and intensity (Secunda
et al., 1998; Rupert, 1999; McLay et al., 2001). Finally pro-
posals about incorporating DRASTIC with other procedures
or models, like capture zone delineation or finite element
flow and transport models, have been made (Foster, 1987;
Merchant, 1994).
Fewer attempts have been made to validate and verify
the model performance. In most cases, correlation of model
results with actual pollution occurrence was done for that
purpose (Kalinski et al., 1994; Rupert, 1999; McLay et al.,
2001).
For the assessment of pollution potential in this study, a
modification of the DRASTIC method proposed by Panagop-
oulos et al. (2006) is used. The modification is based upon
simple statistical procedures involving
1. Revision of the rating scale of each parameter
2. Revision of the factor weights and
3. Addition and subtraction of parameters, based on their
correlation to nitrates concentration.
A revision of the rating scales is accomplished by using
the mean of every class of each parameter defined in the
initial model. Following the check that was carried out using
the Wilcoxon rank-sum nonparametric statistical test (Wil-
Development and testing of three hybrid methods for the assessment of aquifer vulnerability 293

coxon, 1945), it was ascertained that the mean of two (parameters with discrete classes, e.g. aquifer type, vadose
neighboring classes, did not differ statistically. Classes were zone type and soil type) all the categories existing in the
grouped in such cases, while for non-continuous parameters area were maintained, regardless of statistical diversity.

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Figure 3 Box plots showing the distribution of groundwater nitrates concentration for the statistically different classes of all the
DRASTIC parameters and land use.
294
The box plot diagrams of all the statistically divergent clas-
ses of all the DRASTIC parameters are illustrated in Fig. 3. In
Table 1 the parameter classes, as well as the corresponding
rating of each class, the average nitrates concentration and
the respective modified rating of every class or group of
classes are presented. Modified rating values were derived
using the mean nitrates concentration of each class reduced
to a ten-grade scale.
The next step of the initial model modification is the
revision of the weighting factors, with which each DRASTIC
parameter participates in Eq. (1). This revision is achieved
by the study of the correlation of each parameter with
the nitrates concentration for the 224 sampling points of
the research area. For the calculation of the quantitative
correlation between the discrete (nominal) parameters
and the nitrates concentration, their factor scores were
used. Additionally, due to the fact that the factor scores
vary with an interval scale, the correlation was calculated
using the Spearmans q and Kendalls s correlation coeffi-
cients (Kendall, 1975), which are advisable for such type
of parameters. Based on these coefficients and after their
values were reduced to a scale with a maximum value of
5, as it is defined by the DRASTIC model, the new weighting
factors were calculated. In the case when one of the coef-
ficients is not statistically significant, the corresponding
parameter will be excluded from the equation of vulnerabil-
ity. Table 2 shows the correlation coefficient values and the
revised weighting factors, where it becomes evident that
the Soil type Recharge and Hydraulic conductivity
parameters are not statistically significant and should be ex-
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cluded. It is also seen that the largest weighting factor is
attributed to the Topography parameter, while the
Depth to groundwater, Aquifer type and Impact of
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the vadose zone weighting factors are degraded with re-
spect to the initial ones, although they remain relatively
high.
The original DRASTIC model application, as well as mod-
ifications of the method, is related to the intrinsic vulnera-
bility calculation, which is the most important factor
affecting the nitrates concentration in the groundwater.
However, as mentioned before, the contaminant loading ap-
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plied to the ground surface of the research area has a major
impact upon the nitrates concentration of the groundwater,
and combined with the intrinsic vulnerability constitutes
the specific vulnerability or pollution risk of the aquifer.
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For the calculation of this quantity, one more factor should
be added to the modified DRASTIC equation in order to ex-
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press the contaminant loading in each point of the research
area. Panagopoulos et al. (2006) suggest theland use as a
surrogate variable for the contaminant loading parameter
and specifically the spatial mean of the land use rating over
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an area of 300 m surrounding the sample point. It is known
that high nitrate concentrations in the urban part of the
study area are attributed to the use of septic tanks in con-
junction with the disposal domestic effluent into abandoned
wells. The method tries to incorporate this fact by assigning
the maximum rating to the urban land use category.
The grade of each land use category was derived simi-
larly in accordance with the revision of the rating scales
of the DRASTIC parameters. Namely, the mean nitrates con-
centration in each land use category was used, reduced in a
ten-grade scale. For land use categories where no data
A.K. Antonakos, N.J. Lambrakis
points were available, the grade of each category was
derived from the literature (Secunda et al., 1998; Rupert,
1999; McLay et al., 2001). The grades of land use categories
are presented in Table 3. The bottom right box plot diagram
of Fig. 3 displays the nitrates distribution characteristics for
each land use category.
The relative weight of this factor is produced in the same
way as the other factors revised weights based on the corre-
lation index (Spearman q = 0.32; Kendall s = 0.23) between
the spatial mean of the land use rating over an area of
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300 m and the nitrates concentration as it is proposed by
Panagopoulos et al. (2006).
With the addition of the new parameter, Eq. (2) now ex-
presses the specific vulnerability of the aquifers, such as
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V specific Aquifer Pollution Risk
3:5  D 3:8  A 5  T 3:4  I 4  L; 2
where V(specific) is the specific vulnerability, D the depth to
groundwater, R the recharge, A the aquifer type, T the
topography, I the impact of the vadose zone and L the con-
taminant loading per land use category.
The specific vulnerability or pollution risk map, which re-
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sults from the application of the above equation, is pre-
sented in Fig. 4a. Correlation between pollution risk and
natural logarithm of nitrates concentration was calculated
on
for the 244 sample points with a Spearmans r correlation
factor of 0.64 and for the entire study area using the Spear-
mans r correlation coefficient between all unit cells of the
two distributions in raster format (Bonham-Carter, 1994),
which was 0.65. Transformation of nitrates concentration
to a log scale was done in order to obtain a normally distrib-
uted parameter suitable for the calculation of Pearsons r
coefficient.
The scatter diagram of Fig. 6a illustrates the correlation
between specific vulnerability and the natural logarithm of
nitrates concentration for the 224 sample points.
Logistic regression
As it was mentioned before Point Count System Models
(PCSM) like DRASTIC use a simple linear equation to esti-
mate aquifer vulnerability. This equation is similar to those
produced by regression models. The main difference be-
tween these two procedures is that parameter weight coef-
ficients are subjectively estimated for PCSM models and
objectively calculated with the use of the existing data in
the case of regression models.
Regression models have been widely used in environmen-
tal studies (Giblin et al., 1981; Rao et al., 1997; Kreuger and
Tornqvist, 1998; Xinde et al., 2000), and particularly in
aquifer vulnerability assessment (Mueller et al., 1997; Teso-
riero and Voss, 1997; Rupert, 1998; Nolan et al., 2002). Mul-
tiple linear regression, which is the most widely used
regression model, uses the Ordinary Least Squares (OLS)
method for the determination of parameter weight factors.
The Least Squares method has some limitations regarding
the data used for analysis. The most important of those lim-
itations consider residuals which must have normal distribu-
tion and constant variance. If a linear equation is to be
generated using OLS method with nitrate concentration as
the independent variable and DRASTIC parameters plus land
Table 1 Original and modified ratings of the seven DRASTIC factors
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Depth to ground water Recharge Aquifer Type Soil Type
Range Original Mean Modified Range Original Mean Modified Aquifer Original Mean Modified Soil Original Mean Modified
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(m) rating NO
3 rating o (mm) rating NO
3 rating type usual NO
3 mg=L rating type rating NO
3 rating
mg=L mg=L rating mg=L
01.5 10 67.9 10 050 1 50.8 6.3 Holocene 5 66.5 8.5 Clay 1 58.9 9
1.54.5 9 50100 3 65.0 10 Conglomerate 4 17.4 2.1 Clay loam 3 46.2 7.1
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4.59 7 100180 6 49.1 5 Karstic 8 78.2 10 Sandy clay 4 14.8 2.1
loam
915 5 180250 8 Pleistocene 7 57.0 7.3 Loam 5 64.9 10
1523 3 51.0 7.5 250+ 9 Marl 6 39.5 5 Sandy Clay 5
2330.5 2 42.6 6.1 Flysch 3 33.4 4.2 Sandy Loam 6 24.0 3.7
30.5+ 1 Silty clay 2 60.6 9.3
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Topography Impact of the vadose zone type Conductivity (hydraulic)
Range Original Mean Modified Geological
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Original Mean Modified Range Original Mean Modified
slope (%) rating NO
3 mg=L rating formation usual NO
3 mg=L rating (m/day) rating NO
3 mg=L rating
rating
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02 10 64.6 10 Holocene deposits 8 66.5 8.4 0.011.3 1 41.8 6.1
26 9 Conglomerate 6 17.4 2.1 1.33.9 2 56.3 8.3
612 5 34.1 5.3 Flysch 3 33.4 4.2 3.98.6 4
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1218 3 20.4 3.1 Tyrrhenian sea terrases 6 38.8 4.8 8.613 6 67.3 10
18+ 1 Limestone 6 78.2 10 1324.2 8 17.4 2.5
Development and testing of three hybrid methods for the assessment of aquifer vulnerability

Marl 2 39.5 5 24.2+ 10

Pleistocene deposits 6 63.5 8
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296 A.K. Antonakos, N.J. Lambrakis

Table 2 Original and modified factor weights and correlation coefficients of the factors with the nitrates concentration
Drastic factors Original Spearmans q Kendalls s Modified factor
weight coefficient coefficient weight (derived from coefficients)
Depth to ground water 5 0.34* 0.19* 3.5
Recharge 4 0.05 0.01
Aquifer type 3 0.39* 0.22* 3.8
Soil type 2 0.00 0.02
Topography 1 0.47* 0.28* 5
Impact of the vadose zone type 5 0.35* 0.18* 3.5

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Conductivity (hydraulic) 3 0.08 0.03
Land use 0.33* 0.24* 4
*
p < 0.05.

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probabilities P of a binary variable into a continuous re-
Table 3 Land use ratings
sponse variable. The transformed response is predicted
Landuse type Mean NO3 Rating from one or more explanatory variables, and subsequently
concentration retransformed back to a value between 0 and 1.
Coniferous forest 15.9 1 The equation produced from a logistic regression proce-
dure has the general form

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Broad leaved forest 1
Mixed forest 1
eb0 b1 X 1 bn X n
Transitional woodland/shrub 17.1 2 P 3
1 eb0 b1 X 1 bn X n
Principally agricultural land 26.5 3
on
Sclerophylous vegetation 32.0 4 For the computation of slope coefficients, a more gen-
Mineral extraction sites 4 eral method than ordinary least squares, valid for both bin-
Natural grassland 5 ary and continuous variables as input data, the Maximum
Non-irrigated arrable land 5 Likelihood Estimation (MLE), is used. Maximum Likelihood
rs

Pastures 5 optimizes the likelihood that the observed data would be

Olive groves 41.7 6 produced from a given set of slopes. It is an iterative proce-
Road and rail networks 50.9 7 dure available in the more complex statistical software
packages. A function called the log likelihood (l) of the
pe

Fruit trees 53.4 8

Sport and leisure facilities 8 overall regression model is written as
Complex cultivations 67.7 9 X
n
Vineyards 67.2 9 l fy i  lnPi  1  y i  ln1  Pi g 4
Discontinuous urban fabric 72.0 10 i1

where yi are the 1, n binary observations and P are the pre-

dicted probabilities. The log of either P or 1  P will be neg-
use as dependent variables, then those variables must be in ative and therefore l is a negative number which is
r's

continuous or at least interval scale. The only way to ex-
press discrete variables like aquifer type, vadose zone type,
soil type and land use type is to use their DRASTIC ratings
which have an interval scale.
o
maximized by iteratively substituting estimates of P derived
from estimates of slopes and intersect. The log likelihood
may be alternately reported as the positive number G, the
2 log likelihood, which is minimized by the MLE procedure.

Using the DRASTIC parameters plus land use in a multiple An overall test of whether a logistic regression model fits
regression analysis for the study area revealed that residuals the observed data better than an intercept-only model
th

did not satisfy the limitation of normality as it can be seen
from the normal probability plot of residuals and the Shap-
iro-Wilk W statistic (W = 0.859, p = 0.0000) (Shapiro et al.,
1968). For this reason an alternative regression model suit-
Au
(where all slopes bi = 0), analogous to the overall F test in
multiple regression, is given by the overall likelihood ratio
(L):

able for the study area data, known as logistic regression
was used (Helsel and Hirsch, 1992). For the evaluation of
this method the independent variable must have a binary
form. Continuous parameters like nitrate concentration
can be transformed to binary by the use of a threshold. Val-
ues above that threshold are considered as presence (1) and
below that threshold as absence (0). The threshold value
used for this study was 50 mg/L. This value was chosen be-
cause it has a conventional meaning (potable limit) and be-
cause it divides the dataset in to two almost equal subsets
(109115). Logistic regression transforms the estimated
L G0  G 5
where G0 is 2 log likelihood of the intercept only model
and G is the 2 log likelihood of the tested model.
To compare nested logistic regression models (one model
is a more complex version of the other), similar to the par-
tial F tests in OLS regression, the test statistic is the partial
likelihood ratio LP:
LP Gc  Gs 6
where Gc is the 2 log likelihood for the more complex mod-
el, and Gs is the 2 log likelihood for the simpler model.
Development and testing of three hybrid methods for the assessment of aquifer vulnerability 297

py
co
al
on
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Figure 4 Distribution maps for the study area: (a) distribution of specific vulnerability (pollution risk) produced by the modified
DRASTIC method; (b) distribution of probability of nitrates exceeding the value of 50 mg/L (pollution risk) generated by the logistic
pe

regression method; (c) distribution of probability of nitrates exceeding the value of 50 mg/L generated by the indication kriging
procedure; (d) distribution of probability of nitrates exceeding the value of 50 mg/L (pollution risk) generated by the weights of
evidence method.

Another test to compare nested and especially non- concentration and therefore will be included in the logistic
nested logistic regression models, where partial likelihood regression model. They are the same parameters that were
ratios are not appropriate, is the Akaikes Information Crite- included in the final modification of the DRASTIC model as it
r's

rion (AIC) (Akaike, 1973). AIC includes a measure of model was decided based on Spearmans q and Kendalls s correla-
error (l) and a penalty for additional variables. tion coefficients (Kendall, 1975). This is an additional evi-
dence that those parameters are really meaningful for
AIC l k 7
aquifer vulnerability assessment.
o

where l is the log likelihood and k is the number of explan- For the selection of the best combination of the five sig-
atory variables. Better models are those with small AIC. nificantly related parameters, all possible subsets (nested
th

In the present study, for the evaluation of logistic regres-
sion, the seven parameters used by the DRASTIC model plus
the land use were used as independent variables. The
choices of these parameters made the results of logistic
Au
models) were compared based on their log-likelihood ratio
and the Akaikes Information Criterion (AIC). Results for
the five more favourable models based on the above men-
tioned criteria are presented in Table 5. Among those five

regression model directly comparable to those of the mod-
ified DRASTIC model and maintain the original physical base
of vulnerability assessment. Individual (univariate) relations
between those eight parameters and binary form of nitrate
concentration were investigated using logistic regression
(log-likelihood ratio and Walds statistics) (Wald, 1945) in
order to determine which variables were significantly re-
lated. Table 4 summarizes the results of this analysis. As
it is shown only five out of eight parameters, namely, Depth
to groundwater, Aquifre type, Topography (slope), Vadose
zone type and Land use, are significantly related to nitrate
models, the one containing all five parameters was chosen
because it has the better (smaller) log-likelihood ratio (G)
and a relatively small deference in AIC criterion with the
model containing the parameters, Depth to groundwater,
Topography (slope) and Land use which is the one with the
smallest AIC criterion. Another reason to maintain all five
parameters, besides statistical tests, is to insure that
parameters which have been proven to have an important
effect on aquifer vulnerability will not be excluded.
Using the estimates produced by the MLE procedure for
those five parameters, we conclude to the following equa-
298 A.K. Antonakos, N.J. Lambrakis

Table 4 Log-likelihood and Walt statistic values for the parameters used for pollution risk assessment
Log-likelihood v2 p-Value Wald t p-Value
Intersept 155.18
Depth to ground water 148.77 12.821 0.0003 12.10 0.0005
Recharge 155.18 0.009 0.9256 0.01 0.9256
Aquifer media 147.07 16.228 0.0001 14.93 0.0001
Soil media 155.00 0.360 0.5486 0.36 0.5490
Topography 138.11 34.146 0.0000 22.05 0.0000
Impact of the vadose zone media 148.71 12.959 0.0003 11.77 0.0006

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Conductivity (hydraulic) 155.12 0.125 0.7240 0.12 0.7241
Land use 143.30 23.768 0.0000 20.12 0.0000

co
Table 5 Values for the G and AIC statistics for the five preferable logistic regression subsets of parameters
Model definition Degrees of freedom G v2 p-Value AIC v2 p-Value
DATIL 5 265.83 44.54 0.00 277.83 44.54 0.00
DATL 4 266.35 44.02 0.00 276.35 44.02 0.00
DTL 3 267.06 43.31 0.00 275.06 43.31 0.00
ATL 3 267.93 42.44 0.00 275.93 42.44 0.00

al
TL 2 269.44 40.93 0.00 275.44 40.93 0.00
D is depth to groundwater, A is the aquifer type, T is the topography (surface slope), I is the vadose zone type L is the land use type, G the
2 log-likelihood and AIC the Akaikes criterion.
on
tion for the estimation of the possibility that nitrate con- where m(h) is the number of pairs of samples separated by
centrations will exceed 50 mg/L: the lag distance h. For the needs of the indicator kriging
rs

interpolation, a theoretical model must be fitted to the

e5:160:067D0:0426A0:192T0:225I0:279L
P 8
1 e5:160:067D0:0426A0:192T0:225I0:279L
where D is the depth to groundwater, A the aquifer type, T
pe
experimental data semivariogram. The theoretical model
chosen for the transformed nitrate concentration, based
on a least squares approach, was the spherical model

the topography (surface slope), I the vadose zone type and L (range = 3000 and sill = 0.12) with a nugget effect of 0.12,
the land use rating. as shown in Fig. 5. Using that theoretical semivariogram
By the use of this equation and the map calculator func-
tion of ArcGIS software,the distribution of the possibility
that nitrates concentration exceeds 50 mg/L was con-
structed (in raster format) (Fig. 4b). To examine the corre-
lation between logistic regression model predictions and
r's

actual nitrates occurrence,it is best not to use actual ni-

trate concentration at each sample point but the probability
of exceeding the threshold of 50 mg/L as it can be esti-
mated for each point of the study area by the use of indica-
o

tor kriging.
Instead of the actual value of a parameter indicator kri-
ging uses an indicator binary parameter created using a
th

threshold as follows:

1 if zx P zc
xx 9
Au

0 otherwise

where x(x) is the indicator parameter, z(x) is the initial con-

tinuous parameter (nitrate concentration) and zc is the
threshold value (50 mg/L).
Similar to simple kriging the expected semivariances can
be estimated from indicator data as follows (Webster and
Oliver, 2001; Goovaerts, 1997):

Xmh Figure 5 Semivariogram of the indicator parameter used for

1
czxc  fxx i ; zc  xx i h; zc g2 10 the interpolation of the probability of nitrates exceeding the
2  mh i1 value of 50 mg/L.
Development and testing of three hybrid methods for the assessment of aquifer vulnerability 299

and ArcGIS Geostatistical analyst extension, the distribution

of nitrates probability exceeding 50 mg/L was created (in
raster format) (Fig. 4c).
Correlation between logistic regression probability and
probability produced by indicator kriging was calculated
for the 244 sample points with a Spearmans r correlation
factor of 0.69 (Fig. 6b) and for the entire study area using
the Spearmans r correlation coefficient between all unit
cells of the two distributions in raster format (Bonham-Car-
ter, 1994), which was 0.62.

py
Weights of evidence

Weights of evidence is a quantitative method for combin-

ing evidence in support of a hypothesis. The method was

co
originally developed for a nonspatial application in medical
diagnosis. The first spatial application of Weights of evi-
dence was for mineral potential mapping with GIS (Asadi
and Hale, 1999; Bonham-Carter et al., 1988). Lately
Weights of evidence was used for environmental applica-
tions and specifically for aquifer vulnerability assessment
(Alberti et al., 2001; Baker et al., 2002).

al
The weights of evidence is the log-linear version of the
general Bayesian model which is based on the idea of prior
(unconditional) and posterior (conditional) probability. In
on
a raster based approach if the area of the unit cell is u
and the area of the base map (T) is A(T), then A(T)/
u = N(T) is the area of the base map in unit cells. The num-
ber of training points (wells with nitrate concentration
above 50 mg/L) within the base map is denoted as N(D)
rs

which is always an integer number, and independent of u.

Suppose an indicator pattern, used for prediction of points
with nitrate concentration above 50 mg/L, is denoted by
pe

B, then A(B) is the area where B is present and A(B)/

u = N(B) the same area expressed in unit cells. Similarly
NB is the area expressed in unit cells where B is absent.
The prior probability P(D) per unit area that the region occu-
pied by the study area containing a deposit (a point where
nitrate concentration is above 50 mg/L) is assumed to be
constant equal to the training points density:
ND
r's

PD 11
NT
The posterior probability of a deposit given the presence
of an indicator pattern will either increase or decrease (as
compared to the prior probability). Given the presence of
o

an evidential theme B, the posterior probability, P(DjB),

can be calculated from the prior probability, P(D), by
th

PBjD
PDjB PD  12
PB
A similar expression can be derived for the posterior
Au

probability of a deposit occurring given the absence of B

Figure 6 Scatter diagram for the 224 ample points of the
study area between: (a) specific vulnerability (pollution risk) PBjD
PDjB PD  13
produced by the modified DRASTIC method and groundwater PB
nitrates concentration (logarithmically transformed); (b) prob- Using the odds form, the logit transformation and alge-
ability of nitrates exceeding the value of 50 mg/L generated by braic manipulations, we can obtain an equation giving the
the logistic regression method and probability of nitrates probability of a deposit occurring given the presence of an
exceeding the value of 50 mg/L generated by the indication indicator pattern B in logit form: !
kriging procedure; (c) probability of nitrates exceeding the PBjD
value of 50 mg/L generated by the weights of evidence method logitDjB logitD logit ) logitDjB
PBjD
and probability of nitrates exceeding the value of 50 mg/L
generated by the indication kriging procedure. logitD W 14
300
Similar algebraic manipulations lead to logit of odds for
the conditional probability of D given the absence of the
indicator pattern B:
! Another important consideration for the correct applica-
PBjD
logitDjB logitD logit ) logitDjB
PBjD
logitD W  15 with a Bayesian model. CI is always violated to some degree
If we assume that we have n indicator patterns, the
above equations take the form:
X
n ble pairings of the binary maps being combined using the
logitDjB1 \ B2 \ . . . Bn logitD W 16 v2 independence statistical test between predicted and ob-
i1
and
X
n
logitDjB1 \ B2 \ . . . Bn logitD W 17
i1
Weights W+ and W are estimated from the measured
association between known points where nitrate concentra-
tion is above 50 mg/L and the values on the maps to be used
as predictors. The hypothesis is then repeatedly evaluated
for all possible locations on the map using the calculated
weights, producing a pollution potential map in which the
evidence from several map layers is combined.
For the evaluation of weights of evidence in the study
area, a model in the form of an extension for ArcGIS soft-
ware, called ArcSDM (Kemp et al., 2001; Sawatzky et al.,
2004), was used. The ArcSDM model can be applied to evi-
dential themes (indicator patterns) with binary (presence/
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absence) classes, or to multi-class maps. Binary evidence
is relatively simple to interpret and produce weights with
smaller variances, and is therefore more stable. Neverthe-
pe
less most datasets used for vulnerability assessment are
multi class or continuous. For example geological maps,
even after they have been simplified, usually comprise sev-
eral units and parameters like groundwater depth or aquifer
recharge are continuous and the only possibility is to group
their values in several classes.
Weights calculated for a small number of classes are
more robust than the ones calculated using a large number
r's
of classes, and this is particularly critical when a relatively
small number of points are in the training data. On the other
hand, including more classes may reflect the real picture of
favourable or unfavourable evidence with more precision.
o
Considering the above comments, it may be assumed that
DRASTIC classification of the parameters used for aquifer
th
vulnerability assessment must be satisfactory for the appli-
cation of the weights of evidence model. Furthermore, the
classification arisen after the first step modification of
DRASTIC method due to the fact that classes for continuous
Au
variables are minimized to those statistically independent
must be even more suitable. Land use parameter was
grouped into seven classes according to the rating of each
original class and flysch aquifer type was grouped with con-
glomerates aquifer due to the lack of training points in the
flysch aquifer type which takes up a very small part of the
study area namely 3 km2. The grouping of the two aquifer
types was based on the similarity of their original ratings.
Based on the fact that both Spearmans r correlation factor
and log-likelihood ratios of simple logistic regression indi-
cate that only four (out of seven) factors of the DRASTIC
A.K. Antonakos, N.J. Lambrakis
model plus the land use factor are statistically correlated,
these factors were included in the weights of evidence
model as well.
tion of weights of evidence is conditional independence (CI)
that is assumed to exist when combining two or more maps
and the question is what degree of violation is acceptable.
CI can be checked with statistical tests in two ways. The
first method involves testing pairwise CI between all possi-
py
served number of deposits. Multiclass maps containing n
number of classes can be encountered as n binary maps with
each class being present in each binary map, but they pro-
co
duce a huge number of possible pairs making the method
practically not applicable for multiclass maps. The second
method involves a simple overall statistical test based on
the ratio of total number of observed and predicted depos-
its. Values over 0.85 may indicate a problem. A more sophis-
ticated overall independence test proposed by Agterberg
and Cheng (2002) uses one tail v2 statistical test for the
al
ratio:
NDcalc  NDobs
18
sNDcalc 
on
where N(D) is the number of observed deposits, N(D)calc the
number of predicted deposits, and s[N(D)calc] the standard
deviation of N(D)calc. The number of predicted deposits
can be determined by adding together the product of the
area in unit cells N(A), times the posterior probability P
for all polygons (or pixels in a raster based approach) on
the map, thus
X
n
NDcalc P k  NAk 19
k1
After conducting the overall independence test for the
model containing the five aforementioned parameters, a ra-
tio of observed to predicted number of deposits with a value
of 0.695 was obtained indicating conditional dependency
while Agterberg and Chung test also indicated that condi-
tional independency hypothesis should be rejected. The
two parameters having greater spatial dependency are
those of vadose zone type and aquifer type as they are both
resulted from the geological map of the study area. Conse-
quently, the parameter among those two with the smallest
influence (based on correlation factor), namely vadose zone
type, was decided to be excluded from the model. After the
exclusion of the vadose zone parameter, the observed to
predicted number ratio became 0.87 indicating a small but
acceptable violation of CI and the Agterberg and Chung test
also indicated that conditional independency hypothesis
should not be rejected.
W+, W and weight difference C for all classes of the four
parameters participating in the final weights of evidence
model are illustrated in Table 6. Large values of C indicate
greater influence of the specific class to model results and
small values of C variance indicate more reliable results
for the specific class.
Correlation between the response theme of posterior
probability resulting from weights of evidence model
Development and testing of three hybrid methods for the assessment of aquifer vulnerability 301

Table 6 Values of W+, W, C and their variances used for the weights of evidence model
Class Area (km2) Training points W+ s(W+) W s(W) C s(C)
Depth to ground water
015 m 532.0 23 1.111 0.213 0.788 0.123 1.899 0.246
1523 m 162.3 19 0.033 0.244 0.007 0.113 0.040 0.269
>23 m 208.5 67 1.242 0.148 0.758 0.159 2.000 0.218

Aquifer type
Conglomerate aquifers + Flysch aquifer 128.2 1 2.835 1.004 0.161 0.104 2.995 1.009

py
Marl aquifer 335.3 10 1.496 0.321 0.430 0.111 1.926 0.340
Pleistocene aquifers 107.5 25 0.786 0.228 0.150 0.115 0.936 0.256
Holocene aquifers 189.1 72 1.500 0.150 0.921 0.169 2.421 0.226
Karstic Aquifer 142.5 1 2.970 1.004 0.188 0.104 3.158 1.009

co
Topography
06 374.9 4 2.545 0.503 0.593 0.109 3.139 0.514
612 166.7 3 2.017 0.583 0.204 0.105 2.221 0.592
>12 360.8 102 1.053 0.117 2.350 0.380 3.403 0.398

Land use
Coniferous forest + broad leaved 356.6 3 1.776 0.585 0.150 0.105 1.926 0.594
forest + mixed forest + transitional

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woodland shrub + land principally
occupied by agriculture
Schlerophylous vegetation + mineral 99.9 12 0.088 0.308 0.011 0.109 0.099 0.326
extraction sites
on
Natural grassland + non-irrigated 119.0 10 0.484 0.330 0.065 0.108 0.549 0.348
arrable land + pastures
Olive groves 26.9 1 1.354 1.019 0.027 0.103 1.381 1.024
Fruit trees + sport and leisure facilities 193.3 73 1.407 0.148 0.929 0.172 2.336 0.227
rs

Complex cultivations + vineyards 8.1 3 1.394 0.730 0.021 0.104 1.415 0.738
Discontinuous urban fabric 37.1 7 0.449 0.420 0.025 0.106 0.474 0.433
 
W logit PBjD .
pe

PBjD
 
W  logit PBjD .
PBjD
C = W+  W.
s = variance.

(Fig. 4d) with the probability of nitrate concentration background for the creation of hybrid methods for the
exceeding the value of 50 mg/L which was obtained from assessment of pollution risk of an aquifer if a hydrochem-
indication kriging, as it was discussed in the previous para- ical database from samples points of that aquifer is
r's

graph, was tested based on Spearmans r factor. The value available.

of r was 0.68 for the 224 sample points, slightly higher than The utilization of simple statistical quantities like arith-
those of modified DRASTIC methodology and comparable to metic mean or simple statistical tests like tests of depen-
the one obtained from logistic regression. However, the cor- dency and correlation between parameters used as
o

responding r factor for the entire study area was signifi- predictors of aquifer pollution risk and hydrochemical
cantly smaller, namely 0.56. The significant difference parameters can lead to DRASTIC method modifications,
th

between the two correlation factors denotes that a weight
of evidence method probably produces poor predictions in
areas where there are no available training points. As it
can be seen from the scatter diagram of Fig. 6c, between
Au
which may predict aquifer pollution risk more accurately
than the original model.
More complicated statistical methods like logistic regres-
sion or weights of evidence can make use of DRASTIC param-

posterior probability resulted from weights of evidence
model with the probability of nitrate concentration exceed-
ing the value of 50 mg/L, which was obtained from indica-
tion kriging for the 224 sample points. There is a gathering
of posterior probabilities to edge values probably reflecting
the binary nature of the weights of evidence model.
Conclusionsdiscussion
DRASTIC model originally used for intrinsic aquifer vulner-
ability assessment can be used as an initial theoretical
eters, classification and rating for the production of
pollution risk distribution with the form of probability of
exceeding a certain pollutant (i.e. nitrates) value achieving
fair correlation with obtained values of the specific
pollutant.
Table 7 demonstrates the Pearsons r correlation factors
between pollution risk estimated from the three above
developed hybrid methods with the nitrates concentration
for the 224 sample points as well as for the entire distribu-
tion of these parameters for the whole extent of the study
area.
302
Table 7 Pearsons r correlation factors between estimated values of aquifer pollution risk and actual nitrates occurrence for
the three methods used for pollution risk assessment
Pollution risk model definition
Modified DRASTIC approach (Panagopoulos et al., 2006)
Logistic regression model
Weights of evidence model
As it can be seen the more complicated statistical meth-
ods provide a higher correlation factor than the method pro-
posed by Panagopoulos et al., but a significantly smaller one
for the entire distribution. That piece of evidence can be
attributed to the fact that both logistic regression and
weights of evidence methods are clearly data driven and
produce relatively poor estimates in areas where few or
no sample points exist. On the other hand, Panagopoulos
et al.s method preserving more of the original DRASTIC
model subjectivity provides more reliable results in areas
with missing data points.
However, because the entire analysis procedure is based
upon the occurrence of one specific pollutant namely ni-
trates, it remains to be investigated if the three above
developed methods attain the same success in the estima-
tion of specific aquifer vulnerability for other common pol-
lutants like pesticides or heavy metals.
rs
Acknowledgements
pe
The authors thank two anonymous reviewers for their kind
and helpful comments and suggestions for improving the
manuscript and Mr. Richard Boswell for syntax and grammar
review of the manuscript prior to submission. This research
was conducted under the K. Karatheodoris project,
funded by the Research Committee of the University of
Patras.
r's
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