Journal of Hydrology 528 (2015) 249–263

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Journal of Hydrology
journal homepage: www.elsevier.com/locate/jhydrol

Hydrochemical changes due to intensive use of groundwater in the

carbonate aquifers of Sierra de Estepa (Seville, Southern Spain)
S. Martos-Rosillo a,1, F. Moral b,⇑
a
Instituto Geológico y Minero de España, Departamento de Investigación y Prospectiva Geocientífica, Urb. Alcázar del Genil, 4, Edificio Zulema Bajo, 18006 Granada, Spain
b
Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Carretera de Utrera km 1, 41013 Seville, Spain

a r t i c l e i n f o s u m m a r y

Article history: The carbonate aquifers of Sierra de Estepa, situated in southern Spain, are undergoing intensive ground-
Received 16 January 2015 water exploitation. Consequently, the volume of pumping surpasses the average recharge for periods of
Received in revised form 10 June 2015 several consecutive years. Under such conditions, nearby springs have either dried up or only function
Accepted 11 June 2015
during short time periods, after very rainy episodes followed by long droughts. During the brief periods
Available online 20 June 2015
This manuscript was handled by Corrado
when the springs are active, their water and the water extracted by pumping are calcium bicarbonates,
Corradini, Editor-in-Chief, with the with a spatial–temporal variability of their physico-chemical characteristics that is mainly conditioned
assistance of Dongmei Han, Associate Editor by the degree of functional karstification of each system. When the springs are inactive, the pumping
water gradually increases in salinity and becomes HCO3ClCaNa, ClHCO3NaCa and ClNa. Under the new
Keywords: conditions caused by so much pumping, the main factors determining the hydrochemical changes are
Carbonate aquifer the mixing of waters and the subsequent reactions of dissolution–precipitation between (1) the recharge
Intensive use coming from rainwater, (2) the hypersaline inputs from the clay-evaporite aquitards situated on the
Salinization edges and at the base of the aquifer, and (3) the water stored in each aquifer. The hydrochemical infor-
Sustainable management mation acquired allowed us to characterize and model the groundwater of these aquifers, to study the
causes of its great spatial and temporal variability, and explain the influence of exploitation. This research
shows that making sustainable use of water resources associated with carbonate aquifers calls for sound
knowledge of the relationship between the aquifer and other bodies of groundwater or surface water, the
hydrochemical quality of these possible inputs, and the vulnerability of the aquifer to exploitation, which
in turn is conditioned by the ratio between water reserves and recharge.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction deriving from the intensive exploitation of aquifers are concen-

Before submergible electropumps came into use and today’s
techniques of well drilling were developed, groundwater was a
practically non-exploited resource, and its use was sustainable. In
the past five decades, however (Burke et al., 1999; Llamas and
Custodio, 2003; Shah et al., 2007), the situation has changed dras-
tically. At present, groundwater is one of the most exploited natu-
ral resources below the earth’s surface (Zektser and Everett, 2004).
Depletion of groundwater, often accompanied by a deterioration in
water quality, is a common environmental problem in areas of
North America, Northern Africa, the Arabian Peninsula, Northern
China, India and Southeast Asia (Llamas and Custodio, 2003; Van
der Gun, 2012; Wada et al., 2010). In Europe, the main problems
⇑ Corresponding author. Tel.: +34 954349829.
E-mail addresses: s.martos@igme.es (S. Martos-Rosillo), fmormar@upo.es
(F. Moral).
1
Tel.: +34 958183143.
trated in the east and the south of Spain, where semi-arid climatic
conditions prevail. In this region, unlike others, most aquifers pla-
gued by problems due to intensive use are aquifers of a carbonate
nature. In this sense, we may underline that around the
Mediterranean Basin 50% of the population is supplied through
groundwater associated with carbonate aquifers (Margat, 2008),
as opposed to the 25% world average (Ford and Williams, 2007).
When an aquifer is exploited, pumping produces a decrease in
the water reserves, a reduction in natural discharge and/or an
increase in recharge from other bodies of water (Bredehoeft
et al., 1982). Hence, it is important to stress that the management
and hydrological planning of an aquifer will be conditioned, among
other aspects, by its renewal period (Custodio, 2003; Margat et al.,
2006; Margat and Thauvin, 1989; Martos-Rosillo et al., 2014), by
the possible deterioration of the water quality as a consequence
of its intensive exploitation (Vrba, 2003) and by environmental
problems stemming from the new hydrodynamic situation
(Sophocleous, 2003). Margat et al. (2006) define renewal period

http://dx.doi.org/10.1016/j.jhydrol.2015.06.021
0022-1694/Ó 2015 Elsevier B.V. All rights reserved.
250 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263
as the quotient between the volume of the aquifer storage
(reserves) and the average recharge. For these authors, it is a com-
parative concept, not absolute, and it is conditioned by numerous
factors such as aquifer thickness, drainable porosity and climatic
parameters (especially rainfall). In this regard, various authors pro-
pose different groundwater management strategies depending on
the renewal period for each aquifer (Margat and Thauvin, 1989;
Margat et al., 2006; Martos-Rosillo et al., 2014).
Water resources associated with carbonate aquifers are strate-
gic, supplying domestic water and serving as a resource for irriga-
tion and industry (Ford and Williams, 2007). Moreover, karstic
systems contribute significantly to increase the biodiversity pre-
sented in both, surface and underground (Goldscheider, 2012).
The particular hydrogeological characteristics of carbonate
aquifers, with heterogeneous porosity and permeability (White,
1999; Worthington, 1999; Hartmann et al., 2014), are made man-
ifest in the processes of infiltration (diffuse and/or concentrated),
fluxes in the saturated and non-saturated zones (rock matrix and
network of fractures and karstic conduits) and discharge (diffuse
and/or concentrated) (Bakalowicz, 2005; Kiraly, 2003). Such condi-
tioning factors can give rise to problems involving carbonate aqui-
fers much more quickly than when the exploitation involves a
detritic aquifer.
In carbonate aquifers with a well developed network of con-
duits, the zone of ‘‘dynamic storage’’ (the one above the level of
drainage of the principal springs) is drained very quickly, above
all if it is subjected to exploitation, given that the influence of
pumping is compounded by the high capacity of these aquifers
to empty via karstic springs. The long and frequent dry periods that
characterize arid and semi-arid regions and the exploitation of
these aquifers favor changes in the direction of the underground
flow, even when they are exploited below average recharge.
Under these circumstances, if the aquifers are in contact with the
sea or with bodies of surface or groundwater of poor quality, con-
tamination results. In turn, during periods when the springs
remain inactive, serious environmental problems may arise, affect-
ing the ecosystems associated with the natural dischange of these
systems.
The hydrochemical processes in carbonate aquifers in a natural
regime and their hydrogeological implications are well docu-
mented (Busenberg and Plummer, 1982; Cardenal et al., 1994;
Moral et al., 2008; White, 1988), yet the same is not true of
research about the deterioration of groundwater quality caused
by its intensive use. In most cases the focus is on coastal aquifers
undergoing advancement of the saline front (saltwater intrusion
into coastal aquifers) (Calvache and Pulido-Bosch, 1994; Grassi
and Tadolini, 1991; Pulido-Leboeuf, 2000; Sánchez-Martos et al.,
1999). There are reports of contaminated water entry affecting
agricultural activity (Edmunds and Walton, 1983; Llamas et al.,
1992). There are also a few detailed papers about the deterioration
of water quality due to the influx of poor-quality water (with high
salinity) coming from aquifer or aquitard materials in contact with
the carbonate aquifer exploited. In this sense, Rosenthal (1988)
studied the increasing flow of Ca-chloride brines from
deep-seated and confined reservoirs as a result of overexploitation
of groundwater in Israel. This author determined the spatial distri-
bution of areas where salinity increased as a result of the inflow of
deep brines into the aquifers. Pulido-Bosch et al. (1995) related the
progressive deterioration of water quality, with significant
increases in chloride, sulfate and sodium, with the groundwater
mining of the Crevillente aquifer (Alicante, southeastern Spain).
They studied the temporal evolution of temperature, electrical con-
ductivity of water, major ions and saturation indexes of calcite,
dolomite and gypsum. Near to here, Pulido-Bosch et al. (1998)
described an increasing salinity degree with depth in the carbonate
aquifer of Cid. The base of this aquifer is constituted by rocks with
halite and gypsum. Finally, Reynauld et al. (1999) studied the evo-
lution of piezometric levels, volume of pumped water, rainfall, and
groundwater chemical composition in Pinchinad Graben aquifer
(Mouans Sartoux, France) along four years. The authors observed
that the drop in the piezometric level caused the deterioration of
water quality because of the inflow of saline water from the
Triassic materials.
The use of multiple research techniques in this work has
allowed the modeling of hydrochemical processes and mixing of
waters caused by the exploitation as well as to establish the rela-
tionships between changes in water quality, the recharge rate
and the storage capacity for each investigated aquifer.
The zone investigated here takes in the carbonate aquifers of
the Sierra de Estepa (Sevilla province, southern Spain), considered
as typical models of aquifers subjected to an intensive use of
groundwater for urban and agricultural supply (Martos-Rosillo
et al., 2013). The abundant hydrogeological information generated
by means of different research projects carried out by the
Geological Survey of Spain (IGME, 2006) and the diverse exploita-
tion/recharge and recharge/reserve ratios of the systems studied
provide a very adequate arena for the approach we use, putting
forth measures oriented to manage and plan the sustainable use
of groundwater.
The work carried out allowed us to characterize and model the
hydrochemical evolution of the groundwater and study the causes
behind its noteworthy variability over space and time. In the frame-
work of this study, it is apparent that identifying and understanding
hydrochemical processes is key to modify the hydrodynamic condi-
tions of aquifers in order to achieve their sustainable use.
2. Study area
Sierra de Estepa is located in southern Spain, 120 km east of the
city of Sevilla (Fig. 1). This range is a small carbonate massif formed
by several outcrops of Jurassic limestones and dolostones.
Although the total exposed permeable surface is relatively small
(34 km2), the carbonate aquifers of Sierra de Estepa supply water
to some 36,000 people and around 600 ha of irrigation land
(Martos-Rosillo et al., 2013).
In Sierra de Estepa average precipitation during the studied per-
iod (1976–2006) and its associated standard deviation are
500 ± 150 mm/year. The months with the highest rainfall are
November, December and January. Three drought events occurred
during the analyzed period (1983–1986, 1990–1995 and 2004–
2006). The annually-averaged air temperature is between 15.9
and 17.6 °C, while the average annual potential evapotranspiration
is between 1190 and 1300 mm/year (1976–2006).
Geologically, Sierra de Estepa lies in the External Zone of the
Betic Cordillera, where the more competent Jurassic limestones
commonly constituted isolated ranges, surrounded by the
Antequera–Osuna Unit. Most of this unit is a mélange, and has a
mixed tectonic, halokinetic and sedimentary origin. It largely
involves Triassic clays, anhydrite, gypsum, halite, marls, and a
minor amount of Mesozoic–Miocene limestone and siliciclastic
rocks. It is a heterogeneous unit with a chaotic organization where
hardy blocks are enclosed in a matrix composed by clays and evap-
orites (Flinch et al., 1996; Pedrera et al., 2012; Ruiz-Constán et al.,
2012). The presence of hypersaline water associated to this geolog-
ical unit is historically well-known because it has been used to
obtain salt since the Roman times (Pérez, 2004). The distribution
of salt bodies and their associated hypersaline waters is heteroge-
neous and irregular within the Antequera–Osuna unit. The geo-
chemical signature of the water in the Antequera–Osuna aquitard
is mostly sulfated because of the gypsum prevalence.
The carbonate aquifers of Sierra de Estepa are composed by
200–300 m of massive limestone and dolomitic breccias at the
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263 251

Fig. 1. Hydrogeological map of Sierra de Estepa.

base. The limestones are very pure with 99% calcite and less than Table 1 shows the main hydrogeological characteristics of the
1% quartz (Ortiz, 1994). Five independent aquifers with different aquifers and indicates their annual water balance updated to
hydrogeological behavior are recognized in Sierra de Estepa: 2006. These aquifers are recharged by the infiltration of rainwater,
Becerrero, Mingo, Hacho, Águilas, and Pleites aquifers (Fig. 1). whereas discharge takes place mainly by pumping to satisfy the
252 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263

Table 1 balance of the aquifer, its size, and the bulk porosity of the sector
Main hydrogeological characteristics of studied aquifers of Sierra de Estepa. where the water level fluctuates (IGME, 2006; Martos-Rosillo,
Aquifer Becerrero Águilas Mingo Hacho Pleites 2008).
2
Outcrop area (km ) 26.2 4.4 0.65 1.65 1.5 Water exploitation in Águilas and Mingo aquifers entails a con-
Mean aquifer thickness (m) 400 350 200 200 200 tinued reduction of the water reservoir. A similar balance is found
Reserves (hm3) 397 56 1 4.7 5.1 for Hacho aquifer (with 0.33 hm3/year pumped and a recharge of
Transmissivity (m2/day) 117 2200 1700 1300 1700 0.30 hm3/year), which is progressively reducing the quality of the
Recharge (hm3/year) 5.6 0.99 0.17 0.34 0.27
Pumping (hm3/year)* 4.6 1.81 0.28 0.35 0.35
water (IGME, 2006; Martos-Rosillo, 2008). The progressive loss of
Outflow spring 0.7 0 0 0 0 water quality because of groundwater withdrawal has limited
Renewal Period (year) 71 57 6 14 19 the rate of exploitation of these aquifers.
⁄
Period 2003–2006.
3. Material and methods
population’s water supply and agricultural demand. Springs drain-
ing the Becerrero aquifer have a maximum flow of 200 L/s. In the A total of 135 samples of groundwater and 58 of precipitation
Águilas aquifer, before the spring drying up, the maximum regis- were collected in the period 2003–2006. The main sampling points
tered flow was 65 L/s (IGME, 2006). Boreholes have depths of are identified in Fig. 1. Coinciding with the sampling, in situ mea-
100–300 m. Most of them have been drilled by percussion, having surments were made of the electric conductivity, temperature
diameters of 250–400 mm and are entirely screened within the and pH of the water by means of a conductivity-meter and a
saturated zone. pH-meter, both brand WTW, and both equipped with integrated
In natural conditions, the groundwater flow in Becerrero aquifer temperature probes. The samples were analyzed at the laboratory
advances southward across the karstic network to springs 4–24, 8– of Geological Survey of Spain (IGME). The technical procedures car-
4 and 1–1 (Fig. 1), at heights between 466 and 467 m.a.s.l. At pre- ried out were electrometry, in the case of the electrical conductiv-
sent, the most important pumping sectors are grouped around ity and pH, atomic emission spectrometry for the determination of
these springs. The piezometric data available made it possible to K+ and Na+, atomic absorption spectrometry for Ca2+, Cl , Mg2+,
test the presence of a single water table in Becerrero aquifer NO3 , NO2 , Si and SO24 , and volumetry in the case of HCO3 .
(Fig. 2), which fluctuates coevally and homogeneously. The piezo- In addition, to have further hydrochemical information, we took
metric response after precipitation is fast. Intensive exploitation of into consideration 235 additional water samples collected previ-
the aquifer and the prolonged dry period induced a cumulative ously in the area under study by the Geological Survey of Spain
piezometric downfall, reaching more than 20 m below the springs and analyzed in the same laboratory.
in some periods. After intense rainy periods, the piezometric levels The analysis of hydrochemical data has enabled to develop a
recover and the springs flow again. preliminary model of processes and hydrochemical evolution of
In Águilas aquifer, and in natural conditions, the groundwater groundwater in Sierra de Estepa aquifers. Subsequently, this model
flows to the east, toward the Miocene and Quaternary rocks. The was tested and improved by hydrochemical modeling.
main natural discharge point of Águilas aquifer was Almarjal spring Data treatment of the hydrochemical database was carried out
(4), located 335 m.a.s.l. a spring that has been inactive for decades. using the program AQUACHEM 4.0 (Waterloo Hydrogeologic,
In Mingo, Hacho, Águilas and Pleites aquifers, abundant piezo- 2003), which incorporates the hydrochemical modeling code
metric information (Fig. 2) confirms an independent behavior, with PHREEQC (Parkhurst, 1995; Parkhurst and Appelo, 1999).
different piezometric levels and dissimilar temporal evolution. At PHREEQC is widely used, especially to solve problems related with
present, substantial exploitation of these aquifers induces a func- the hydrochemistry of carbonate rocks (Barberá et al., 2011;
tioning similar to a dammed deposit, where the recharge occurs Cardenal et al., 1994; González-Ramón et al., 2012; Ma et al.,
by rainwater infiltration and the discharge by water pumping. 2011; Moral et al., 2008; Plummer et al., 1990). In our case, this
Therefore, the piezometric fluctuation depends on the hydrological software made it possible to calculate the states of saturation of

Fig. 2. Evolution of piezometric levels and comparison with daily rainfall in Sierra de Estepa aquifers.
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263
the main mineral phases, the dissolution of CO2, and the processes
of evaporation/evapotranspiration, mixing and dissolution/precip-
itation of the main minerals.
The groundwater exploitation degree for each aquifer has been
analyzed by means of controlling the volume of pumping water
and spring discharge and calculating the recharge and the ground-
water reserves (IGME, 2006; Martos-Rosillo, 2008). Finally, the
hydrochemical evolution for all types of water has been related
to the renewal period of groundwater and the degree of exploita-
tion for each aquifer.
4. Results
4.1. Spatial variability of groundwater: major ions
2+ +
The value of the nCa /nNa ratio, the electric conductivity (EC)
and the concentrations of Cl , Na+, HCO3 and Ca2+ allowed us to
discern four groundwater groups. They are shown in Fig. 3, where
the samples are distinguished by different colors, according to the
source aquifer (Becerrero, Hacho, Mingo, Águilas and Pleites).
Meanwhile, Table 2 gives the main statistics regarding the major
ions, pH, and EC of the four groundwater groups.
Group I. These waters are fundamentally HCO3Ca, although in
some particular points and after drought periods the facies may
become HCO3Cl–CaNa (points near the contact between Jurassic
and Triassic materials) or HCO3–CaMg (only in the case of well
1-1). They are relatively low in mineralization (269 < CE < 813
lS/cm) and all 22 sample points pertain to the Becerrero aquifer.
Group II. The waters in this group are HCO3ClCaNa and
ClHCO3NaCa, and they are more mineralized than those of group
I (610 < CE < 1472 lS/cm). All the water points pertaining to this
group are associated with the aquifers of Águilas and Pleites,
except for one sample from well 8-4 (collected in November
1993) and two from well 1-37, in Becerrero aquifer.
Detailied analysis of the hydrochemical information of this
water group reveals that the groundwater from the Águilas aquifer
is most often of the type HCO3Cl–CaNa; notwithstanding, the
water facies is more often ClHCO3NaCa in periods of low water
level.
Fig. 3. Piper diagrams and nCa2+/nNa+ vs. electric conductivity of groundwaters of Sierra de Estepa aquifers.
253
Group III. In this case, the waters are sodium chloride facies, and
they are highly mineralized (2280 < CE < 9196 lS/cm). All these
water samples were obtained from well 44, situated in Mingo aqui-
fer, except for the two least mineralized samples, taken at the end
of the phase of execution of well 4-59, in the central sector of Sierra
de Becerrero, when detritic-evaporitic aquitards were drilled.
Group IV. The facies of this group is sodium chloride. With the
exception of a samplegathered at well 4-59, in Becerrero aquifer,
this group corresponds to well 42, situated in Hacho aquifer.
They are highly mineralized waters (3210 < CE < 14256 lS/cm).
4.2. Partial pressure of CO2 and saturation indexes of calcite, dolomite,
gypsum and halite
The mean values of partial pressure calculated from the water
samples taken at the main water points of Sierra de Estepa, in
ascending order, are presented in Table 3. The partial pressures
of apparent equilibrium of CO2 are between 10 2.5 and 10 1.6 atm.
As seen in Table 3, nearly all the water samples from Becerrero
aquifer are subsaturated in dolomite, gypsum and halite, and
slightly oversaturated in calcite. In the case of Águilas and Pleites
aquifers, the waters are saturated in calcite and dolomite, and sub-
saturated in gypsum and halite. Waters from Mingo and Hacho
aquifers are supersaturated in calcite, saturated in dolomite, and
subsaturated in gypsum and halite.
4.3. Temporal variability of groundwater
Figs. 4–6 reflect the temporal evolution of the physico-chemical
parameters of the waters sampled in different wells exploiting the
aquifers of Sierra de Estepa. The evolution of the piezometric level,
hydrograms of the springs when available (Fig. 4), and the daily
recharge in each aquifer, calculated in view of the soil water bal-
ance (Martos-Rosillo et al., 2013), are also included.
In the case of well 4-24, situated in Becerrero aquifer, the sam-
ple periods comprise 1977–2006 (Fig. 4A) and 2003–2006 (Fig. 4B).
From 1977 to 2006, the waters of well 4-24 presented an EC rang-
ing from 370 to 565 lS/cm, and they are of the type HCO3–Ca and
HCO3–CaMg. The periods in which the spring remains inactive
254 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263

Table 2
Main statistics on electric conductivity, pH and major constituents of Sierra de Estepa groundwaters (SD: standard deviation, VC: variation coefficient, N = number of analyses).

Parameter EC (lS/cm) pH HCO3 (meq/l) Cl (meq/l) SO24 (meq/l) Ca2+ (meq/l) Na+ (meq/l) Mg2+ (meq/l) NO3 (meq/l)
Group I
Average 483.68 7.53 3.67 0.68 0.46 4.16 0.60 0.59 0.34
S.D. 85.91 0.23 0.76 0.51 0.29 0.85 0.48 0.30 0.19
C.V. 17.76 3.11 20.75 74.74 63.61 20.46 80.76 51.73 56.66
N 260 260 260 260 260 260 260 260 260
Group II
Average 942.94 7.51 4.18 4.11 1.53 4.70 3.89 1.89 0.40
S.D. 153.81 0.23 0.83 1.20 0.44 0.83 0.88 0.53 0.10
C.V. 16.31 3.15 20.02 29.33 29.25 17.71 22.70 28.38 26.23
N 55 55 55 55 55 54 54 54 55
Group III
Average 3996.04 7.15 4.38 28.36 5.76 7.62 28.75 3.49 1.02
S.D. 1400.92 0.35 0.30 12.59 1.44 1.12 14.41 0.77 0.79
C.V. 35.05 5.023 7.039 44.41 25.04 14.72 50.14 22.24 77.42
N 26 26 26 26 26 26 26 26 26
Group IV
Average 9127.96 6.96 3.65 74.23 13.39 15.71 68.95 7.54 0.79
S.D. 2137.95 0.42 0.52 19.38 3.07 2.57 20.73 1.58 0.93
C.V. 23.42 6.046 14.33 26.10 22.94 16.37 30.06 21.01 117.60
N 29 29 29 29 29 29 29 29 29

Table 3
Average values of apparent partial pressure of CO2, saturation indixes, pH and temperature (°C) measured in situ, and contents in bicarbonates (mg/l) measured in the laboratory,
in the main water points of Sierra de Estepa.

Well ID Aquifer Log PCO2 pH Temp. HCO3 SI Calcite SI Dolomite SI Gypsum SI Halite
4-61 Becerrero 2.495 7.6 16.6 150.0 0.009 0.929 2.570 8.513
4-44 Becerrero 2.368 7.5 17.9 160.0 0.027 1.107 2.872 8.811
1-1 Becerrero 2.245 7.5 16.8 197.6 0.104 0.774 2.436 8.893
4-6 Becerrero 2.243 7.6 17.6 199.7 0.130 0.529 2.439 8.512
4-46 Becerrero 2.234 7.5 17.7 167.5 0.103 0.394 2.519 8.854
4-59 Becerrero 2.170 7.5 18.3 244.0 0.272 0.660 2.242 2.170
4-48 Becerrero 2.149 7.4 18.4 199.5 0.047 0.990 2.136 8.764
5-47 Becerrero 2.098 7.1 18.3 187.0 0.125 1.037 2.474 8.087
8-4 Becerrero 2.096 7.4 18.7 237.7 0.167 0.444 2.468 7.661
36 Pleites 2.093 7.4 18.6 254.6 0.128 0.077 1.600 6.036
44 Mingo 2.040 7.3 19.8 261.5 0.189 0.134 1.084 4.850
42 Hacho 1.990 7.2 20.7 229.4 0.175 0.127 0.688 3.902
25 Águilas 1.892 7.2 19.9 260.3 0.033 0.289 1.701 6.552
4-24 Becerrero 1.885 7.2 18.4 262.4 0.058 0.696 2.170 8.226
1-37 Becerrero 1.650 7.0 18.1 251.2 0.262 1.464 2.548 8.486

coincide with those when the piezometric level in the well is under
467 m.a.s.l. In the main recharge periods there are dilutions, with
values most commonly of the order 10–12%. During the dry period,
like the one between March of 2004 and December of 2006 (see
Fig. 4B), the cumulative drop in the piezometric level (21.1 m) is
accompanied by an increase in salinity, mainly due to the greater
concentrations of Cl , Na+ and SO24 and a decrease in the HCO3
and Ca2+ contents.
Fig. 5 shows the chemiograms of supply wells 8–4, situated in
Becerrero aquifer, and 25, in Águilas aquifer. In the first case
(Fig. 5A) the water from 8–4 presents a mean value for EC of
518 lS/cm, which varies between 430 and 853 lS/cm (period
1976–2006). When the piezometric level surpasses 467 m.a.s.l.,
Pedrera spring is activated and the water is HCO3Ca; yet when
the piezometric level declines during dry periods, the water pre-
sents HCO3ClCaNa facies, and on occasion even ClHCO3NaCa.
Indeed, during dry spells such as that of 2003–2006 (Fig. 5A), there
is a cumulative drop in the level, of 16.3 m, accompanied by a rise
in EC, due to the greater concentrations of Cl , Na+ and SO24 .
Likewise, as the piezometric level drops, there is a lesser content
in bicarbonate and calcium, while the contents in magnesium
and nitrates increase slightly (Fig. 5A). In turn, well 25 witnessed
a decline of over 33 m during the period 2003–2006, and of 46 m
since mid 1998 (IGME, 2006). These waters are HCO3ClCaNa,
though during the dry periods the predominant facies is
ClHCO3NaCa. The EC is between 610 and 1060 lS/cm, with a mean
value of 898 lS/cm. The dilutions recorded after the drought peri-
ods are from 10% to 29%. During the dry periods the major ions fol-
low an evolution very similar to that of well 8-4.
In Fig. 6 we find the chemiograms of the main wells exploiting
the aquifers of Hacho (Fig. 6A) and Mingo (Fig. 6B), both used to
irrigate olive orchards. Noteworthy in this figure is the high salinity
of the water and its evident seasonal variation. In both cases, the
waters are always sodium chloride.
In well 42 (Fig. 6A), the water presents a mean EC of
9078 lS/cm, comprised between 3210 and 14256 lS/cm. The
cumulative decrease of the piezometric level amounted to 28.6 m
in the period 1999–2006, and 9 m from March 2004 to December
2006. This drop was accompanied by an average 33% increase of
the EC as well as a rise in the concentrations of the major ions,
all except nitrates. The increase in the HCO3 contents is less
marked than in the rest of the components.
Furthermore, in 1999–2006, the piezometric surface in well 44
descended 11.6 m (Fig. 6B). Its waters present an EC in the range
2280–9196 lS/cm, with a mean value of 3986 lS/cm. The seasonal
variation in the salinity of the water is evident, and implies annual
dilutions of 35–50%, during recharge episodes. In the period ana-
lyzed (1999–2006), there is a progressive increase in the EC of
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263
Fig. 4. Evolution of piezometric level and main physico-chemical parameters of groundwater in well 4-24, compared to daily recharge and to Gilena spring discharge. (A)
1977–2006; (B) 2003–2006.
the water and in the concentration of the main constituents, with
the exception of bicarbonate.
5. Discussion
5.1. Hydrochemical processes and preliminary hydrochemical model
In Sierra de Estepa there are a number of carbonate aquifers of
small size and short renewal period. Groundwaters have physico-
chemical characteristics that are specific to each system and that
should be explained by means of hydrochemical hypotheses that
constitute a preliminary hydrochemical model. To enhance our
understanding of the hydrochemical evolution of the groundwater
in these aquifers, this section describes the temporal sequence of
the main reactions and chemical processes.
(A) Atmospheric contributions. It is assumed that rainwater (Type
0 in Table 4) is in balance with the partial pressure of atmo-
spheric CO2 (PCO2 = 10 3.5 atm.).
255
(B) Evapotranspiration and evaporation. The degree of evapora-
tion and transpiration produced, once the water from pre-
cipitation reaches the surface and infiltrates into soil, leads
to an increase in the concentration of salts. This process is
evident when comparing the rainwater data to water shal-
lower of wells located in main recharge zone of the
Becerrero aquifer (wells 4–61 and 4.54 in Fig. 1).
(C) Dissolution of CO2 and calcite. The recharge waters, infiltrated
preferentially between November and February, when the
mean temperature is some 10–12 °C, are enriched in CO2
after passing through the non-saturated zone of the aquifer,
including the soil and the epikarst. In the air of the
non-saturated zone, partial atmospheric pressures of CO2
must range from 10 2.9 to 10 1.6 (Table 3). The main
recharge zones are situated in the carbonate high plains at
heights of 650 and 840 m.a.s.l., where today there are karren
fields and a greater development of the epikarst
(Martos-Rosillo et al., 2013). The predominant vegetation
in these sectors, which may include more than half of the
256 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263

Fig. 5. Evolution of piezometric levels and main physical–chemical parameters of groundwaters in wells 8–4 (A) and 25 (B), compared to daily recharge (2003–2006).

total surface, consists of dense and dispersed brush forma-
tions, combined with treed areas. The acid waters resulting
from dissolution of CO2 promote calcite dissolution, the
main reaction taking place in these aquifers. Because of this
reaction is very quick reaction, most of the calcite is dis-
solved in the zones near the surface. Examples of groundwa-
ter whose chemistry is substantially related to calcite
dissolution are presented in wells of the Becerrero aquifer
(4–61, 4–59, 4–48, 4–6 in Fig. 1).
(D) Incongruent dissolution of dolomite. The dissolution of dolo-
mite incorporates calcium, magnesium and bicarbonate in
the groundwater and originates the supersaturation and
posterior precipitation of calcite, which gives rise to an
increase in the nMg2+/nCa2+ ratio in the sense of flow. This
process is known as incongruent dissolution of dolomite
(Drever, 1997; Freeze and Cherry, 1979) and it plays sec-
ondary role in the aquifers of Sierra de Estepa, due to the fact
that dolomies are much less abundant than limestones.
(E) Exsolution-dissolution of CO2. The exsolution-dissolution of
CO2 is related with seasonal changes in the partial pressure
of carbon dioxide in the atmosphere of the non-saturated
zone. It is usual for a supersaturation in calcite to occur—
and on occasion, in dolomite—in the surgence zones, where
good communication with air from the exterior exists.
(F) Mixing. Out of all the hydrochemical processes that occur in
Sierra de Estepa aquifers, mixing is, without a doubt, the one
making the most significant difference in groundwater,
owing to the presence of hypersaline water associated with
the detritic-evaporitic aquitards of Triassic substrate.
Exploitation of the groundwater and the piezometric
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263 257

Fig. 6. Evolution of piezometric levels and main physico-chemical parameters of groundwaters in wells 42 (A) and 44 (B), compared to daily recharge (2003–2006).

Table 4
Average hydrochemical values of representative rainwater and groundwater of the different Jurassic outcrops of Sierra de Estepa. Mean values in wells drilled in Triassic brine-
bearing aquitard also are included.

Type Name pH Na+ (mg/l) K+ (mg/l) Ca2+ (mg/l) Mg2+ (mg/l) Cl (mg/l) HCO3 (mg/l) NO3 (mg/l) SO24 (mg/l) Log PCO2 SICal SIDol SIGyp
0 Rainfall 7.00 1.6 0.40 7.9 1.9 4.5 25.5 3.6 4.7 3.50 2.12 4.50 3.50
IA Bece.A 7.30 7.9 0.28 88.4 5.7 13.1 232.9 30.6 17.7 1.94 0.15 0.54 2.23
IB Bece. B 7.40 19.5 0.41 76.6 7.3 33.3 238.7 33.9 17.7 2.11 0.12 0.42 2.28
IIA Águilas 7.23 81.9 0.69 97.2 22.4 132.9 299.4 31.7 72.2 1.84 0.10 0.08 1.69
IIB Pleites 7.41 140.2 1.83 98.0 34.7 260.5 254.7 43.3 102.8 2.04 0.24 0.38 1.59
III Mingo 7.47 766.5 7.40 162.0 45.8 1132.4 259.4 63.8 322.6 2.13 0.37 0.54 1.12
IV Hacho 7.34 2075.7 22.0 320.5 93.5 3228.7 228.5 44.8 673.2 2.09 0.49 0.78 2.09
V Saltwater 6.94 44287.3 1007.2 402.1 43.4 67254.5 99.6 0 1511.5 2.19 0.49 1.46 0.97

descent in carbonate aquifers cause recharge by saline reactions deriving from the combination of two waters with
waters coming from the aquitards. The geochemical pro- different ionic strength, different CO2 partial pressure and
cesses in this mixing zone are very important due to the different ionic activity of the calcium and the bicarbonate.
258 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263
This process is obvious in most of the wells of Sierra de
Estepa, particularly in smaller systems such as Mingo aquifer
(well 42 in Figs. 1 and 6) and the Hacho aquifer (well 44, in
Figs. 1 and 6).
(G) Dedolomitization. Another important hydrochemical process
in these aquifers is dedolomitization. This irreversible reac-
tion, which has been described by different authors
(Hanshaw and Back, 1979; Plummer, 1977), is due to the
incorporation of gypsum in the groundwater of a carbonate
aquifer. This incorporation causes, simultaneously, the pre-
cipitation of calcite (due to the common ionic effect) and
subsaturation in dolomite. In this sense, the study of the
relationships among nCa2+/nSO24 /, nMg2+/nSO24 / and
nHCO3 /nSO24 allows us to observe the process of dedolomi-
tization that takes place in the aquifers of Sierra de Estepa.
Dedolomitization produces an increase in the concentration
of sulfate, calcium and magnesium, and a slight decrease in
the bicarbonate content, although the latter effect may also
be influenced by other factors (increased temperature,
changes in the CO2 partial pressure, etc.). The consequences
of this process are manifest in the water samples
Fig. 7. Ionic relationships (nCa2+/nSO24 , nMg2+/nSO24 , nHCO3 /nSO24 and nCl /nSO24 ; n = meq/l) in groundwater samples associated with carbonate outcrops of Sierra de
Estepa.
corresponding to the aquifers of Hacho and Mingo, and in
the two samples collected during the execution of well
4-59, in Sierra de Becerrero (Fig. 7), when perforation
reached the detritic-evaporitic substrate.
5.2. Hydrochemical model of mass balance
In order to further validate the preliminary hydrochemical
model, the previous reaction hypotheses were tested by construct-
ing geochemical mass balance models by means of Aquachem.
In the proposed hydrochemical model, it is considered that the
aquifer materials are only made up of calcite and dolomite.
Nevertheless, the possibility of dissolution of gypsum is consid-
ered, if the aquifers have a reduced saturated thickness and their
waters are in contact with the detritic-evaporitic materials of the
substrate, or else if they have circulated nearby or along the bor-
ders of the aquifer in contact with clays with evaporites.
In winter, when cold rainwater (Type 0) passes trough the soil
and unsaturated zone, three main changes occur: water tempera-
ture rises to 16.5 °C (underground temperature is almost constant
and similar to average air temperature), the content in major ions
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263 259

increases due to evaporation of 65% of the rainwater, and the par-
tial pressure of CO2 rises to 10 1.85 atm. This process is responsible
for concentrating all the major ions of the water. However, bicar-
bonate and calcium contents increase due to the rapid dissolution
of calcite in unsaturated zone (Type IA).
On the other hand, Type V waters corresponding to the hyper-
saline water founds in a saline exploitation, are considered repre-
sentative of the detritic-evaporitic aquitard that limits the
different carbonate aquifers. This water comes from wells situated
in the saline mine of Pedrera (1.8 km southwest of the village of
Pedrera), which takes up different levels of halite, intercalated in
the Triassic marls and clays of the Antequera–Osuna unit.
Taking into account the low permeability of clay-evaporitic
aquitards and the very low hydraulic gradient under natural flow
regime, the water flow between the limestone aquifers and the
clay-evaporitic aquitards must be very limited. In conditions of a

Fig. 8. General hydrochemical model of different types of water in Sierra de Estepa. The model starts with local rainwater and in some cases, as a consequence of the intensive
exploitation of the aquifers, it is considered to exist mixing with briny water associated with the detritic-evaporitic substrate.
260 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263

modified regime, the hydrodynamic situation changes substan-
tially; the decrease in hydraulic charge in the aquifers favors the
entry of hypersaline waters from the aquitards. Mixing between
the water of the limestones (Type IA) and the saltwater of the clays
and evaporites (Type V), together with the hydrochemical pro-
cesses indicated above, would allow us to explain the different
types of water existing in the aquifers of Sierra de Estepa (Table 4).
The sources of chloride in the carbonate aquifers of Sierra de
Estepa are the rainwater and the inflow of groundwater from the
Triassic aquitards; since chloride minerals are absent in carbonate
rocks. So, as first approach, the proportions of mixing of both
end-members have been calculated from chloride concentrations.
Different proportions of mixing of the waters Type IA and V would
allow us to reproduce all the other types (IB, IIA, IIB, III and IV)
identified in the aquifers of Sierra de Estepa by means of the hydro-
chemical modeling program PHREEQC (Table 4).
Fig. 8 illustrates the general hydrochemical model of Sierra de
Estepa, elaborated from field observation and laboratory data,
which served as the basis for our hydrochemical modeling of the
groundwaters.
Once the different types of water had been reproduced, a hydro-
chemical model was put forth, in which the repercussion of the
intensive exploitation could be demonstrated (Fig. 8 and Table 5).
Because of the chloride content, to simulate the transition from
water IA to IB, it was necessary to consider the mixing of IA water
with hypersaline water (Type V). Actually, this mixing process only
happens in the wells that exploit the aquifer of Sierra de Becerrero
near the contact with the Triassic materials, during the dry periods.
The balance of mass at this stage implies the dissolution of mini-
mal amounts of dolomite and gypsum, and a slight precipitation
of calcite (Table 5).
The aquifers having physico-chemical characteristics that were
highly affected by intensive exploitation are (from less to most
affected), those of Becerrero (IA and IB), Águilas (IIA), Pleites
(IIB), Mingo (III) and Hacho (IV). The degree of impact is reflected
in a higher percentage of hypersaline water in the mixing
(Fig. 8). The percentages of participation of saltwater necessary
to explain the chloride concentrations of the aquifer groundwater
were between 0.0027% (Type IB) in Becerrero aquifer and 4.23%
in Hacho aquifer (Type IV). Table 5 and Fig. 8 show how, as the per-
centage of brine in the mixing increases, the model predicts a
decrease in the pH of the water, an increase in the partial pressure
of CO2, and a substantial increase in chlorides, calcium, magnesium
and sulfates (see Fig. 9).
The waters evolutionary state observed in the aquifers most
affected by intensive exploitation is mainly a consequence of the
dissolution of halite and the dedolomitization reaction.
5.3. Intensive exploitation, pumping, recharge and renewal period
Given the data presented in Table 1 and with the mean EC of the
groundwater of each one of the aquifers of Sierra de Estepa we drew
Fig. 10, showing the relationship between the EC and the pump-
ing/recharge ratios (Fig. 10A), pumping/total storage (Fig. 10B) and

Table 5
Probable evolution of groundwater in Jurassic aquifers of Sierra de Estepa. Contents (elements, ions, mineral or gaseous phases) are expressed in mmol/kg water. In the case of
mineral and gaseous phases, numbers refer to amounts that reacts (positive for dissolution and negative for precipitation). Numbers in bold were imposed in the simulation. The
remaining values were obtained from the model PHREEQC. 0Rec is the recharge water in winter (recharge period) before flowing into unsaturated zone. It is the result of
evaporation of 65% of rainwater in a soil poor in CO2.

0 0Rec IA IB IIA IIB III IV

Temp. 12.0 15.0 16.5 18.0 18.0 18.0 20.0 20.0
Log PCO2 3.50 3.00 1.85 1.91 1.73 1.70 1.57 1.50
pH 7.87 7.84 7.22 7.26 7.14 7.13 6.97 6.86
Alc (meq/kg) 0.42 1.32 4.41 4.17 5.00 5.26 5.10 5.23
Ca2+ 0.20 0.56 2.16 1.94 2.32 2.40 3.87 5.68
Mg2+ 0.08 0.22 0.22 0.30 0.82 1.34 1.91 3.65
S 0.05 0.14 0.19 0.19 0.73 1.16 3.34 7.03
Cl 0.13 0.36 0.36 0.94 3.79 8.29 32.07 90.98
Calcite 0.07 0.13 1.54 0.29 1.03 1.82 3.11 6.60
Dolomite 0.08 0.14 0.00 0.10 0.66 1.12 1.68 3.50
Gypsum 0.00 0.00 0.05 0.01 0.52 0.92 2.94 6.37
CO2 0.00 0.00 2.11 0.24 0.45 0.63 0.79 1.02
ISCalcite 0.00 0.42 0.00 0.00 0.00 0.00 0.00 0.00
ISDolomite 1.25 0.97 0.77 0.38 0.21 0.23 0.10
ISGypsum 2.76 2.22 2.29 1.69 1.52 0.99 0.65

Fig. 9. Graphic representation of modeling results of hydrochemical evolution of the groundwater of Sierra de Estepa.
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263
Fig. 10. Relationship between groundwater electric conductivity and ratios of pumping/recharge, pumping/total storage (year
(year) in the aquifers of Sierra de Estepa.
renewal period (Fig. 10C), which in turn represents the total stor-
age/recharge ratio. The aquifers of smaller size and those of smaller
renewal period are more vulnerable to the entry of saline waters
from the detritic-evaporitic materials surrounding them and defin-
ing the aquifer base. The aquifers with greater renewal period and
those having a lower pumping/total storage ratio present less saline
waters. Overall, we should point out that the response of Hacho
aquifer is anomalous in that the salinitiy is greater than in the others.
This would appear to be related with the greater proximity of the
bottom of well 44 with respect to the aquifer base, and the possible
ascent of hypersaline water caused by pumping in the contact zone
between the limestone and the aquifer substrate.
5.4. Final hydrogeological conceptual model
Hydrochemichal modeling and analysis of the exploitation have
allowed us to propose an improved conceptual model of Sierra de
Estepa which considers hydrochemical and geological features and
vulnerability to salinization. On the one hand, the structure of each
aquifer, the storage capacity, the existence of evaportitic materials,
and, in some cases, the overlying Miocene detritic materials are the
main natural factors conditioning the mixing with water from
beyond the carbonate aquifers and the posterior hydrochemical
processes associated with such mixing. On the other hand, the
increase in the ratio pumping/storage involves a drop of piezomet-
ric levels and, consequently, an increase in groundwater
salinization.
In Becerrero aquifer, which is the largest one studied and has
the greatest renewal period, exploitation is near the mean recharge
of the system. However, the periodic decline in the hydraulic
potential produced in the drought periods, favors the flow from
aquitards situated at the borders of the aquifer. Hence, mixing with
more mineralized water takes place. Likewise, during the dry peri-
ods, the deepest waters in Jurassic aquifers are mobilized, and they
contain higher sulfate, calcium and magnesium contents than the
shallower waters, due to the dedolomitization in the contact zone
between Jurassic materials and Triassic substrate (Fig. 11).
Obviously, the greatest increases in salinity are seen in the wells
most adjacent to the contact with the detritic-evaporitic materials;
such is the case of well 8-4 (Fig. 5).
In aquifer systems where exploitation is greater than average
recharge to the system (Águilas, Hacho and Mingo) the decline in
the piezometric level does not stabilize. Thus, over time, the differ-
ence of hydraulic potential between the carbonate system and the
aquitard materials increases, leading to an increasing groundwater
influx from the boundaries. In Águilas aquifer (Fig. 11), the greater
volumen of reserves makes the proportion of brine lesser, unlike
the case of Mingo and Hacho aquifers. Meanwhile, the overlying
261
1
) and total storage/recharge o renewal period
Miocene materials, where olive trees are intensively cultivated,
would explain the increase in nitrates seen to accompany the emp-
tying of Mingo aquifer (Figs. 6 and 11).
6. Conclusions
The results of this study allowed us to determine the effects of
intensive exploitation of groundwater in a series of small carbon-
ate aquifers situated in southern Europe. These aquifers, made up
of limestones and dolomites, are delimited largely by a set of sat-
urated detritic-evaporitic aquitard materials with hypersaline salt-
water. The high permeability of the carbonates, the scarce reserves
and the limited size of the aquifers favor a rapid hydrodynamic
response to exploitation.
In the aquifers where pumping is less than recharge, during
drought periods, the piezometric level drops below the level of
the springs. The springs draining HCO3Ca waters dry up, and the
water from the wells undergoes a rise in salinity due to increased
concentrations of Cl , Na+ and SO24 . During wet periods following
the droughts, dilutions take place, these being more significant in
the aquifers with more highly mineralized waters and with a lesser
amount of reserves. In aquifers where pumping is systematically
higher than the recharge, the increased mineralization of the water
is continuous.
Despite the proximity and similarity of the studied aquifers, the
spatial variability of the physico-chemical characteristics of the
groundwater is noteworthy. In Becerrero aquifer water is HCO3Ca
and the mean EC is 470 lS/cm. However, Hacho aquifer has ClNa
facies, with a mean EC of 9780 lS/cm. This study demonstrates
that the degree of loss of water quality is controlled by the pump-
ing/renewal period ratio of each aquifer and by the greater or lesser
presence of detritic-evaporitic materials at the base and at the
margins of each one of the aquifers.
Modeling the different types of waters with the PHREEQC code
led us to confirm that the mixing of saline waters and the processes
of dedolomitization are greater in the aquifers having a lesser stor-
age capacity.
As for the analyis of the temporal evolution of the hydrochem-
ical characteristics of groundwater, it was found that during dry
periods there is an increase in the salinity of the water, due to
the increased concentration of chlorides, sulfate, sodium and cal-
cium. In this way, the control of water salinity can be considered
as a tool to detect and prevent mixing process.
Aquifers with greater reserves are less vulnerable to saliniza-
tion, since the contact zone between the aquifer and the aquitard
is relatively smaller and, in case of intensive exploitation of
groundwater, lower piezometric drops take place.
262 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263

Fig. 11. Conceptual model of aquifers of Sierra de Estepa. Number 1 indicates rainfall recharge to the carbonate aquifers. Numbers 2, 3, 4 and 5 indicate water inputs to the
carbonates from different lithologies. T, transmissivity; S, Salinity; P, Pumping. (T1: 1–6
10 3 m2/s; T2: 10 4 m2/s; T3: 10 6–10 7 m2/s; T4: 10 7–10 8 m2/s; T5: 10 5 m2/s;
Martos-Rosillo, 2008).

Improving hydrogeological knowledge of aquifers in Sierra de
Estepa has led to carried out a series of measures to make progress
in groundwater management. They can be summarized as: estab-
lishment of a stakeholder community, reduction of groundwater
withdrawal (particularly for irrigation), relocation of pumping
wells in other sectors of the aquifer less vulnerable to salinization
and implementation of a monitoring network.
This study makes manifest that in order to achieve sustainable
exploitation of groundwater, without deteriorating its quality, it is
necessary to have previous hydrogeological knowledge of the aqui-
fer to be exploited. Carbonate aquifers with limited renewal peri-
ods situated in semi-arid zones are highly vulnerable to
exploitation. Pumping groundwater generated quick drops in the
piezometric surface during drought periods, a situation favoring
the entry of external water into the system. For these reasons,
hydrogeological and hydrochemical research should be extended
to the bodies of water having a possible hydrogeogical connection
with the aquifer to be exploited.
Acknowledgements
The autors thank M. Martín-Machuca, A. Martínez-Sánchez and
T. Bros (Geologcial Survey of Spain) for their efforts in the monitor-
ing of these aquifers. This study was supported by the projets CGL
2010 21048 of Spanish Ministry of Science and Education, as well
as by Research Group of Andalucía RNM-126. We would also like
to acknowledge the careful review and thoughtful comments of
the reviewers and editor.
 S. Martos-Rosillo, F. Moral / Journal of Hydrology 528 (2015) 249–263 263

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