Research Article

Geochemical and isotopic evidence of groundwater salinization

processes in the Essaouira region, north‑west coast, Morocco
Otman EL Mountassir1 · Mohammed Bahir1,2 · Driss Ouazar3 · Abdelghani Chehbouni2,4 · Paula M. Carreira4,5

Received: 23 November 2020 / Accepted: 3 May 2021

© The Author(s) 2021  OPEN

Abstract
The city of Essaouira is located along the north-west coast of Morocco, where groundwater is the main source of drinking,
domestic and agricultural water. In recent decades, the salinity of groundwater has increased, which is why geochemical
techniques and environmental isotopes have been used to determine the main sources of groundwater recharge and
salinization. The hydrochemical study shows that for the years 1995, 2007, 2016 and 2019, the chemical composition of
groundwater in the study area consists of ­HCO3–Ca–Mg, Cl–Ca–Mg, ­SO4–Ca and Cl–Na chemical facies. The results show
that from 1995 to 2019, electrical conductivity increased and that could be explained by a decrease in annual rainfall in
relation to climate change and water–rock interaction processes. Geochemical and environmental isotope data show
that the main geochemical mechanisms controlling the hydrochemical evolution of groundwater in the Cenomanian–
Turonian aquifer are the water–rock interaction and the cation exchange process. The diagram of δ2H = 8 * δ18O + 10
shows that the isotopic contents are close or above to the Global Meteoric Water Line, which suggests that the aquifer
is recharged by precipitation of Atlantic origin. In conclusion, groundwater withdrawal should be well controlled to
prevent groundwater salinization and further intrusion of seawater due to the lack of annual groundwater recharge in
the Essaouira region.

Keywords Stable isotopes · Essaouira · Groundwater · Climate change · Geochemistry

1 Introduction The geochemistry of groundwater in coastal aquifers

represents previous geological conditions and current
In most of the arid and semiarid regions of the world, the anthropogenic processes that affect the quality of ground-
availability of sufficient freshwater has become a factor water [7–10]. However, the local and regional meaning of
limiting growth [1–3]. In parts of North Africa, where water these aquifers, the key hydrogeological trends, hydro-
scarcity has always been a dominant problem, interference chemical characteristics and groundwater origins remain
with the natural hydrological cycle through overexploita- poorly known [11–13]. The combination of geochemistry
tion of groundwater resources and changes in land use and isotopic tools can lead to relevant information on
has caused not only reduction of available water, but also the origin of mineralization of karst water [14–17]. Sta-
degradation of water quality [4–6]. ble isotopes integrated with major ions in groundwater

* Otman EL Mountassir, [email protected] | 1High Energy and Astrophysics Laboratory, Faculty of Sciences Semlalia,
Cadi Ayyad University, Marrakech, Morocco. 2International Water Research Institute (IWRI), Mohammed VI Polytechnic University (UM6P),
Benguerir, Morocco. 3Mohammadia School of Engineers, Mohammed V University, Rabat, Morocco. 4Institut de Recherche Pour Le
Développement (IRD), Unité Mixte de Recherche (UMR), Centre D’études Spatiales de La Biosphère (CESBIO), Université de Toulouse,
Toulouse, France. 5Centro de Ciências e Tecnologias Nucleares, C2TN/IST, Universidade de Lisboa, Lisbon, Portugal.

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Research Article SN Applied Sciences (2021) 3:698 | https://doi.org/10.1007/s42452-021-04623-3

have been employed in regional groundwater studies at aquifers (Plio-Quaternary and Cenomanian–Turonian).
different locations across the world. The works of [18–24] The goal of the current study system is to provide base-
have demonstrated effectiveness of this approach in line information on: (1) the hydrochemical characteristics
understanding recharge pattern, origin and residence of groundwater, (2) the key processes that deteriorate the
time of groundwater from specific sites to basin-scale quality of groundwater and (3) the sources of groundwater
hydrogeological investigations. Most of these studies recharge and their mixing pathways.
have contributed vital information and knowledge that
are useful in global groundwater resource management.
Dissolved major ions and stable environmental isotopes 2 Climate
(δ18O and δ2H) have been used to describe the sources
of salinization and hydrogeochemical processes affecting The Meskala–Ouazzi sub-basin is located in the north-
groundwater quality in this complex system [25–27]. In eastern part of Essaouira city (Fig. 1). It is bordered on
addition, the objective of this research is to determine the the north by Jbel Hadid, on the south by Igrounzar Wadi,
main source(s) of groundwater mineralization in different on the east by the Bouabout region and on the west by

Fig. 1  Study area and locations

of groundwater samples

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the Atlantic Ocean (Fig. 1). This study is crossed by Wadi pH, electrical conductivity and TDS) were taken in the field
Ouazzi and Wadi Igrounzar whose natural outlet is the using the multi-parameter HI9828. The depth to water
Atlantic Ocean and has a total area of 1260 ­km2. The basin in each well was measured using a sound piezometric
is under semiarid climate with irregular rainfall of about probe. The water samples were taken after pumping for
300 mm ­year−1 and the temperature oscillates around 10–15 min to obtain representative values under ambient
20 °C [9, 22]. aquifer conditions. Samples were collected in clean poly-
ethylene bottle of 500 mL and then stored at a tempera-
ture below 5 °C before analysis in the laboratory.
3 Geological and hydrogeological settings Chemical analyses were carried out at the Laboratory
of Geosciences and Environment of the Ecole Normale
Geologically, the upstream part of the study area (Fig. 2) Superieure of Marrakech (Morocco). The contents of chlo-
is dominated by the middle and upper Cretaceous out- ride ­(Cl−) and sulphate (­ SO42−) anions were determined to
crop (Albian, Vraconian, Cenomanian and Turonian). adopt the Mohr technique and the nephelometric tech-
These formations consist of banks of limestone and nique, respectively. ­Ca2+ and ­Mg2+ concentrations were
dolomitic intercalated with marls and sandstones. The determined using the EDTA titrimetric method. ­HCO3− and
Albian and Vraconian are represented by green marls ­CO3− contents were analysed by titration using 0.1 M HCl
(thickness 160 m) and dolomitic limestones (thickness acid. ­Na+ and ­K+ were measured by flame spectrometry at
140 m). The Cenomanian is characterized by an alterna- the University Center for Analysis, Technology Transfer &
tion of grey marls with anhydrite, lumachellic limestones Incubation Expertise (CUAE2TI) at the Faculty of Sciences
and sandstones in small proportions (thickness 200 m) (Ibn Tofail University, Kenitra, Morocco). The ionic balance
[28, 29]. The Turonian consists of limestones where silica for all samples was within ± 10%.
is very abundant. The downstream part of the study area Stable isotope levels were measured by laser spectros-
is characterized by the outcrop of the Plio-Quaternary copy. The measurements are expressed in per mille com-
formations. These are represented by conglomerates, pared to the international Standard Mean Ocean Water
alluviums, colluvium and sandstones (Fig. 2). (SMOW) with an analytical uncertainty of ± 0.1‰ for δ18O
Hydrogeologically, two major aquifer systems have and ± 1‰ for δ2H. The analyses of stable isotopes (δ2H and
been identified: the first is a multi-layered aquifer consist- δ18O) were carried out at Centro de Ciências e Tecnologias
ing primarily of Plio-Quaternary detrital deposits (sand- Nucleares laboratory (CTN/IST, Universidade de Lisboa).
stones, conglomerates and sands), responsible for much The methodology adopted thus makes it possible to
of the population’s water supply. This comes into close explore the potentials of a multidisciplinary approach,
contact with the formations of the Triassic and Cretaceous centred on the use of stable isotopes, to determine the
below. The second is the calco-dolomitic layers of the recharge areas of the main sources studied. The technique
Cenomanian–Turonian age [28, 29], reflecting the karstic of interpolation (IDW) via a geographical information sys-
aquifer; according to [28, 29], the Turonian horizon flour- tem (GIS) was used to compile spatiotemporal distribution
ishes between 400 and 700 m altitude (a.s.l.) on the Jbel maps of electrical conductivity.
Kchoula, while the Plio-Quaternary layers grow between
sea level and 300 m altitude (a.s.l.). Transmissivity levels
are approximately 4.5 × ­10–5 to 6 × ­10–2 ­m2/s from pump- 5 Results and discussion
ing experiments conducted inside the Plio-Quaternary
aquifer [28], while the hydraulic has a permeability of 5.1 Piezometry
3.2 × ­10–2 m/s in the downstream part of the study area
[29]. Four piezometers (a-d) were used to track the
Meskala–Ouazzi sub-basin piezometric level. Furthermore,
Fig. 3 shows that heavy rains cause a continuous increase
in the piezometric level, indicating that groundwater levels
4 Methodology are highly dependent on precipitation. The four piezom-
eters studied display a general downward trend, despite
Four water sampling campaigns (112 boreholes, wells and a small increase in the piezometric level with intense pre-
springs) were performed in 1995 (18 samples), 2007 (25 cipitation [4]. Like other basins in coastal areas [30], the
samples), 2016 (19 samples) and 2019 (50 samples) in the Essaouira basin has not been spared the effect of climate
Meskala–Ouazzi region of Essaouira basin (Fig. 1). Meas- change, which is added to the effect of the overexploi-
urements of physico-chemical parameters (temperature, tation of groundwater. This effect is manifested by (a) an

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Fig. 2  Geology map in the study area

increase in population of 9% leading to an increase in irri- of groundwater with an increase in salinity. This deple-
gated land (1300 ha), (b) upward trend in temperatures tion is due to marine intrusion and a decline in aquifer
with 1.5 °C warming and a general downward trend in recharge rates due to the drop in precipitation result of
precipitation of 12% and (c) a deterioration in the quality climate change [4, 17].

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Fig. 3  Piezometric levels for the period 2006–2016 in the study area

5.2 Hydrochemistry is represented by samples showing slight dominance of

­Ca2+ + ­Mg2+ over ­HCO3− + ­SO42−, and the third group is
The results of chemical analyses are plotted on the represented by samples showing a marked increase in
Piper diagram [31] (Fig. 4a). This diagram shows that the concentration of ­Ca2+ + ­Mg2+. The high concentration
there are four chemical facies in the groundwater of the of ­Ca2+ + ­Mg2+ relative to S­ O42− + ­HCO3− can be a result
Meskala–Ouazzi: ­HCO3–Ca–Mg, Cl–Na, Cl–Ca–Mg and of reverse ion exchange [30].
­SO4–Ca, with domination of the Cl–Ca–Mg water type. This Similarly, increasing calcium and bicarbonate levels
transition from one facies to another illustrates the impor- in the groundwater are considered to be responsible for
tance of the hydrogeochemical processes that control the the dissolution of carbonate minerals. This suggests that
salinity of the aquifer’s waters. For 24 years, the groundwa- reverse ion exchange reactions and weathering are the
ter in the study area retains the same facies. dominant processes controlling the groundwater chem-
The ­Ca 2+ + ­M g 2+ versus S­ O 42− + ­H CO 3− plot (Fig. 4b) istry due to the excess ­HCO3− [33], and this is confirmed
shows that the cation exchange is not the only process by Fig. 8.
controlling the composition of groundwater. The dia- To determine the major elements that contribute to
gram (Fig. 4b) can be divided into three groups. Sam- water mineralization, a correlation between major ele-
ples fall along the 1:1 equiline showing the dissolution ment content and EC was established (Fig. 5). For the
of gypsum, calcite and dolomite [32]. The second group groundwater from Meskala–Ouazzi sub-basin, ­C a 2+ ,

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Fig. 4  Hydrochemistry of the four campaigns 1995, 2007, 2016 and 2019 in the study area. a Piper diagram; b correlation between
­Ca2+ + ­Mg2+ (meq/L) and ­HCO3− + ­SO42− (meq/L)

Fig. 5  Bivariate plots of electrical conductivity (EC) plotted against chemical constituents of groundwater

­Mg2+, ­SO42− and ­Cl− were found to be the main contribu- calcite, dolomite and gypsum dissolution is prevailing in
tors to groundwater mineralization. For the groundwater the aquifer. If the samples fall below the 1:1 line, it reflects
from the study area, the main elements responsible for the dominance of ion exchange reactions, but if they plot
groundwater mineralization were M ­ g2+, ­SO42−, ­Na+ and above the 1:1 line, then there is the presence of reverse ion
−
­HCO3 [6, 21]. exchange reactions [32].
The diagram of ­Ca2+ vs ­Mg2+ (Fig. 6a) indicates that The ­Na+ vs ­Cl− diagram (Fig. 6b) indicates that most
most points are aligned on the straight line of slope 1. samples are aligned or before on the 1:1 axis, and
This reflects the contribution of dolomite dissolution to the concentration of ­C l − is correlated with ­N a + with a
the mineralization of groundwater, especially in waters strong correlation R2 = 0.9, indicating that halite disso-
sampled in 2016. If the samples plot close to the 1:1 line, lution may be the major reaction influencing the water

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Fig. 6  Correlation diagram: a ­Ca2+ vs M

­ g2+, b ­Na+ vs C ­ CO3−, d ­Ca2+ vs S­ O42
­ l−, c ­Ca2+ vs H

chemistry; high values of ­C l − and ­N a + can be resulted involvement of calcite dissolution in groundwater min-
from evaporation and the seawater intrusion in ground- eralization in the study area.
water in coastal areas. The water sample points with low On a plot of C ­ a2+ and S­ O42− (Fig. 6d), majority of the
densities of ­N a + and ­C l − are basically distributed near samples for the four campaigns (1995, 2007, 2016 and
the 1:1 line under the action of atmospheric precipi- 2019) plot close to the 1:1 line and thus, with high corre-
tation and rock–water interactions. When entering the lation R2 = 0.8, indicate gypsum dissolution. However, the
discharge area (downstream area), the groundwater is samples that plot below and above the 1:1 line suggest
gradually affected by surface water recharging, human interplay of ion exchange and reverse ion exchange reac-
activities and evaporation. Both ­N a + and ­C l − begin to tions due to excess ­SO42− and ­Ca2+, respectively (Fig. 6d).
increase and the distribution of the groundwater sam-
ple points along y = x also begins to show a trend of 5.3 Spatiotemporal evolution of electrical
unevenness [34]. This is also confirmed by the plot conductivity
shown in Fig. 8. No relation had been mentioned
between ­Ca2+ and H ­ CO3−. For the four campaigns (1995, Electrical conductivity (EC) values range from 615 to
2007, 2016 and 2019), the interaction between C ­ a2+ and 5738 μS/cm with an average of 2449 μS/cm for 2019
−
­H CO 3 (Fig. 6c) is poor. This illustrates the negligible samples, 803 to 4450 μS/cm with an average of 2345 μS/

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Table 1  Chemical composition Sample pH T EC Ca2+ Mg2+ Na+ K+ HCO3− Cl− SO42− NO3− IB
of analysed samples of four
campaigns 1995, 2007, 2016 °C μS/cm meq/L %
and 2019
Campaign 1995
E1 19 1980 17.13 17.65 9 0.12 8.4 17.13 22.79 0.14 −5
E2 18 2600 16.21 17.73 19.01 0.12 7.56 30.54 16.35 1.09 −2
E3 17 3060 24.59 14.85 23.01 0.08 3.6 49.67 13.19 0 −3
E4 19 1800 11.44 1.24 12.01 0.13 7.84 21.13 3.8 0.93 − 15
E5 20 2230 13.33 23.15 10 0.15 6.92 27.43 13.13 0 −1
E6 18 1820 8.38 11.57 16.01 0.1 6.44 25.04 2.25 0.47 3
E7 20 804 5.35 5.48 5.5 0.03 5.28 9.92 0.88 1.52 −4
E8 19 2460 4.19 8 16.12 0.05 6.44 17.53 2.07 1.33 2
E9 19 1330 8.09 6.4 9.5 0.07 6.32 13.72 2.01 2.81 −2
E10 19 1080 7.35 5.8 6.5 0.05 5.32 13.22 0.81 1.3 −2
E11 16 382 2.63 3.18 2.5 0.09 2.76 6.41 0.49 0.36 −9
E12 20 1410 7.78 10.98 8.5 0.19 7.12 12.32 10.26 1.33 −6
E13 19.5 1460 7.27 7.92 10.5 0.42 7.48 14.32 3.15 5.24 −7
E14 18 640 4.35 6.8 3.02 0.08 6.52 5.21 2.91 0 −1
E15 18 1080 8.1 9.04 5 0.12 6.8 7.61 6.47 2.21 −2
E16 17.5 795 6.23 6.48 4 0.04 5.88 9.01 4.32 1.14 − 10
E17 18 700 6.07 5.73 3 0.03 6.24 7.11 3.75 0.78 −9
E18 19 1290 8.58 10.41 6.5 0.11 6.4 12.82 7.52 0 −2
Campaign 2007
E19 7.28 22 2600 7.49 8.52 7.27 0.14 6.2 17.9 1.79 1.38 −8
E20 7.24 20 1500 4.77 6.85 3.13 0.06 5.6 4.35 4.06 0.8 0
E21 7.5 17.4 998 3.92 2.9 2.96 0.08 5.25 2.82 0.49 0.75 3
E22 7.39 21.9 1065 3.14 4.56 2.17 0.05 5.5 3.07 1.57 0.64 −4
E23 7.69 21.3 994 3.64 4.22 1.89 0.06 5 1.93 1.42 0.69 4
E24 7.64 17.4 3880 34.03 27.81 2.44 0.32 4.4 4.98 49.81 0 4
E25 7.6 18.3 1600 3.59 6.21 2.84 0.11 5.65 4.67 4.59 0.36 −9
E26 7.11 21.5 2750 17.91 19.95 2.27 0.21 5.75 3.23 27.62 0 5
E27 6.9 26.6 2500 13.36 13.09 9.93 0.18 6 16.08 8 1.23 8
E28 6.9 22.8 2800 10.61 14.72 10.06 0.14 6.6 15.83 7.61 1.23 6
E29 6.75 22.2 3100 12.75 16.49 13.45 0.12 5.5 23.73 8.65 1.05 5
E30 6.65 24.8 2700 9.4 14.66 11.11 0.12 7.5 17.22 7.77 1.02 3
E31 7.35 24.4 2540 11.64 14.48 8.43 0.18 6 14.03 8.71 1.05 8
E32 7.35 22.2 2970 15.02 7.41 11.11 1.7 3 18.83 4.46 3.45 8
E33 7.8 23.2 900 3.88 4.37 5.18 0.36 5.83 4.05 3.68 0 1
E34 7.1 22.1 1900 10.97 10.44 8.4 0.12 3.28 31.03 0.16 0 −7
E35 7.65 26.4 3740 28.88 23.26 4.43 0.28 4.1 8.84 49.94 0.39 −5
E36 7.4 25 1220 2.46 4.33 5.38 0.36 5.5 3.61 4.47 0 −4
E37 7 26.2 2300 6.51 11.5 4.74 0.14 6.5 12.12 7.4 0.21 −7
E38 7.15 24.4 966 2.92 4.63 2.06 0.06 6.75 2.03 0.47 0.31 1
E39 6.85 29.5 1810 10.53 9.49 4.84 0.16 6.7 11.97 7.8 0.35 −3
E40 7.1 25.8 1400 8.18 6.39 4.49 0.11 6.4 10.21 1.87 0.73 0
E41 7.35 23.5 1500 4.87 4.25 6.98 0.09 3.61 13.88 1.86 0.15 −9
E42 7.1 22.8 1500 6.29 9.95 4.21 0.11 7.5 6.61 6.41 0.63 −1
E43 7.05 20 1867 6.84 8.15 5.29 0.35 6.26 8.52 6.55 0.58 −3
Campaign 2016
E44 7.49 19.5 2190 10.69 8.87 4.62 0.24 5.2 7.98 10.34 1.27 −1
E45 7.63 21 1188 5.78 5.24 1.61 0.1 4.2 2.17 5.74 0.52 0
E46 7.37 19.2 1300 5.62 5.97 2.48 0.09 5.6 3.35 5.03 0.47 −1
E47 7.23 22.1 1249 5.64 4.61 2.35 0.07 4.7 3.52 3.72 0.69 0

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Table 1  (continued) Sample pH T EC Ca2+ Mg2+ Na+ K+ HCO3− Cl− SO42− NO3− IB
°C μS/cm meq/L %

E48 7.31 19.8 803 3.79 1.14 2.61 0.01 3.6 2.35 0.37 1.3 0
E49 7.11 18.5 2050 9.36 9 4.8 0.14 3.8 5.79 11.91 2.05 −1
E50 7.23 18 3250 10.14 9.23 14.16 0.05 6.1 22.56 2.61 1.55 1
E51 7.03 22.1 3050 27.03 10.59 3.08 0.13 3.6 3.52 32.77 0 1
E52 6.91 23.7 1800 8.78 7.99 4.21 0.09 6.2 8.02 5.91 0.32 2
E53 6.87 20.9 1883 5.12 3.53 8.57 0.02 4.1 10.25 1.55 1.58 −1
E54 6.99 23 4150 9.28 15.55 19.25 0.05 5.8 29.27 5.62 1.83 2
E55 7.15 23.3 1894 6.85 6.73 5.55 0.17 6.5 8.27 4.29 0 1
E56 7.07 21.2 1933 6.82 6.48 6.59 0.13 6 7.73 4.88 1.07 1
E57 6.99 23.4 2550 13.28 12.54 5.59 0.07 6.4 8.01 16.68 0.58 0
E58 7.04 22.1 2020 5.97 5.97 8.01 0.33 7.1 11.3 1.43 0 1
E59 7.33 24 2550 7.48 9.89 8.73 0.09 5 12.66 7.06 0.97 1
E60 6.99 23.2 3100 10.62 11.85 11.28 0.08 6 17.57 8.49 0.99 1
E61 7.32 19.6 3150 9.63 9.58 16.24 0 4.1 24.28 3.06 1.13 4
E62 7.11 20.5 4450 14.55 6.87 22.21 2.62 4.5 29.08 4.31 6.31 2
Campaign 2019
E63 7.44 21.48 4530 14.64 18.93 17.18 1.11 8.16 34.05 19.67 0.49 −9
E64 7.82 18.02 2249 7.60 7.94 8.59 0.26 6.12 16.01 5.59 0.97 −8
E65 7.13 21.71 2179 9.42 11.64 5.47 0.25 9.40 18.03 1.98 0.87 −6
E66 8.38 17.8 615 4.09 3.38 1.42 0.13 4.00 5.23 0.81 0.07 −6
E67 7.71 20.75 2381 9.04 8.40 5.69 0.22 9.80 13.20 4.77 0.19 −9
E68 7.45 20.18 3842 18.24 8.16 9.82 0.39 6.96 18.23 16.91 0.23 −7
E69 7.55 20.27 2199 13.12 7.39 6.93 0.20 5.88 15.22 5.90 0.13 1
E70 7.2 23.63 1075 5.92 7.89 1.19 0.06 8.00 9.21 0.39 0.29 −9
E71 7.21 24 972 5.12 5.12 6.66 0.05 8.00 6.01 0.57 1.74 2
E72 7.51 22 1888 6.72 8.07 5.25 0.12 6.96 12.82 2.34 0.48 −6
E73 7.45 21.06 4380 21.47 6.16 17.16 0.32 8.60 38.05 3.69 1.94 −7
E74 7.66 21.35 2500 7.50 7.71 12.74 0.37 7.80 24.03 0.26 0.11 −6
E75 7.6 20.9 3016 8.40 6.00 12.41 0.50 8.00 19.23 2.04 2.58 −8
E76 7.78 19.96 736 6.99 4.61 0.79 0.04 4.76 5.33 0.73 0.39 5
E77 7.55 18.91 882 9.03 7.31 0.65 0.09 9.00 6.81 1.24 0.29 −1
E78 7.76 20.95 796 5.16 6.64 0.54 0.04 8.20 5.21 0.32 0.21 −6
E79 7.45 21.44 1510 8.00 9.09 3.54 0.07 8.00 11.62 3.14 0.31 −5
E80 7.42 20.8 1559 6.60 7.88 3.61 0.08 6.96 13.22 1.68 0.19 − 10
E81 7.08 19.45 3690 12.88 13.57 13.01 0.13 9.40 32.45 3.69 1.35 −8
E82 7.16 20.3 5738 24.16 8.40 23.51 0.30 9.20 51.27 5.59 1.13 −9
E83 7.78 21.26 1020 5.60 6.67 1.92 0.10 7.96 6.41 1.55 0.35 −6
E84 7.76 19.3 1336 6.78 7.83 2.84 0.25 7.16 8.41 5.47 0.28 −9
E85 7.99 18 2750 13.44 13.78 4.30 0.32 6.20 12.82 17.05 1.03 −8
E86 7.47 21.4 1411 6.72 8.29 3.26 0.08 8.20 7.61 5.34 0.23 −8
E87 7.4 19.63 1584 7.84 9.10 4.37 0.14 7.80 8.81 8.71 0.08 −8
E88 7.98 14.85 1843 7.28 7.51 4.35 0.55 7.80 11.62 1.61 1.26 −6
E89 7.08 16.5 1574 5.12 7.48 3.53 0.13 6.72 8.49 2.68 0.48 −6
E90 7.57 20.3 1543 9.12 14.47 4.19 0.43 7.12 10.41 7.98 0.23 5
E91 7.09 17.25 3646 38.40 8.96 2.43 0.25 8.80 9.61 40.42 0.19 −8
E92 7.59 18.04 3389 20.96 21.43 6.60 0.29 11.20 18.83 26.95 0.65 −8
E93 7.53 17.5 1192 6.72 5.53 3.46 0.12 6.23 8.81 2.16 0.23 −5
E94 7.2 22.15 1261 6.24 8.01 2.43 0.07 6.56 8.41 4.49 0.39 −8
E95 7.8 21.03 862 4.40 2.61 2.45 0.02 4.96 3.19 0.58 0.48 1
E96 7.24 20.5 4965 15.60 24.47 15.21 0.16 10.40 26.44 24.38 2.82 −7

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Table 1  (continued) Sample pH T EC Ca2+ Mg2+ Na+ K+ HCO3− Cl− SO42− NO3− IB
°C μS/cm meq/L %

E97 7.01 22.83 2939 27.52 10.72 2.16 0.15 10.40 8.81 29.40 0.03 −9
E98 7.65 22.05 2440 9.51 11.95 4.98 0.85 14.72 13.62 3.63 0.06 −8
E99 7.4 22.9 3220 13.04 13.81 13.27 0.17 9.80 26.84 6.81 0.60 −4
E100 7.56 20.96 2230 6.48 3.20 9.13 0.06 6.87 12.53 1.89 0.23 −7
E101 7.56 21.45 2266 6.16 6.68 8.32 0.05 6.92 13.60 3.86 0.40 −8
E102 7.22 20.68 4277 12.32 6.08 16.88 4.33 7.40 31.24 3.26 2.74 −6
E103 7.28 20.8 2657 8.32 11.08 8.06 0.13 7.00 19.23 6.02 0.73 −9
E104 7.3 19.15 4216 21.04 24.39 7.82 0.33 9.60 18.83 34.67 0.14 −8
E105 7.27 20.8 4349 9.77 15.11 19.72 0.19 8.16 36.67 8.16 1.05 −9
E106 7.43 20.8 3286 14.00 9.71 9.52 1.57 6.60 26.84 6.08 1.13 −8
E107 7.38 20.95 2140 5.38 7.38 8.37 0.11 8.56 13.20 2.22 0.46 −7
E108 7.18 22.2 2277 9.22 7.20 7.87 0.32 10.76 16.01 2.10 0.05 −8
E109 7.5 22.7 2148 7.72 10.14 6.31 0.09 8.40 15.22 3.88 0.35 −7
E110 7.32 21.5 2650 10.51 10.10 7.00 0.13 7.80 19.63 4.85 0.19 −8
E111 7.4 20.8 1873 5.76 3.84 8.07 0.08 5.32 12.40 2.34 0.48 −7
E112 7.4 19.2 4370 15.68 20.99 12.13 2.18 9.80 33.25 14.28 0.40 −6

cm for 2016 campaign waters, 900 to 3880 μS/cm with 5.5 Environmental isotopes (δ2H and δ18O)
an average of 2044 μS/cm for 2007 campaign waters
and 382 to 3060 μS/cm with an average of 1495 μS/ A total of 19 samples collected in 2016 were analysed for
cm for 1900 campaign waters (Table 1). However, an stable isotopes (δ18O and δ2H). Seven samples represent
increase in EC values has been observed from 1995 to the downstream of study area (Plio-Quaternary aquifer),
2019. The spatial distribution of EC values (Fig. 7a–d) for and 12 samples represent the upstream of study area
the four campaigns indicates that the salinity of ground- (Cenomanian–Turonian aquifer). For the upstream sam-
water in the study area where groundwater discharges ples, the oxygen-18 contents vary between a minimum of
into the Atlantic Ocean has risen over time, especially − 6.01‰ vs SMOW and a maximum of − 3.28‰ vs SMOW,
in 2019. with an average of − 5.04‰ vs SMOW. For deuterium, the
maximum value is − 21.2‰ vs SMOW and the minimum
5.4 Mechanisms controlling groundwater chemistry value equal to − 34.5.8‰ vs SMOW with an average of
− 29.8‰ vs SMOW (Table 2). As for the downstream sam-
The Gibbs diagram is an important tool for identifying ples, the contents of oxygen-18 vary between a minimum
these geochemical processes [35]. This consists of a of − 5.08‰ vs SMOW and a maximum of − 3.9‰ vs SMOW,
plot of the ratio of dominant cations Na/(Na + Ca) and with an average of − 4.63‰ vs SMOW. For deuterium, the
anions Cl/(Cl + ­HCO3) against the TDS to determine the maximum value is − 20.2‰ vs SMOW and the minimum
general mechanisms controlling the chemical composi- value equal to − 28.7‰ vs SMOW with an average of
tion of the studied groundwater. Essentially, groundwa- − 24.87‰ vs SMOW (Table 2). The results of isotopic analy-
ter chemistry is controlled by three dominant natural sis, the global meteoric water line [38] and the local mete-
mechanisms, including rock weathering dominance, oric line [39], were reported on the deuterium–oxygen 18
evaporation dominance and precipitation dominance diagram; this diagram (Fig. 9a) shows that two groups of
[36, 37]. As indicated in Fig. 8, the possible causes of cati- water can be distinguished.
ons and anions dominance in groundwater samples are For the isotopic characterization of study area, two
the water–rock interaction and evaporation processes. reference lines were used: the global meteoric water line
The dominance of calcium and bicarbonate ions in the (GMWL) following Eq. (1) [38],
groundwater samples is due to weathering process in
aquifer rocks. Evaporation greatly increases concentra- 𝛿 2 H = 8 ∗ 𝛿 18 O + 10. (1)
tions of ions formed by chemical weathering, leading to And the local meteoric water line of Essaouira basin
higher salinity. (LMWL) according to Eq. (2) [39]:

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Fig. 7  Spatial distribution of EC in 1995 (a), 2007 (b), 2016 (c) and 2019 (d)

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Fig. 8  Gibbs diagrams for the major ion composition of the groundwater in the study area

modification of their content isotopic. The values of δ2H

𝛿 2 H = 7.95 ∗ 𝛿 18 O + 11.3. (2)
and δ18O on the intersection were the recharge (initial)
The first group is characterized by the most enriched isotope values from precipitation to the groundwater [41].
samples, generally from the upstream of study area, that The plot of C ­ l− versus δ18O is utilized to identify the
plot below the two reference lines (GMWL and LMWL), dominant mechanism controlling groundwater saliniza-
as like samples (El 4, El 2, El 1, El 5, El 7). These water tion (Fig. 9b). From the plot of ­Cl− vs δ18O, some number of
samples are located in the zone of the aquifer recharge, groundwater showed fairly constant δ18O with increased
which are mainly characterized by the absence of soil chloride concentration. This suggests that dissolution of
(Fig. 1). This trend could indicate recharge of the aqui- minerals is significant in this area. Furthermore, the analy-
fer by evaporated meteoric water and/or the return sis of the ­Cl− vs δ18O relationship (Fig. 9b) shows that the
flow of evaporated irrigation water. Evaporation can be most groundwater samples recorded low chloride concen-
produced either before recharging when precipitation tration with high δ18O values. This may suggest that such
passes through the atmosphere with low water content groundwaters are likely recharged by an enriched source
or after recharging by leaching heavy isotopes accumu- or maybe interacting with some surface water with low
lated during the dry season in the unsaturated zone. The chloride and enriched δ18O.
upstream study areas, which are characterized by an alti- On this basis, three distinct trends can be observed
tude above 350 m a.s.l [40], constitute the beginning of which reflects the impacts of the mixing process and
the recharge chain. evaporation on the isotopes and salinity of groundwater
The second group represents the majority of samples, (Fig. 9b).
situated close to the LMWL and GMWL. These waters As shown in Fig. 9b, the increase in the values of δ18O is
come from rapid meteoric water infiltration without any greater than that of the concentration of ­Cl−, indicating a

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Table 2  Isotopic composition of analysed samples campaign 2016 salinity of the infiltration water that is ultimately attached
in Meskala–Ouazzi sub-basin to the water table. Infiltration water salinity is derived from
Sample pH T EC δ2H δ18O both the surface water and the soil along the paths [43,
°C µS/cm ‰ vs. SMOW 44]. Furthermore, independently of the isotopic exchange,
high concentrations of ­Cl− with low values of δ18O are
Upstream
associated with the processes of salt accumulation inside
EL1 7.2 19.5 2190 − 31.9 − 4.83
the aquifer (mineral dissolution and transpiration) as in
EL2 7.8 21 1188 − 34.4 − 5.16
samples El 16 and El 17.
EL3 7.4 19.2 1300 − 34.1 − 5.73
EL4 7.3 22.1 1249 − 34.5 − 5.52
EL5 7.5 19.8 803 − 28.8 − 4.63
6 Conclusion
EL6 7.7 18.5 2050 − 28.4 − 4.89
EL7 7.5 18 3250 − 21.2 − 3.28
The socio-economic development in the Essaouira
EL8 6.9 22.1 3050 − 32.9 − 6.01
basin depends heavily on groundwater resource; thus,
EL9 7.1 23.7 1800 − 28.8 − 5.5
the hydrochemical and isotopic studies made in this
EL10 7.5 20.9 1883 − 27.6 − 5.06
article aim to assess the process of salinization and
EL11 7.3 23 4150 − 24.3 − 4.61
recharge of the Plio-quaternary aquifer and Cenom-
EL12 7.1 23.4 2550 − 30.7 − 5.35
ano-Turonian aquifer given its strategic importance
Downstream
in the study area. Regarding hydrochemistry, with the
EL13 7.4 23.3 1894 − 24.2 − 4.34
observed increases in salinity, the chemical composi-
EL14 7.4 21.2 1933 − 26.8 − 4.88
tion of groundwater at a given sampling point did not
EL15 7.2 22.1 2020 − 22.7 − 4.58
improve. Furthermore, groundwater is mineralized,
EL16 7.2 24 2550 − 28.7 − 5.08
since EC values are between 1495 μS/cm for 1995 to
EL17 7.1 23.2 3100 − 27.8 −5
2449 μS/cm for 2019, explained by the decrease in the
EL18 7.3 20.8 3150 − 23.7 − 4.63
precipitation due to climate change and overexploita-
EL19 7.4 20.5 4450 − 20.2 − 3.9
tion. The main phenomenon controlling the salinity of
Min 6.9 18 803 − 34.5 − 6.01
the groundwater seems to be the dissolution of evapo-
Max 7.8 24 4450 − 20.2 − 3.28
rites (halite, gypsum and anhydrite) in the study area
Mean 7.33 21.38 2345.26 − 27.98 − 4.89
of Meskala–Ouazzi sub-basin. The results obtained in
Sd 0.22 1.82 983.68 4.42 0.64
the isotopic study showed that the groundwater of the
Cenemano-Turonian and Plio-Quaternary aquifer comes
from precipitation. According to the reports on deute-
recharge of groundwater (i.e. irrigation water, river water rium and oxygen-18, water quickly enters the aquifer
or precipitation) with a low ­Cl− the concentration contrib- without major change in the relative abundances of
utes to the enrichment of isotopic values as like in samples these two elements due to the phenomenon of evapo-
El 3 and El 4. ration, except for a few samples which are located in
The increase of the δ18O values along with C ­ l− con- the recharge zone. The combination of chemical and
centrations enrichment could be a result of evaporation isotopic parameters, in particular C­ l− and δ18O, supports
(either during recharge, from shallow water levels, or the hydrochemical approach’s results by confirming that
seepage of sewage from the village of Meskala due to the the dissolution process is one of the key phenomena
absence of sanitation channels) as like in sample EL7, as leading to groundwater mineralization in the study
the evaporation process enriches both δ18O values and area. Knowledge of sources of groundwater recharge is
­Cl− concentrations [42]. The δ18O values of groundwater essential for the protection and management of global
are enriched by surface water recharge (Wadi Igrounzar), aquifer systems, especially in regions where rainfall is
while the variation of ­Cl− concentrations depends on the likely to be significantly affected by climate change.

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Fig. 9  Isotopic data in the study area. a δ18O versus δ2H for 2016 campaign; b δ18O versus ­Cl− diagram

Acknowledgements The authors are grateful to our colleagues for 2. Carreira PM, Marques JM, Nunes D (2014) Source of groundwater
their assistance in data collection and field investigation. Special salinity in coastline aquifers based on environmental isotopes
thanks go to the Editor-in-Chief and the reviewers for their critical (Portugal): natural vs. human interference. A Rev Reinterpret
reviews and valuable suggestions. We thank the people of Tensift Appl Geochem 41:163–175. https://​doi.​org/​10.​1016/j.​apgeo​
Hydraulic Basin Agency (ABHT) of the city of Marrakech for their chem.​2013.​12.​012
help in the data piezometry, especially Mrs. Najar Insaf, Mr. Benaddi 3. Bouteraa O, Mebarki A, Bouaicha F, Nouaceur Z, Laignel B (2019)
Rabia and Mr. Qachar Mohammed. We do not forget to thank the Pr Groundwater quality assessment using multivariate analysis,
Ebn Touhami Mohamed, dean of the Faculty of Sciences of Kenitra, geostatistical modeling, and water quality index (WQI): a case
for his assistance during the chemical analyses of ­K+ and ­Na+ of the of study in the Boumerzoug-El Khroub valley of Northeast
groundwater collected in 2019. Algeria. Acta Geochim 38:796–814. https://​doi.​org/​10.​1007/​
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Declarations 4. Bahir M, Ouhamdouch S, Ouazar D, Chehbouni A (2020) Assess-
ment of groundwater quality from semi-arid area for drinking
purpose using statistical, water quality index (WQI) and GIS
Conflict of interest The authors declare that they have no conflict of
technique. Carbonates Evaporites 35:1–24. https://​doi.​org/​10.​
interest.
1007/​s13146-​020-​00564-x
5. El Mountassir O, Bahir M, Ouazar D, Carreira PM (2021) Nitrate
Open Access This article is licensed under a Creative Commons Attri- pollution in groundwater of the Ouazi Basin: case of Essaouira
bution 4.0 International License, which permits use, sharing, adap- (Southwestern Morocco). In: Abrunhosa M, Chambel A, Pep-
tation, distribution and reproduction in any medium or format, as poloni S, Chaminé HI (eds) Advances in geoethics and ground-
long as you give appropriate credit to the original author(s) and the water management: theory and practice for a sustainable devel-
source, provide a link to the Creative Commons licence, and indicate opment. Advances in science, technology and innovation (IEREK
if changes were made. The images or other third party material in this interdisciplinary series for sustainable development). Springer,
article are included in the article’s Creative Commons licence, unless Cham. https://​doi.​org/​10.​1007/​978-3-​030-​59320-9_​49
indicated otherwise in a credit line to the material. If material is not 6. El Mountassir O, Bahir M, Ouazar D, Carreira PM (2021) For a
included in the article’s Creative Commons licence and your intended better understanding of recharge and salinization mechanism
use is not permitted by statutory regulation or exceeds the permitted of a Cenomanian–Turonian aquifer. In: Abrunhosa M, Chambel
use, you will need to obtain permission directly from the copyright A, Peppoloni S, Chaminé HI (eds) Advances in geoethics and
holder. To view a copy of this licence, visit http://​creat​iveco​mmons.​ groundwater management: theory and practice for a sustain-
org/​licen​ses/​by/4.​0/. able development. Advances in science, technology and innova-
tion (IEREK interdisciplinary series for sustainable development).
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