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Groundwater hydrogeochemistry of Mateur Alluvial Aquifer (Northern

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DOI: 10.4172/2325-9647.1000128

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Tlili-Zrelli et al., J Hydrogeol Hydrol Eng 2016, 5:1
http://dx.doi.org/10.4172/2325-9647.1000128
Research Article
Groundwater hydro-
geochemistry of Mateur
Alluvial Aquifer (Northern
Tunisia)
Besma Tlili-Zrelli1, Moncef Gueddari1, Rachida Bouhlila2 and
Oueslati Mohamed Naceur3
Abstract
The sustainable management of the ground water resources of the
Mateur alluvial aquifer (Northern Tunisia), which is threatened by
salinization related to the infiltration of saline waters of Ichkeul lake
in the discharge zone, is carried out by integrating, the geochemical
data, presented in the form of GIS-based geochemical maps, the
hydrogeochemical and the multivariate statistical methods, to
understand the spatial and temporal vaiation of water mineralization
and assign the major hydrochemical processes controlling its
composition. Water samples were collected from 40 sites in wet and
dry season, and analyzed for temperature, pH, salinity, dissolved
oxygen, electrical conductivity and major ions.
This study reveals that the origin of the groundwater mineralization
was controlled by several coexisting processes, including : water
origin (leaching of low mineralized water in the recharge zone
and salt water into decharge zone), dilution in the wet season and
evaporation in the dry season, thickness, grain size and lithology of
the unsaturated zone. It’s noteworthy that the water-rock interaction
does not contribute significantly to the solutes aquisition since
minerals within aquifer are sparingly soluble. The spatial distribution
maps of the major ions contents, especially Cl- and Na+, are similar
with that of salinity, which increases down gradient. The principal
component analysis (PCA), demonstrates that groundwaters are
divided into two main groups: Moderately to weakly mineralized
waters with Ca-Na-Cl and SO4-Ca-Na-HCO3-Cl facies, which are
those of natural recharge area of ​​the aquifer : Highly mineralized
waters, with NaCl facies, characterizing the down Stream part,
which is influenced by Salt water infiltration, from El Melah river,
Ichkeul marshes and salty soils).
Keywords
Groundwater; Alluvial aquifer; Salinization; Geochemistry; Mateur;
Tunisia
Introduction
The chemical composition of groundwater is controlled by
several natural factors including aquifer lithology, interaction
with soils and geological formations of the vadose zone, as well as
the relative groundwater flow velocity and the residence time [1].
In addition, anthropogenic activities such as overexploitation of
*Corresponding author: Besma Tlili-Zrelli, Université Tunis El Manar, faculté des
sciences de Tunis, UR géochimie et géologie de l’environnement, 2092, Tunis,
Tunisie; E-mail: besma_fst@yahoo.fr
Received: November 14, 2015 Accepted: December 15, 2015 Published:
December 21, 2015
All articles published in Journal of Hydrogeology & Hydrologic Engineering are the property of SciTechnol, and is protected by
International Publisher of Science, copyright laws. Copyright © 2016, SciTechnol, All Rights Reserved.
Technology and Medicine
Journal of Hydrogeology &
Hydrologic Engineering
a SciTechnol journal
groundwater resources, agriculture and industry have an impact on
the groundwater quality [2,3].
Understanding the principal processes that control groundwater
chemistry is either crucial, in terms of sustainable management of
groundwater resources, or scientifically challenging, especially in
complex geological and hydrogeological settings [4]. In Tunisia,
where the climate is dry over most of its territory, water resources
are both scarce and in equally a parted in time and space. The quality
of water resources is being increasingly degraded as a consequence
of its intensified exploitation, groundwater salinisation, exploitation
of non-renewable deep aquifer, and pollution. Northern Tunisia is
characterized by a Mediterranean climate which receives the largest
amount of rainfall (more than 400 mm / year) and includes the main
rivers in Tunisia. Consequently, it has about 55% of groundwater
resources from phreatic aquifers and only 18% from deep aquifers
[5].
The quaternary alluvial aquifer is a crucial water resource of
the Mateur region supporting local domestic and agricultural water
supply. Despite the importance of groundwater in Mateur plain, a few
studies were conducted about the natural phenomena that govern the
groundwater chemistry in the area. Previous studies have reported its
nitrate contamination [6,7,12].
In the present study, water samples were collected from 40 sites
in wet and dry season, and analyzed for temperature, pH, salinity,
dissolved oxygen, electrical conductivity and major ions. Distribution
maps of chemical parameters, Piper diagram [8], plots of chemical
parameters and geochemical modeling PHREEQC [9], are used 1)
to determine the hydro chemical characteristics of groundwater, in
dry and wet season, 2) to study the causes of spatial and temporal
variation of the groundwater salinity and 3) to identify major
natural and anthropogenic process governing alluvial groundwater
geochemistry
Site Description
Location and climate
The Mateur Plain is located in Bizerte region, in the North
of Tunisia (Figure 1) and has a surface area of 260 Km2 in the vast
Ichkeul catchment (2600 Km2). The climate of the area studied is
typically Mediterranean, sub humid with a considerable variation
in mean monthly temperatures: the coldest month is January, with
a mean temperature of 11 °C and the hottest is August, with a mean
temperature of 27°C. The mean annual precipitation in the area
is 570 mm and the potential evapotranspiration values stand at
approximately 1800 mm/year.
Geology and hydrogeology
The Mateur plain is characterized by distinctive lithostratigraphic
units i.e., Trias, to Quaternary age (Figure 1). The stratigraphic
sequence primarily consists of carbonate formations which
characterize Tertiary deposits of Ichkeul Mountains. In the plain
of Mateur, outcrops prior to Quaternary age are found only on
the three Campanian hills of Sidi Mbarek, Mateur and Ras El Ain
[10]. The Quaternary and recent alluvium cover the major part of
Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.
Figure 1: Location, geology and sampling points of the study area [11,12].
the plain and are consisted by silt and detrital formations. In these
alluvium sediments, the existence of a multilayered aquifer system
is considered: confined and unconfined aquifers as a result of the
variability of textural and structural conditions of the alluvial beds.
This alluvial aquifer consists of alluvial (sand and gravel), eolien
(fine- grained sand) and minor lacustrine (sandy clay) deposits and
refers to Quaternary formations which are unevenly arranged on top
of the Miocene sediments (Mateur - Ras E Ain) where exists a deep
confined aquifer which consists of limestone, marl and clay (Figure 2).
Alluvial and limestone aquifers are interconnected and form a single
hydrogeological unit [13]. For this work, the groundwater samples
were taken from alluvial aquifers. The main sources of recharge to
the groundwater are rainfall infiltration, leakage of rivers (Joumine,
Tine, Sejnane, Melah, Rezala). The groundwater flow in Mateur
aquifer was determined by water level measurements taken in about
twenty water supply wells (Figure 3). Groundwater flow direction is
roughly oriented South-North and Southeast Northwest directions
in the upstream part of the plain, but in the downstream part, it’s
strongly controlled by the draining action of the Joumine River.
Piezometric level is higher during wet season than during dry season.
Water loss from the aquifer is through discharge to the lake Ichkeul,
pumping for irrigation and direct evaporation in areas with low
hydraulic gradient and poor permeability. The water table generally
lies within 8-10 m of land surface, allowing additional groundwater
Volume 5 • Issue 1 • 1000128
doi:http://dx.doi.org/10.4172/2325-9647.1000128
loss via evapotranspiration. Transmissivity values range from 0 to
60 10-4 m2/s and from 60 to 32010-4 m2 /s in the alluvial aquifer and
the limestone aquifer respectively. Groundwater abstracted from
the Mateur alluvial aquifer is used in domestic and agriculture
purposes.
Materials and Methods
Groundwater sampling and analysis
Groundwater samples were obtained from monitoring wells in
the alluvial aquifers. A total of 80 samples were collected in wet and
dry season. The piezometric level, pH, electrical conductivity (EC),
dissolved oxygen and temperature were measured in situ.
Samples were kept at 4 °C for their subsequent chemical analyses.
Afterwards, a split of the sample was filtered through a 0.45 µm
Millipore filter. Nitrate, nitrite, ammonium and phosphorus were
performed by colorimetric methods, described by Rodier [14].
Chloride was determined by standard AgNO3. Sulfate (SO42-) content
was measured by the gravimeter method using BaCl2. Sodium (Na+)
and potassium (K+) were measured by flame photometry and calcium
(Ca2+) and magnesium (Mg2+) with atomic absorption. Alkalinity was
determined by titration with HCl. The quality of chemical analysis
was checked by doing an ionic mass balance, accepting an error lower
than 5%.
• Page 2 of 8 •
Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.

doi:http://dx.doi.org/10.4172/2325-9647.1000128

Figure 2: Hydrogeological cross sections [8].

[a] [b]
Figure 3: Piezometric maps of Mateur plain: (a) Wet season (b) Dry season.

Volume 5 • Issue 1 • 1000128 • Page 3 of 8 •

Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.

doi:http://dx.doi.org/10.4172/2325-9647.1000128

Hydro-geochemical methods
The groundwater samples were classified into water types based
on the dominant anion (or cation) exceeding 50% of total anionic
(or cationic) charge Piper. Speciation and saturation state modeling
using the program was performed to evaluate the possibility of
solubility control by several dissolved specie. Positive values indicate
precipitation or a stable condition for minerals; zero value indicates
that the solution is in equilibrium with a mineral; and negative values
indicate dissolution of a mineral [15].
Multivariate Statistical Analyses
Multivariate statistical analyses are increasingly being used to
analyze water quality data analyses often bring out information that is
not easily deciphered using univariate statistics [16]. There are several
multivariate statistical techniques including correlation matrix,
principal component analysis (PCA) and cluster hierarchical
analysis (CHA). In this study, only PCA was carried. The PCA was
used as a quantitative and independent approach for groundwater
classification enabling grouping of the groundwater samples
and making of correlations between chemical parameters and
groundwater samples, respectively [17]. The PCA is a multivariate
statistical technique used for data reduction and for identifying
patterns within large set of variables [18]. All mathematical and
statistical computations were made using Excel 2007 (Microsoft,
2007) and a statistical computer code “Andad” [19]. In order
to avoid erroneous results caused by the large variance in the
parameters distribution, the above statistical analyses are applied
on experimental data standardized to a range of -1 to 1, using
a following equation zi = xi - mean/s [20] where zi indicates the
standardized value, xi represents the data for variation, s the
standard deviation of the same variable [21,22].
Results and Discussion
General hydrochemistry
Groundwater samples were collected in the dry (October 2008)
and wet (May 2008) seasons in order to capture seasonal variability
in water quality. Statistical summaries of the parameters analyzed for
this study are presented in Table 1. The pH values of groundwater
in the study area varied between 7.02 and 9.08 in dry season and
between 6.18 and 8.39 in wet season. These pH values indicate the
neutral to slightly alcalin aspect of water. The temperatures reflected
the seasonal pattern showing higher values in the dry season. It varied
from 18.2 to 26.7 °C in the dry season and from 18.9 to 25.6 °C in the
wet season.
The spatial distribution maps of salinity (Figure 4a) show that
the lowest values ​​are registered, in wet and dry season, in northwest
and southwest part of the aquifer, which correspond to the natural
recharge zone (dilution effect), with a trend of increasing with the
flow direction. The higher salt loads are linked to the leaching of salts
from the Ichkeul marshes and salty soils located in south of Ichkeul
and to weathering of gypsiferous formation of Messeftine Montain in
the south east part of the aquifer.
The order of the cation abundance is Na>Ca>Mg>K in wet and dry
season, whereas the order of the anion abundance is Cl>SO4>HCO3
in wet and dry season.
Groundwater geochemical characteristics and evolution
Groundwater samples were collected in wet and dry season
in order to seize a seasonal variability in water geochemistry. Na
and Cl show a strong positive correlation with salinity and among
themselves (Figures 5a and Figure 6a) indicating that these ions seem
to be dominant in groundwater mineralization process and have a
same origin: the dissolution of halite occurring in saline surface
deposits in March around Ichkeul lake and salty soils.
The spatial distribution maps of Na+ and Cl- levels show that
the highest values characterize the northeastern part of the aquifer
and the south part of the Ichkeul Mountains (Figure 4b and 4c).
An increasing trend with the flow direction is registered, especially
during the dry season.
A cross plot of Mg++ with Ca++ (Figure 5c) showed a good
correlation suggesting a same origin which is dissolution of calcite.
Groundwater samples are above line 1:1 indicating that the calcium
does not come only from the dissolution of calcite. Furthermore, a good
positive correlation 2Ca++ versus 2 HCO3- + SO4- (Figure 7) shows that
the calcium comes, in addition to the dissolution of the calcite (Eqn 1),
from the dissolution of gypsum following (Eqn 2), where dissolution of
one mole of calcite and one mole of gypsum put into solution two moles
of Ca++, one mole of SO4-- and two moles of HCO3-.
CaCO3 + H2O + CO2 (g) Ca ++ + 2 HCO3- (1)
CaSO4 + 2 H2O Ca + SO4 + 2 H2O
++ --
(2)
Ca and SO4 are strongly correlated (Figure 5c), showing that
sulfate would have a common origin with Ca via sulfato-calcic
minerals, but it has different geochemical behavior with calcium
especially in salt water [23]. A positive relationship between SO4-- and
salinity (Figure 6c) is in favor of sulfate conservation in solution.
Table 1: Statistical summary of hydrochemical parameters

Dissoved Oxygen (DO) varied between 0.6 and 5.2 mg/l in dry   Wet season (May) Dry season (October)
season and between 1.2 and 7.6 mg/l in wet season. This temporal   unit min max sd min max sd
variation is under the control of the depth of the water table, the Cl- mg/l 67.45 2406.90 524.66 106.50 4402.00 844.89
recharge rate, the transfer speed of oxygenated water from upstream SO4-- mg/l 223.53 2483.48 497.45 221.89 3591.36 583.38
to downstream, and the temperature. Electrical Conductivity (EC) HCO3- mg/l 54.92 622.40 150.35 86.65 693.19 146.93
varied considerably from 769 to11900 µs/cm and from 887 to 13180 Ca++ mg/l 20.00 480.00 82.33 10.00 763.40 135.97
µs/cm of 2801 µs/cm in wet and dry season respectively. Na+ mg/l 49.00 1728.00 376.45 39.33 2576 491.23
Mg++ mg/l 12.70 140.00 27.33 11.25 170.13 40.3
The salinity of the alluvial aquifer ranged between 0.1 and 4.5
K+ mg/l 0.78 101.60 17.84 0.00 169.00 29.88
g/l in wet season and 0.1 to 8.4 in dry season. The highest values are
​​
T °C 16.20 26.80 2.16 18.20 26.70 1.98
recorded during the dry season (October), while the lowest values ​​are
cond ms/cm 0.54 8.64 1.94 0.72 14.59 2.98
recorded during the wet season (May). The slight variation is due to
the dilution effect with fresh water in the recharge areas during the Sal g/l 0.41 6.55 1.47 0.54 11.07 2.26

wet season, and the direct evaporation, during dry season, in areas pH 6.18 8.39 0.39 7.13 9.08 0.33

with low hydraulic gradient and poor permeability. O2 mg/l 1.20 7.60 1.36 0.60 5.20 1.09

Volume 5 • Issue 1 • 1000128 • Page 4 of 8 •

Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.

doi:http://dx.doi.org/10.4172/2325-9647.1000128

Figure 4: Spatial distribution maps of (a) salinity, (b) Chloride, (c) Sodium

Volume 5 • Issue 1 • 1000128 • Page 5 of 8 •

Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.
Figure 5: Plots of majors ions (a)Cl versus Na, (b)Mg versusCa, (c) Ca versus SO4.
Figure 6: Plots of major ions with salinity (a) Na versus salinity, (b) Ca versus salinity, (c) SO4 versus salinity.
A plot of Na+ + K+ - Cl- in meq/l against (Ca++ + Mg++) -
(HCO3 + SO4--) in meq/l (Figure 8) shows negative slope that suggests
-
an exchange with cations in alluvial clay [17] following Eq 3.
XNa + K+ XK + Na+
Saturation index
Changes in saturation state are useful to distinguish different stages
of hydrochemical evolution and help to identify which geochemical
reactions are important in controlling water chemistry [24]. Most of
groundwater samples are saturated and oversaturated with respect to
Calcite indicating that mineralization is not influenced by carbonate
minerals. However they are under saturated with respect to gypsum
suggesting that their soluble component Ca and SO4 concentrations
are not limited by mineral equilibrium and they contribute to
groundwater mineralization. Indeed, a positive correlation between
SI of sulfate minerals (gypsum) and salinity confirms the sulfate
enrichment of the aquifer from upstream to downstream (Figure 9).
Hydrochemical facies
The chemical data of the groundwater samples collected from the
study area are plotted on the Piper’s diagram (Figure 10). On the basis
Volume 5 • Issue 1 • 1000128
doi:http://dx.doi.org/10.4172/2325-9647.1000128
of this diagram, groundwater’s of the study area are classified into two
predominantly facies;
- A mixed facies with no dominant anions and cations: Ca-Na-
(3) SO4-Cl and Ca-Na-HCO3-Cl type;
- Na-Cl facies which characterize, discharge zone and well
influenced by leaching of salt deposits (Ichleul marsh, river El Melah
and salty soils).
Multivariate statistical analysis
The Varimax rotation reduces all of the variables to three different
PCs, which explains more than 74% of the total variance (Table
2). PC1, accounting 50.9 % of total variance, has a strong positive
loading for conductivity, salinity, Na, Cl, Ca, SO4 and Mg. This can be
attributed to a mineral component of the groundwater. PC2 explains
14.78 % of total variance with a strong loading with Ca and HCO3 and
moderate loading with Ca and SO4. PC3 explains only 10.08 % of total
variance and has a moderate loading with pH AND K. Furthermore,
the spatial distribution of the variables ‘chemical parameters and
individuals (samples) in the axe systems F1-F2 shows the presence of
two groups of waters: group I characterizes waters of wells strongly
correlated with major ions participating in water mineralization, and
• Page 6 of 8 •
Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.

doi:http://dx.doi.org/10.4172/2325-9647.1000128

The results of multivariate statistical analysis corroborated by geo-

chemical interpretations and GIS-based geochemical maps, show that
the dominant geochemical processes influencing the groundwater
mineralization are: i water origin (leaching of low mineralized water
in the recharge zone and salt water into decharge zone), ii dilution in
the wet season and evaporation in the dry season, iii thickness, grain
size and lithology of the unsaturated zone.
It’s noteworthy that the water-rock interaction does not
contribute significantly to the solutes aquisition since minerals
within aquifer are sparingly soluble. The spatial distribution maps of
the major ions contents, especially Cl- and Na+, are similar with that
of salinity, which increases down gradient. Using Piper diagram and
principal component analysis (PCA), two major types of groundwater
hydrogeochemical zonality were identified in the Mateur alluvial
aquifer: - the first hydrogeochemical trend, with low salinity,
characterizes the natural recharge zone, presenting a mixed facies
with no dominant anions and cations: Ca-Na-SO4-Cl and Ca-Na-
HCO3-Cl- the second trend , greatly mineralized, which characterize,

Table 2: Summarized the PCA results including the loadings and the Eigen
values of each PC.
Variables Axe 1 Axe 2 Axe 3
Figure 7: Geochemical relationship of (2 HCO3+ SO4) versus 2Ca. O2 -0.2423 -0.5308 -0.4097
Tre 0.2079 -0.7405 0.4553
pH -0.1885 0.3615 0.6011
Sal 0.9435 0.1214 0.1564
Cl- 0.9191 0.1328 0.1683
SO4-- 0.7863 -0.374 0.0012
HCO3- 0.4898 0.5861 -0.3874
Ca++ 0.8257 -0.3267 -0.0886
Mg++ 0.8061 -0.0856 -0.3457
Na+ 0.9028 0.158 0.2036
K+ 0.8512 0.0705 -0.0304
Eigen values 5.60 1.62 1.11
% Variance explained 50.93 14.73 10.08
% Cumulative variance 50.93 65.66 75.74

Figure 8: Geochemical relationship of (Ca + Mg) - (SO4 + HCO3- ) versus

(Na+K-Cl).

it’s situated in discharge zone and influenced by leaching of salt water

from Ichkeul marchs and salty soils; group II characterizes waters of
wells with mixed facies situated in the natural recharge zone (Figure
11).

Conclusion
In the present study, an attempt was made to understand the
spatial and temporal vaiation of groundwtaer mineralization of
Mateur alluvial aquifer and to assign the major hydrochemical
processes controlling its composition. Figure 9: Saturation index (SI) for calcite and gypsum plotted versus salinity.

Volume 5 • Issue 1 • 1000128 • Page 7 of 8 •

Citation: Tlili-Zrelli B, Gueddari M, Bouhlila R, Ouesleti MN (2016) Groundwater hydro-geochemistry of Mateur Alluvial Aquifer (Northern Tunisia). J
Hydrogeol Hydrol Eng 5:1.
Figure 10: Piper diagram.
Figure 11: Spatial distribution of the variables and individuals in the axes
system F.
discharge zone and well influenced by river El Melah and salty soils,
presenting geochemical facies chlorinated sodique NaCl.
The result of this study will be helpful for an effective water
management and a sustainable development of groundwater
resources in the Mateur region.
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Author Affiliations Top
1
Université Tunis El Manar, faculté des sciences de Tunis, UR géochimie et
géologie de l’environnement, 2092, Tunis, Tunisie.
2
Université Tunis El Manar, école nationale des ingénieurs de Tunis,
laboratoire de modélisation en hydraulique et environnement, 1002, Tunis,
Tunisie.
3
Commissariat régional de développement agricole, Ariana, Tunisie.
• Page 8 of 8 •