Environ Monit Assess (2024) 196:365

https://doi.org/10.1007/s10661-024-12533-1

RESEARCH

Geochemical processes, salinity sources and utility

characterization of groundwater in a semi‑arid region
of Iraq through geostatistical and isotopic techniques
Ali Al Maliki · U. Saravana Kumar · Ali Hasan Falih · M.A Sultan ·
Amer Al‑Naemi · Dalal Alshamsi · Hasan Arman · Alaa Ahmed ·
Chidambaram Sabarathinam

Received: 17 November 2023 / Accepted: 5 March 2024 / Published online: 14 March 2024
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2024

Abstract Identifying factors contributing to water isotope analysis revealed that the water originated
salinity is paramount in efficiently managing limited from meteoric sources and underwent significant
water resources in arid environments. The primary evaporation during or before infiltration. The utility
objective of this study is to enhance understanding assessment of water samples indicates that most sam-
regarding the hydrochemistry, source, and mecha- ples are not appropriate for consumption and are sig-
nism of water salinity, as well as to assess the suit- nificantly below the established standards for potable
ability of water for various uses in southern Iraq. water. In contrast, a significant portion of the ground-
The groundwater samples were collected from water water samples were found to meet the criteria for
wells and springs and analyzed for major cations and irrigation suitability by adopting Wilcox and the US
anions along with stable isotopes (δ18O and δ2H) to Salinity Laboratory criteria. The groundwater could
accomplish the objective. The analysis of major ion be considered for irrigation with proper salinity con-
chemistry, hydrochemical techniques, principal com- trol management. Overall, this study has significantly
ponent analysis (PCA), and isotope signatures were improved the understanding of the hydrogeochemical
adopted to determine the primary factors contribut- regimes and acts as a first step toward the sustainable
ing to water mineralization. The study inferred that utilization of water resources.
evaporation and geological processes encompassing
water–rock interactions, such as dissolution precipita-
tion and ion exchange, were key processes. The stable

A. Al Maliki · A. H. Falih · M. Sultan · A. Al‑Naemi D. Alshamsi · A. Ahmed

Ministry of Science and Technology/ Environment, Water National Water and Energy Center, United Arab Emirates
and renewable energy Directorate, Baghdad, Iraq University, Al Ain 15551, United Arab Emirates

U. S. Kumar (*) A. Ahmed

Isotope Hydrology Section, Division of Physical Geology Department, Division of Water Resource, Desert
and Chemical Sciences, International Atomic Energy Research Center, Mathaf El Matariya Street, Cairo 11753,
Agency (IAEA), Vienna, Austria Egypt
e-mail: U.D.Saravana-Kumar@iaea.org; uskumar1@
rediffmail.com C. Sabarathinam
Water Research Center, Kuwait Institute for Scientific
D. Alshamsi · H. Arman · A. Ahmed Research, Kuwait City, Kuwait
Geosciences Department, United Arab Emirates
University, Al Ain 15551, United Arab Emirates

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 365 Page 2 of 18 Environ Monit Assess (2024) 196:365

Keywords Hydrochemical characteristics · identify the various mechanisms by which groundwa-

Statistical analysis · Isotope signatures · Water quality ter undergoes an increase in salinization (Kharroubi
assessment et al., 2012; Abu-Alnaeem et al., 2018; Chidambaram
et al., 2020; Fu, et al., 2018). Multivariate method-
ologies, such as principal components analysis (PCA)
Introduction and hierarchical cluster analysis (HCA), help reduce
the complex datasets’ dimensions and segregate the
Salinization is a major threat to water quality in arid data into separate components or clusters. These fac-
and semiarid regions, especially in the regions that tors or groups are determined based on the correlation
primarily depend on groundwater for basic needs adopting pre-established variables (Kim et al., 2003;
(Kammoun et al., 2018; Boosalik et al., 2022). Iden- Pillai et al., 2020). The application of multivariate
tifying the source and assessing the risks associ- statistics in hydrogeology has demonstrated its effi-
ated with groundwater salinity is a contentious con- cacy in various aspects, such as the identification of
cern among hydrogeologists (Jackson et al., 2013). recharge and discharge locations, determination of the
Although the causes of groundwater salinity have origin of contaminated groundwater, and examination
been subjected to extensive research, many ques- of the groundwater-surface water interaction (Papa-
tions remain as puzzles (Polemio, 2020). Natural theodorou et al., 2007; Guggenmos et al., 2011; Zhang
processes, human activities, or both can cause salini- et al., 2018).
zation (Güler et al., 2012; Han & Currell, 2018; Li The present study targets the groundwater regime
et al., 2019; Mastrocicco et al., 2021). These include in the southern region of Iraq by integrating hydro-
the weathering of sediments and evaporated minerals chemical and isotopic data, employing geochemical
(Lü et al., 2013; Del Pilar Álvarez et al., 2015), vari- and multivariate statistical analysis. This research is
ation in precipitation and temperature (Chen et al., particularly significant since water quality (UN-SDG
2019), agricultural activities (Giambastiani et al., indicator 6.3.2) is a significant factor, and it is hard
2013; Pulido-Bosch et al., 2018; Tomaz et al., 2020), to assess in developing nations due to a lack of data.
inland migration of saltwater (Barlow & Reichard, Hence, addressing the sources of poor water qual-
2010; Najib et al., 2017; Chidambaram et al., 2020), ity and managing the available freshwater resources
hydrogeological factors and water–rock interactions requires a solid dataset and strong interpretations to
(Belkhiri et al., 2012; Ahmed & Clark, 2016), and provide solutions for achieving SDG 6. For the last
over-exploitation of the groundwater from aquifers two decades, the country has been recognized as one
(Khezzani & Bouchemal, 2018; Panda et al., 2020). of the most water-deficient countries globally due to
Multiple processes, such as residence time, oxida- its persistent semi-arid to arid climate, population
tion–reduction, ion exchange, evaporation, precipita- expansion and substantial demand for limited surface
tion, mineral dissolution, aquifer permeability, and cli- and groundwater resources. The primary aim of this
matic conditions, contribute to water salinity’s spatial study is to gain insight into the of groundwater salin-
and temporal variability as it travels from the recharge ity to assess the predominant geochemical processes
to discharge (Ahmed & Clark, 2016). The salinization that contribute to groundwater chemistry, determine
processes of subsurface water and their sources can the source of water recharge, and evaluate the potabil-
be traced using several methods (Aliewi et al., 2022; ity of drinking groundwater.
Chidambaram et al., 2022). It is widely known that
identifying the mechanisms and evolution of miner-
alization can be accomplished by integrating differ- Materials and methods
ent methods (Bennetts et al., 2006; Carol et al., 2009;
Chen et al., 2019; Nair et al., 2020). Many researchers Study area
integrated chemical and isotopic techniques to identify
the ion sources, mechanisms governing the chemistry The region considered for study is a part of the Meso-
of groundwater, and its quality, and utility for differ- potamian plain along the south of Iraq and is about
ent purposes (Xu et al., 2023). Furthermore, the mul- 180 km from Baghdad. The region is characterized as
tivariate statistical methods were also employed to a floodplain flanked by elevated mountain ranges in

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Environ Monit Assess (2024) 196:365 Page 3 of 18 365

the west, arid desert terrain in the east and the Ara- Mesopotamian region, especially in the Euphra-
bian Gulf in the south. The floodplain primarily com- tes sub-region, which led to a paralleled series of
prises sediments from the Tigris and Euphrates rivers northwest–southeast normal faults, where they are
through their flow and flooding events. Throughout traversed by numerous geological formations to the
the study area, topography is variable, gently slop- west of the Euphrates River (Fouad, 2015). In terms
ing towards the southeast (Fig. 1). The region expe- of stratigraphy, the stratigraphic sequence starts with
riences an arid to semi-arid environment, character- the Umm al-Ruduma formation, which was deposited
ized by average rainfall ranging from 3.84–18.04 mm/ during a huge transgression during the late Paleocene
month between May and November and 14.11–22.56 to early Eocene (Jassim & Goff, 2006). The forma-
mm/month from December to February (IMO, tion consists mainly of a dense succession of carbon-
2020). The temperature is high in the summer, which ate and limestone rocks. It is overlaid conformably by
upscales from April with an average of 24.74°C and the alternating anhydrite marl, shale, and limestone of
reaches its highest value in July, recording an average the lower Eocene Rus Formation (Fig. 2). The rocks
of 36.62°C. are overlaid unconformably by upper-middle Eocene
nummulitic limestones formation referred to as the Jil
Geology and hydrogeology (Sissakian & Mohammed, 2007). The Jil formation is
followed by the deposition of the Dammam formation
Geologically, Iraq is an essential part of the huge of the early Eocene, which is mainly of dolomite and
tectonic-strategic sequence of the Arabian Penin- limestone rocks alternating with marly limestones and
sula (Martin, 2001). According to this sequence, Iraq portrayed by the occurrence of fissures, karst chan-
was divided into a stable shelf consisting of three nels, and fractures. On top of the Dammam forma-
main components, including the Mesopotamian Sal- tion, the Euphrates formation of the early Miocene is
man region, the Rutba-Al Jazeera sub-region, and an deposited. This deposition comprises basal conglom-
unstable shelf separated by the Abu Jir fault (Jassim erates and limestone (Jassim & Goff, 2006).
& Goff, 2006; Fouad, 2015). The region considered The shallow groundwater in this region is
for the study is positioned in the weakest unit of the restricted to the unconsolidated, sandy aquifer group

Fig. 1  The basic informa-

tion about the area consid-
ered for study: a study site
in Iraq, b geologic map, c
digital elevation map based
on SRTM (30 m. resolu-
tion) with samples sites and
d water salinity distribution
with high and low value
of TDS of 8820 and 2600
respectively

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 365 Page 4 of 18 Environ Monit Assess (2024) 196:365

Water sampling and analysis

Groundwater samples were taken from 57 wells

and 21 springs for this study, covering 2020 and
2022. The collection of groundwater samples
was preceded by purging the wells for 7–10 min;
field parameters were measured after stabiliz-
ing the physiochemical parameters. This study
employed a multi-parameter analyzer, specifically
the TPS/90FL-T Field kit, to conduct in situ meas-
urements of water temperature, pH, and electrical
conductivity (EC). The water samples were col-
lected in 500-mL-sterilized polypropylene bottles.
These bottles had been previously cleaned using
a solution of 10% nitric acid, followed by a thor-
ough rinse with deionized ultra-pure water and
subsequently with the sample before sampling.
All the samples were sealed immediately, labeled,
stored at 5°C, and transported to the Laboratory
of the Iraqi Ministry of Science and Technology
for further analysis. The major ion contents were
measured according to analytical procedures of
the American Public Health Association (APHA,
2012). The concentrations of calcium and mag-
nesium were determined by titration, potassium
and sodium using flame emission photometry, the
bicarbonate ion by titration with 0.1 M HCl, the
chloride ion using the silver nitrate method, and
the sulfate ion through the gravimetric method.
The accuracy of all samples was assessed by meas-
uring their charge balance error (CBE) using the
Eq. 1:
∑ ∑
Charge balance error (CBE%) = cation − anion
Fig. 2  Generalized hydrostratigraphic section showing the
main water-bearing formation (Rashid et al., 2022)
∑ ∑
∕ cation + anion × 100
(1)
wherein all samples have a CBE within ±5%.
of Quaternary deposits. The Euphrates and Dam- Stable isotope analysis (δ18O and δ2H) was per-
mam formations are recognized as deep aquifers. formed in the Laboratories of Isotopes at the Iraqi
The Dammam formation ranges from 70 to 200 m Ministry of Science and Technology using a liq-
thick, whereas the Euphrates formation has an aver- uid water stable isotope analyzer (LWSIA) and an
age thickness of roughly 80 m, predominantly dip- isotope ratio mass spectrometer (IRMS). Measure-
ping towards the easterly direction. As a result, the ments were compared to Vienna Standard Mean
groundwater predominantly flows towards the east. Ocean Water (VSMOW) from IAEA with a stand-
Both the deep and shallow aquifers contribute to the ard reference code TC 7027. The measured values
Dammam formation. These aquifers are loosely con- were expressed per mill (‰) based on the standard
nected, allowing water to move from the deep aqui- equation.
fer to the shallow aquifer (Rashid et al., 2022).

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Environ Monit Assess (2024) 196:365 Page 5 of 18 365

Multivariate statistical analysis alkaline pH in some water samples. The average

­HCO3− concentration was 132.54 mg/L, while the
Multivariate statical analysis was used to determine average ­CO32− concentration was 12.34 mg/L. The
the set of reactions that govern the process of water ­HCO3− concentration range was 18.69–293 mg/L,
chemistry by analyzing the hydrochemical data while that of ­CO32− varied from below the detec-
and using conventional diagrams, including Piper tion limit (BDL) 0–150 mg/L. Natural sources of
(1944), Durov (1948), and ionic ratios. The results ­HCO3− include the dissolution of carbonate-con-
were achieved through Varimax rotation and Kai- taining minerals and the reaction of carbon dioxide
ser normalization of the analytical data using IBM ­(CO2) with rainwater (Drever, 1988). Salinity lev-
SPSS Statistics v28 and Minitab software. The ana- els in the groundwater were highest in the central
lytical results from the laboratory analysis were regions and lowest in the southern regions, opposite
compared with the WHO standards for drinking and to the predominant groundwater flow direction. Salin-
standards for irrigation water suitability. One of the ity decreased significantly from the area’s perimeter
limitations of this study is that it does not evalu- to its center, as measured by total dissolved solids
ate the bacteriological quality of drinking water, (TDS). The process of rock–water interaction, a long
which is an important factor in determining water residence time, a semi-arid climate, and a high evap-
potability. oration rate are likely contributors to the increase in
the salinity of groundwater, as indicated by the high
TDS values (Boosalik et al., 2022).
Results and discussions Cation concentrations ranged from 19.46 to 1920,
17.85 to 4392, and 19.51 to 29,900 mg/L for ­Ca2+,
Chemical evidence ­Mg2+, and N ­ a+, respectively. These cations were
found to have average concentrations of 592.5, 481.6,
Major ion chemistry and 2398.8 mg/L, respectively. Both C ­ l− (range:
2−
27.2–46860 mg/L) and ­SO4 (range: 18.69–17760
A slightly alkaline groundwater was indicated by a mg/L) were found to be significantly variable, with
pH range of 6.80–8.70 and a mean of 7.44. (Table 1). ­Cl− averaging 4343.4 mg/L and ­ SO42− averaging
−
High concentrations of hard-water constituents, 2610.5 mg/L. C ­ l concentrations can be affected
such as bicarbonate (­HCO3−), may account for the by natural and anthropogenic processes, such as the
leaching of halite (NaCl) and other minerals from
evaporated deposits or anthropogenic processes.
Table 1  Descriptive statistics of the physical and chemical While gypsum-containing carbonate sedimentary
parameters of the water samples rocks and/or soil with varying amounts of gypsum
Parameter Mean Std. dev. Minimum Maximum can be sources of ­SO42− (Chidambaram et al., 2020).
Both ­NO3− and B levels in the area under study var-
pH 7.44 0.36 6.80 8.70 ied from BDL, with ­NO3− rising to 204 mg/L and
EC 15.16 21.30 3.47 106.00 boron to 54 mg/L.
TDS 12011.82 17813.83 2600.00 88,020
Ca2+ 592.53 347.20 19.46 1920.00 Hydrochemical facies
Mg2+ 481.66 796.71 17.85 4392.00
Na+ 2398.82 5038.86 19.51 29,900.00 The Piper diagram was used to depict the hydrogeo-
K+ 119.36 297.00 0.72 1917.00 chemical facies and predominant water types (Fig. 3).
Cl- 4343.4 8511.81 27.23 46,860.00 The water samples showed some chemical similari-
SO42- 2610.54 3153.65 18.69 17,760.00 ties based on their major ion composition. The chemi-
CO32- 12.34 23.95 0.00 150.00 cal compositions of spring and well water was simi-
HCO3- 132.54 58.27 10.15 293.00 lar, with Ca–Mg–SO4 water types reflecting sulfate
NO3- 49.93 57.51 0.00 204.00 predominance and a higher concentration of alka-
B 4.05 8.23 0.00 54.00 line earth ­(Ca2+ and ­Mg2+) than alkali metals ­(Na+
All units are in mg/L, except for EC (μS/cm) and ­K+). Southern and northern regions of the study

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 365 Page 6 of 18 Environ Monit Assess (2024) 196:365

Fig. 3  The major hydro-

chemical facies and water
types of the samples
considered were portrayed
by adopting the standard
Piper plot

area feature low salinity water, while hypersaline 0.75) with N ­ a+, ­K+, ­SO42−, and ­CO32− was depicted
waters dominate inland regions. The water type of ; the correlation was moderately positive (r = 0.5)
this hypersaline water was similar to that of Kuwait, with ­Mg2+ and C ­ l−; and a weak positive correla-
located in the south of the study area (Bhandary et al., tion (r = 0.45) with ­HCO3−. In addition, there was
2018). Hydrochemical facies have a very consistent a highly positive correlation (r > 0.9) of K ­ + with
2+ 2− 2+ 2−
spatial distribution with TDS changes. ­Ca , ­SO4 and C ­ a , ­CO3 with C ­ a , ­Na and ­K+,
2+ +
2− 2− −
Durov diagram (Durov, 1948) has been used to ­CO3 with S ­ O4 , ­HCO3 and N ­ a+, and C
­ l− with
− 2−
indicate the mixing between the surface water and ­HCO3 and ­CO3 was observed. A moderate posi-
ground-water (Figure 7). The majority of ground- tive correlation (r > 0.5) was found between C ­ a2+ and
water samples are plotted in 2, 4 and 5 fields, indi- 2−
­Cl , ­Mg , ­Na , and ­CO3 , ­Na and ­Cl , and ­Cl− and
− 2+ + + −

cating direct recharge of surface water, otherwise ­CO32−. Finally, a weak positive correlation was found
mixed water or simple dissolution with reverse cation between ­Cl− and ­K+, ­SO42− and ­Cl−, ­CO32− and pH,
exchange process. and ­HCO3− and ­Ca2+. Based on the calculated cor-
relation matrices, it can be observed that association
Sources of salinity between ions ­Na+, ­K+, ­Mg2+, ­Cl− ions indicate the
possibility of evaporation process, and that of pH, K ­ +,
2+
The accumulation of dissolved solids in groundwa- ­Ca reflects ion exchange process. Further carbon-
ters is often attributed to various factors, which can ate weathering process is inferred due to the correla-
be determined by analyzing the relative abundance, tion pattern between pH ­Ca2+, ­Mg2+, ­HCO3−, ­CO32−,
ratios, and interactions of different ions, as outlined in and the relationship of different ions (TDS, ­ Ca2+,
Table 2. Investigating the relationship between twelve ­Mg2+, ­Na+, ­K+, ­HCO3−, ­CO32−, ­SO42−, ­Cl−) indicate
chemical variables—pH, TDS, ­Ca2+, ­Mg2+, ­Na+, ­K+, salts originating from the evaporites might have also
­HCO3−, ­CO32−, ­SO42−, ­Cl−, B, and ­NO3− revealed played a substantial role in influencing the hydro-
intriguing observations. Among the parameters chemistry of groundwater (Tarawneh et al., 2019;
measured by TDS, a strong positive correlation (r = Boosalik et al., 2022).

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Environ Monit Assess (2024) 196:365 Page 7 of 18 365

Table 2  Correlation matrix for the analytical values of geochemical variables in the water samples of the study area
pH TDS Ca2+ Mg2+ Na+ K+ Cl- SO42− CO32− HCO3− NO3− Br

pH 1.00
TDS 0.21 1.00
Ca2+ 0.20 1.00 1.00
Mg2+ −0.14 0.64 0.66 1.00
Na+ 0.38 0.82 0.83 0.53 1.00
K+ 0.07 0.94 0.94 0.71 0.81 1.00
Cl- 0.10 0.51 0.51 0.26 0.52 0.47 1.00
SO42− 0.06 0.94 0.94 0.75 0.81 0.99 0.47 1.00
CO32− 0.41 0.76 0.76 0.52 0.95 0.75 0.51 0.74 1.00
HCO3− 0.38 0.45 0.45 0.05 0.69 0.38 0.81 0.37 0.67 1.00
NO3− 0.17 0.18 0.21 0.17 0.37 0.14 0.07 0.15 0.34 0.30 1.00
B 0.12 −0.28 −0.27 −0.14 −0.17 −0.21 −0.21 −0.24 −0.12 −0.11 −0.13 1.00

Interelement relationships corroborated the prevalence of evaporation (Subram-

ani et al., 2010). As the EC value increases, the ­Na+/
The influence of three major processes (rainwater dis- Cl− value also rises (Fig. 5a), which may be due to the
solution, weathering, and evaporation) governing the prevalence of aridity. Thus, evaporation is expected
water chemistry was visualized using a boomerang to impact groundwater element concentrations apart
plot proposed by Gibbs (Gibbs, 1970) and is widely from other additional processes significantly.
used to illustrate the main causes of water mineraliza- The TDS concentrations are highest at the study
tion and salinization (Ahmed & Clark, 2016; Li et al., area’s periphery and gradually increase towards the
2016), and the plot has been adopted in recent geo- center. This variation shows that the residence time
chemical software CHIDAM (Chidambaram et al., of the water in the aquifers and other geochemical
2021). The position of the samples in the plot indi- processes are the main contributing factors of the
cates that they are primarily affected by evaporation, groundwater salinity as it corresponds to the prin-
as a majority of samples are observed in the higher cipal groundwater flow direction. The results in the
TDS region of the plot (Fig. 4). The ­Na+/Cl− ver- Durov diagram reveal that the majority of the sam-
sus EC plot of the investigated water sample further ples can be found at fields 2, 4, and 5, suggesting

Fig. 4  Water samples plot- 100000 (a) 100000 (b)

ted in the Gibbs diagram
depicting the predominance
of evaporation mechanism 10000
10000

1000 1000
Rock Rock
TDS
TDS

Dominance Dominance

100 100

10 10
Surface Water Surface Water
Groundwater Groundwater

1
1
0 0.2 0.4 0.6 0.8 1 1.2
0 0.2 0.4 0.6 0.8 1 1.2
Cl-/(Cl+HCO3) Na+k/(Na+Ca+K)

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 365 Page 8 of 18 Environ Monit Assess (2024) 196:365

Fig. 5  Bivariation 1.00 500

Evaporation dominance
diagrams showing the (a)
0.80 400 (b)
relationship between differ-
ent chemical parameters of 300

Ca+Mg
0.60
the water samples from the

Na/Cl
200
study area 0.40
100
0.20
0
0.00 0 100 200 300 400 500
0 50000 100000 150000 HCO3+SO4
EC

500 120
100 (d)
400 (c)
80
300
60

Ca
SO4

200 40
100 20
0
0
0 10 20 30 40
0 100 200 300 400 500
Ca HCO3

200
(e)

150

100
Ca

50

0
0 100 200 300 400
Mg
6 150 (h)
(g)
Ca+Mg-HCO3-SO4

100
4 50
HCO3

0
2 -200 -100 0 100
-50
-100
0
-150
0 500 1000 1500 2000
Total Cations Na-Cl

dissolution with cation exchange as a possible be attributed to the gypsum and/or anhydrite dis-
source of water mineralization (Fig. 6). The ­Ca2++ solution, while increased levels of H ­ CO3− can be
­Mg2+ against ­HCO3−+ ­SO42− plot (Fig. 5b) sug- ascribed to the weathering process of carbonates
gests the dissolution of both carbonate and sulfate (Prasanna et al., 2010). Most of the water sam-
along with ion exchange may affect groundwa- ples in the C ­ O42− variation diagram were
­ a2+ and S
ter mineralization (Liu et al., 2020). Furthermore, observed to fall above the line 1:1 (Fig. 5c), reflect-
a significant proportion of the water samples are ing the depletion of C ­ a2+ or increase of S ­ O42−.
proximal to the 1:1 equiline, indicating the deficit Such mechanism can be mainly due to calcite pre-
of ­(HCO3−+SO42−) ions for counterbalancing the cipitation triggered by gypsum dissolution, which
presence of alkali ions (­ Na++K+) (Xu et al., 2023). is likely responsible for the enrichment—and
Consequently, elevated concentrations of ­SO42− can referred to as the common ion effect, ­Ca2+ being the

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Environ Monit Assess (2024) 196:365 Page 9 of 18 365

Fig. 6  Durov plot of the

studied samples showing
the dominant hydrochemi-
cal processes

common ion for carbonate and sulfates (Chidam- evaporate deposits within the sedimentary layers of
baram et al., 2020). the aquifer (Liu et al., 2016). Moreover, it reflects a
Consumption of carbonic acid is often found slight surplus of ­Na+ and ­Cl− in a few samples in both
alongside calcite precipitation in water. The increased spring and well waters, primarily attributed to weath-
­pCO2 increases the availability of ­H2CO3 for reaction ering and/or ion exchange reactions. If the sum of cat-
(Samayamanthula et al., 2022). Thus, it subsequently ions and ­HCO3− concentration are almost equal, then
increases the availability of ions in the groundwater, it could indicate a possibility of silicate weathering
resulting in the saturation and precipitation of car- based on the lithology (Kim, 2003). The current study
bonate minerals (Chidambaram et al., 2011). The shows that silicates are also involved in the minerali-
relationship of C ­ a2+ versus ­HCO3− reflects a remark- zation processes (Fig. 5g). The main cause of excess
able deficiency of H ­ CO3- and enrichment of C ­ a2+ ­Na+ is probably due to cation exchange facilitated by
in groundwater samples (Fig. 5d). Additionally, an clay minerals. Thus, it could be inferred that the cati-
excess of C ­ a2+ relative to M
­ g2+ could be explained ons adsorbed on the clay are swapped for other ions
by calcite dissolution during infiltration (Liu et al., during ion exchange. (Meybeck, 1987). The chloro-
2020). The sample points cluster around and below alkaline indices could be used to study the exchange
the 1:1 line, resulting from calcite dissolution equation for ­Na+ and C ­ a2+, which frequently occurs
(Fig. 5e). in many natural groundwater systems (Schoeller,
The scatter plot depicting the relationship between 1967; Chidambaram et al., 2021). CA1 and CA2,
­Na+ and C ­ l− reveals that the majority of the samples which are expressed using the following Eqs. 2 and 3:
are dispersed along the 1:1 line (Fig. 5f). The data )]
presented potentially suggests the potential role of CA1 = Cl− − Na+ + K+ ∕Cl− (2)
(

alkalis derived from chloride (­Cl−) salts found in the

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 365 Page 10 of 18 Environ Monit Assess (2024) 196:365

Table 3  Factors loadings and explained variance ion exchange processes. The correlation associated
Parameter Component with Ca–Mg–SO4–HCO3 and Na–Cl adequately
supports the process of the N­ a+–Ca2+ exchanges on
1 2 3
the water chemistry (Fig. 5h). As a result, the sur-
pH −0.02 0.82 −0.12 plus ­Na+ is postulated mainly due to ion exchange
TDS 0.89 0.23 0.28 or feldspar weathering caused by an increase in
Ca2+ 0.90 0.24 0.27 groundwater residence in contact with aquifer mate-
Mg2+ 0.86 −0.12 −0.03 rials (Maskooni et al., 2021), apart from the pro-
Na+ 0.72 0.57 0.28 cess of evaporation. To summarize, the chemical
K+ 0.94 0.14 0.21 approach revealed that the main causes of salinity in
Cl− 0.27 0.30 0.78 the study area were evaporation, ion exchange, dis-
SO42− 0.95 0.12 0.21 solution of evaporite-bearing rocks, and carbonate
CO32− 0.67 0.60 0.24 weathering caused by the common-ion effect.
HCO3− 0.15 0.68 0.66 Principal component analysis (PCA) was stud-
NO3− 0.14 0.43 0.05 ied for the analytical dataset, showing that there are
B −0.17 0.31 −0.65 only three major factors explaining 78.98% of the
Eigen values 5.24 2.37 1.86 total variation in the data set (Table 3 and Fig. 7).
Variance % 43.70 19.74 15.54 The first factor accounts for 43.70% of the vari-
Cumulative % 43.70 63.44 78.98 ance in water samples, showing very high-positive
loadings for ­ SO42−, ­K+, ­Ca2+, TDS, ­ Na+, ­Mg2+,
and ­CO32−. The process indicates the dissolution of
carbonates and sulfates. Further, the negative repre-
sentation of pH and positive loadings of K­ + indicate
the reverse exchange process (Thilagavathi et al.,
2014).
The second factor accounted for 19.74% of the
overall variance, with the highest positive load-
ing for pH, ­HCO3−, ­CO32−, and ­Na+, reflecting the
sodic silica mineral weathering (probably plagio-
clase feldspars) or redissolution of precipitated car-
bonates of sodium (Nepolian et al., 2022), which
has resulted during the process of evaporation.
The third factor explains 15.54% of the total vari-
ance, showing high-positive loadings for C ­ l− and
−
­HCO3 , indicating the leaching of evaporite salts;
the association of leading indicates the enrichment
of ­Cl− during the process of weathering and further
Fig. 7  Three-dimensional PCA analysis for water samples
from the study area
leaching of the salts subsequently during the wet
season thus infiltrating to the water table (Thilaga-
vathi et al., 2017). As ­NO3− is associated with the
)] ­Na+, ­HCO3−, and pH, in PCA 2, the possibility of
CA1 = Cl− − Na+ + K+ ∕SO2− + HCO−3 (3)
(
4 the nitrate ion in the alkaline environment would
be mainly facilitated by the agricultural or related
Positive values for these indices signify an
anthropogenic activities (Xu et al. 2023). The
exchange process in groundwater, wherein ­Na+ and
results of the PCA analysis validate the predomi-
­K+ are replaced by ­Ca2+ and ­Mg2+, which origi-
nant influence of dissolution, weathering, and evap-
nate from the weathering of rocks (Liu et al., 2020).
oration, which are the three major processes identi-
These two indices have positive and negative val-
fied as major mechanisms for salinity enhancement
ues, indicating the significance of reverse and direct
in the groundwater.

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Environ Monit Assess (2024) 196:365 Page 11 of 18 365

Isotopic evidence The consistent enrichment in stable isotopes

during groundwater evaporation results in devia-
Isotopes in water tions from the LMWL and GMWL along evapo-
ration lines with slopes of typically 4–6 (Gat and
The distribution of δ18O in both spring and water Carmi, 1970). Groundwater tends to be isotopi-
wells ranged from −4.32 to 0.04‰ (mean = cally enriched under deep water level conditions
−2.33‰) and −7.32 to 0.95‰ (mean = −2.86‰), with lesser permeability and slow groundwater flow
respectively, while that of δ2H ranged from −33.50 to rate, facilitating long residence time. The long resi-
4.80‰ (mean = −19.60‰), and −36.16 to −11.84 dence time of water is commonly reported in hard
‰ (mean = −22.36‰), respectively. The δ18O–δ2H rock aquifers (Prasanna et al., 2010). This pattern is
diagram suggests that water is recharged from similar observed in the groundwater samples of the region
sources (Fig. 8a). Both springs and water wells have (Fig. 8a), indicating that the isotope enrichment is
similar trends that deviate from the Local Meteoric one of their defining characteristics. Plotting chlo-
Water Line (LMWL) (Al-Naseri et al. 2022) and the ride against δ18O (Fig. 8b) can help you under-
Global Meteoric Water Line (GMWL) but had a gen- stand groundwater’s evaporation and salinization
tle slope, suggesting that the process of evaporation mechanisms. Two types of water can be noticed in
had occurred before infiltration, or within the vadose the diagram; the first type is salinized water, which
zone. Strong evaporation enriches samples, and they results from the dissolving of soluble salts (Thila-
deviate from the LMWL. Most samples are observed gavathi et al., 2017). Increased chloride concentra-
as a group near the GMWL, and the evaporation line tion in this water type does not correspond with
intersects, displaying a uniform signature. The iso- increased δ18O enrichment. The second water cat-
topic signatures of groundwater and rainfall can differ egory reflects the evaporation signatures observed
greatly in semi-arid regions due to the high isotopic in both samples from springs and wells. In this type,
enrichment during water evaporation. The cluster- an increase in chloride content is accompanied by
ing of samples near LMWL indicates recharging via a steady increase in the δ18O signature. Salinity in
direct precipitation. the springs and shallow wells in the study area can

Fig. 8  a Deuterium vs. 1400 (b)

oxygen-18 diagram of 60 (a)
1200
water samples, b chloride 40

Evaporation
Chloride (mg/L)

vs. oxygen-18, c d-excess

LMWL δ2H = 7.66 * δ18O + 14.19 1000
20
vs. oxygen-18, and d TDS 0 Evaporation 800
δ2H (‰)

(vales in mg/L) vs. d-excess -20

600
(‰) -40
-60 Well 400
-80 Spring Dissolution
200
Linear (GMWL)
-100
Linear (LMWL) 0
-120 -10 -5 0 5
-20 -10 0 10
18O (‰ )
δ18O (‰)

50.00 (c) 100000

90000 (d)
40.00
80000
Evaporation

30.00
70000
TDS (mg/L)

20.00
d-excess

60000
10.00 50000
0.00 40000
-10.00 Evaporation 30000
-20.00 20000 Dissolution
10000
-30.00
-10 -5 0 5 0
-40 -20 0 20 40 60
18O (‰)
d-excess (‰)

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 365 Page 12 of 18 Environ Monit Assess (2024) 196:365

potentially be attributed to the process of evapora- Drinking water quality

tion, and salinity in groundwater, particularly in
deep wells, may be substantially impacted by the Hydrochemical properties such as TDS levels are
dissolving of soluble salts. used to classify the groundwater in this study and
establish its suitability for various uses. The potabil-
ity of water also depends on the physical parameters;
Deuterium excess the sample should have no turbidity and be physically
clear, tasteless, odorless, and colorless. Based on the
Deuterium excess (d-excess), which is calculated as classification of Freeze and Cherry (1979), the sam-
d-excess (‰) = δ2H - 8 *δ18O d (Dansgaard, 1964), ples are brackish to saline based on Davis and DeWi-
has emerged as a useful tool for tracking how evap- est (1966), it is mostly unfit for drinking or irrigation
oration affects the isotopic composition of precipi- (Table 4). As mentioned before, water’s high salinity
tation before groundwater is recharged. D-excess can mainly be due to evaporation and dissolution.
represents evaporation at 85% relative humidity and The groundwater in this study is categorized
has a value of 10 in the Global Meteoric Water Line. using international standards from the World Health
However, the regional precipitation’s d-excess value Organization (WHO, 2004). The pH values of the
could be more than 10 when the relative humidity water samples collected predominantly fall within the
at the source region where the water evaporates is neutral to alkaline range (Table 4). Nearly all water
lower (Gat and Carmi, 1970). In contrast, a higher samples had chloride levels exceeding the prescribed
d-excess of the evaporated vapor could be formed limit for drinking water. 45% and 47.37% of springs
due to the significant near-surface re-evaporation of and wells, respectively, exhibited high concentrations
waters under dry climate conditions. Thus, formed of sodium, exceeding the drinking water permissible
vapor will produce significant d-excess precipitation limit of 200 mg/L. Moreover, it was observed that
if it mixes with the atmospheric reservoir and con- all of the springs exhibited a magnesium concentra-
denses again (Clark and Fritz, 2013). In the present tion that was above the allowable limit. Consequently,
study, it is evident that the d-excess <10 across the this implies that all water samples are thus unfit for
study area, except for two well samples (Fig. 8c). human consumption. In addition, it is evident that
Since most of the study region’s groundwaters have both groundwater and surface water contained ele-
lower d-excess values, it is likely that there has been vated nitrate concentrations which could be often
strong evaporation of rainwater, before recharge from agricultural activities, or an anthropogenic pro-
except for the two-remaining groundwater with cess relating to the alkaline environment as indicated
higher d-excess. The large d-excess values in the in the PCA2.
groundwater samples may indicate a recent or rapid
recharge due to direct infiltration. The relationship Irrigation water quality
between the TDS and d-excess (Fig. 8d) for the well
samples indicate evaporation of rainwater prior to The groundwater quality is extremely important
recharge to the groundwater and that resulting in for agriculture and irrigation in semiarid areas.
higher TDS. The water composition, which impacts the plant
and soil, is the major factor in determining its suit-
ability for irrigation. If irrigation water contains
Suitability of water for different purposes too many dissolved ions, crop productivity may be
affected (Katerji et al., 2003). In order to assess the
One of the most important aspects of groundwater suitability of water for irrigation, various chemical
investigations is assessing the water quality for dif- characteristics were analyzed (Table 5). The ­Cl− ion
ferent utility purposes. Thus, understanding the qual- content is a significant chemical constraint used to
ity of groundwater in terms of whether it is suitable assess the water. According to Stuyfzand (1993),
for drinking, household, agricultural, and industrial there are eight categories of water. The findings of
uses is essential (Arumugam and Elangovan, 2009, this study show that 55% and 36.84% of the water
Memon et al., 2010, Rasouli et al., 2011). samples from springs and water wells, respectively,

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Environ Monit Assess (2024) 196:365 Page 13 of 18 365

Table 4  Classification of water samples based on TDS concentrations and categorizing their utility based on the ionic concentra-
tions of the analyzed parameters. All ion values are in mg/L, except for EC (μS/cm) and pH
Springs Wells

Freeze and Cherry (1979)

TDS concentration Main type Number Percentage Number Percentage
<1000 Fresh water type 0.00 0.00 0.00 0.00
1000–10,000 Brackish water type 15.00 57.69 46.00 80.70
10,000–100,000 Saline water type 5.00 42.31 11.00 19.30
>100,000 Brine water type 0.00 0.00 0.00 0.00
Davis and DeWiest (1966)
500 Desirable for drinking 0.00 0.00 0.00 0.00
500–1000 Permissible for drinking 0.00 0.00 0.00 0.00
1000–3000 Useful for irrigation 0.00 0.00 3.00 5.26
>3000 Unfit for drinking and irrigation 20.00 100.00 54.00 94.74
WHO (2004) Springs Wells
Parameter Maximum Number Percentage Number Percentage
pH 9.00 0.00 0.00 0.00 0.00
EC 1500.00 0.00 0.00 0.00 0.00
TDS 1500.00 0.00 0.00 0.00 0.00
 ­Cl− 600.00 19.00 95.00 56.00 98.25
 ­SO42− 400.00 0.00 0.00 7.00 12.28
 ­HCO3− 240.00 0.00 0.00 0.00 0.00
 ­Ca2+ 200.00 0.00 0.00 0.00 0.00
 ­Mg2+ 150.00 20.00 100.00 3.00 5.26
 ­Na+ 200.00 9.00 45.00 27.00 47.37
 ­K+ 12.00 0.00 0.00 0.00 0.00
B 0.50 0.00 0.00 0.00 0.00
 ­NO3− 50.00 19.00 95.00 51.00 93.00

Table 5  Suitability of Chloride values are expressed in mg/L

water for irrigation based on
Stuyfzand (1993) chloride Springs Wells
classifications
Main type Number Percentage Number Percentage
<5 Very oligohaline 0.00 0.00 4.00 7.02
5–30 Oligohaline 11.00 55.00 21.00 36.84
30–150 Fresh 6.00 30.00 22.00 38.60
150–300 Fresh-brackish 0.00 0.00 3.00 5.26
300–1000 Brackish 3.00 15.00 6.00 10.53
1000–10,000 Brackish-salty 0.00 0.00 1.00 1.75
10,000–20,000 Salt 0.00 0.00 0.00 0.00
>20,000 Hyper-saline 0.00 0.00 0.00 0.00

were not suitable for irrigation. However, 30% and Wilcox (1955) categorized groundwater for irriga-
38.6% were suitable for irrigation, and the remain- tion into categories based on its Na content. In this
ing samples were categorized as brackish or brack- classification, the term “Na content” refers to the
ish-salt water. percentage of soluble sodium (%Na) in groundwater

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 365 Page 14 of 18 Environ Monit Assess (2024) 196:365

(Wilcox, 1955). About 53% of the spring water is including C3S1, C4S1, C5S1, C4S2, C5S2, C5S3,
categorized to represent excellent and good class for and C5S4, where S1 and S2 represent low and
irrigation, whereas 23.23% of the samples are found medium SAR hazard levels, respectively, and C2, C3,
good to permissible, 3.75% are categorized as doubt- and C4 represent medium, high, and very high SAR
ful to unsuitable, and 1.25% are classified as permis- hazard levels, respectively. Percentages of 78.95%
sible to doubtful (Fig. 9a). Water with a high salt and 68.42% of the well and spring samples fell in the
content reduces soil permeability and, consequently, C4-S1 field (Fig. 9b), which denotes high salinity and
crop yield ( Rao 2005). For water wells, 64.91% are low sodium. The water can be considered for irriga-
classified as excellent for irrigation, 15.79% as good tion in most soil types with open drainage. For soils
to permissible, 3.51% as doubtful to unsuitable, and with poor drainage, nevertheless, particular salinity
15.79% as unsuitable for irrigation. High concentra- management strategies may be necessary (Chidam-
tions of ­Na+ in irrigation water, relative to other con- baram et al., 2022). About 1.75%, 3.51%, 3.51%, and
stituents such as ­Ca2+, ­Mg2+, and ­Na+, could lead 10.52% of the water wells and spring samples fall in
to flocculation and reduced soil permeability (Singh the C4S2, C5S2, C5S3, and C5S4 categories, respec-
et al., 2007). Saline soils are produced when sodium tively, suggesting high salinity and relatively increas-
interacts with chloride, while alkali soils are pro- ing order of alkali water. In contrast, high salinity
duced when excess sodium combines with carbonate water (C4 and C5) can irrigate salt-tolerant and semi-
(Fipps, 2003). tolerant crops under favorable drainage conditions.
In addition, an important plot to study the irriga-
tion suitability of water is the US salinity diagram,
which is used to evaluate the alkali/sodium risk Conclusions
to crops (USSL, 1954). EC is considered a salin-
ity hazard in this plot, and the sodium adsorption This study used geochemical investigations, multi-
ratio (SAR) is an alkalinity hazard. The plot shows variate statistical analysis, and isotopic approaches to
the scattering of water samples in seven classes, understand sources of groundwater salinization and

Fig. 9  Wilcox diagram (a) and USSL diagram (b) for the assessment of the water for irrigation

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Environ Monit Assess (2024) 196:365 Page 15 of 18 365

the mechanisms governing groundwater quality. The —review and editing. Alaa Ahmed: conceptualization, meth-
results presented here demonstrated the spatial vari- odology, data curation, writing—review and editing. Chidam-
baram Sabarathinam: methodology, writing—original draft,
ation of salinity from the peripheral region towards writing—review and editing. All authors contributed to the
the center. Multivariate statistics, including Pearson’s article and approved the submitted version.
correlation and PCA, were employed to identify the
sources of mineralization and the factors and sources Data availability Data cannot be shared openly but are avail-
responsible for variation amongst chemical variables able on request from authors.
and reduced the original data matrix into three com- Declarations
ponents that explain 78.98% of the total variance. The
dissolution of carbonates and sulfates, ion exchange Competing interests The authors declare no competing interests.
process, weathering of minerals, and evaporation
were inferred to be the major processes governing the
geochemistry of the region. Therefore, the observed
salinization can be attributed to the disproportionate References
interplay of evaporation and water–rock interaction
Abu-Alnaeem, M. F., Yusoff, T., Alias, N. Y., & Raksmey, M.
processes. The study also infers that the common- (2018). Assessment of groundwater salinity and quality
ion effect induces calcite precipitation gypsum dis- in Gaza coastal aquifer, Gaza Strip, Palestine: An inte-
solution. In addition, isotopic tracers (δ18O and δ2H) grated statistical, geostatistical and hydrogeochemical
show meteoric signatures for waters with the influ- approaches study. Science of the Total Environment, 615,
972–989.
ence of evaporation when compared to the LMWL Ahmed, A., & Clark, I. (2016). Groundwater flow and geo-
and GML. The suitability of water for drinking was chemical evolution in the Central Flinders Ranges,
evaluated using the TDS classification, while irriga- South Australia. Science of the Total Environment, 572,
tion purposes were evaluated using Wilcox’s and US 837–851.
Al-Naseri, S. K., Falih, A. H., & Saravana Kumar, U. (2022).
Salinity Laboratory–based classifications. Though the Moisture sources and spatio-temporal variation of iso-
water was found to be suitable for irrigation based topic signatures in Iraqi precipitation. Environmen-
on the estimated SARs, this water can pose nega- tal Earth Sciences, 81(18). https://​doi.​org/​10.​1007/​
tive effects and further cause irreversible damage in s12665-​022-​10559-7
Aliewi, A., Bhandary, H., Chidambaram, S., & Al-Qallaf, H.
irrigated soils due to high salinity. The geochemi- (2022). A new modified chloride mass balance approach
cal nature of the subsurface water in the semiarid based on aquifer hydraulic properties and other sources
region thus can be further explored with the increased of chloride to assess rainfall recharge in brackish aquifers.
sampling intensity, adopting temperature-governed Hydrological Processes, 36(3). https://​doi.​org/​10.​1002/​
hyp.​14513
thermodynamics using modeling approaches and American Public Health Association (APHA). (2012). Stand-
microbiological parameters to validate the results of ard Methods for the Examination of Water and Wastewa-
the current study further. Increasing the geochemi- ter (27th ed.).
cal database in the arid regions can help manage and Arumugam, K., & Elangovan, K. (2009). Hydrochemical char-
acteristics and groundwater quality assessment in Tirupur
decide the future course of action to achieve the UN- region, Coimbatore district, Tamil Nadu India. Environ-
SDG6 in the studied regions. mental Earth Sciences, 58(7), 1509–1520.
Barlow, P. M., & Reichard, E. G. (2010). Saltwater intru-
Authors’ contributions Ali Al Maliki: conceptualization, sion in coastal regions of North America. Hydrogeol-
methodology, formal analysis and investigation, software, data ogy Journal, 18(1), 247–260. https://​doi.​org/​10.​1007/​
curation, validation, writing—original draft, writing—review s10040-​009-​0514-3
and editing. U. Saravana Kumar: conceptualization, methodol- Belkhiri, L., Mouni, L., & Boudoukha, A. (2012). Geochemi-
ogy, supervision, validation, writing—review and editing. Ali cal evolution of groundwater in an alluvial aquifer: Case
Hasan Falih: formal analysis and investigation, data acquisi- of El Eulma aquifer, East Algeria. Journal of African
tion, validation, writing—original draft, writing—review and Earth Sciences, 66–67, 46–55. https://​doi.​org/​10.​1016/j.​
editing. Maitham Sultan: conceptualization, methodology, jafre​arsci.​2012.​03.​001
data curation, writing—review and editing. Amer Al-Naemi: Bennetts, D., Webb, J. A., Stone, D. J., & Hill, D. M. (2006).
formal analysis and investigation, data curation, supervision, Understanding the salinisation process for groundwater in
writing—review and editing. Dalal Alshamsi: formal analysis an area of south-eastern Australia, using hydrochemical
and investigation, data curation, validation, writing—review and isotopic evidence. Journal of Hydrology, 323(1–4),
and editing. Hasan Arman: data curation, validation, writing 178–192. https://​doi.​org/​10.​1016/j.​jhydr​ol.​2005.​08.​023

Vol.: (0123456789)
13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 365 Page 16 of 18 Environ Monit Assess (2024) 196:365

Bhandary, H., Chidambaram, S., & Al-Khalid, A. (2018). Fipps, G. (2003). Irrigation water quality standards and salinity
Occurrence of hypersaline groundwater along the coastal management strategies Texas a&M AgriLife Extension.
aquifers of Kuwait. Desalination, 436, 15–27. https://​doi.​ http://​infoh​ouse.​p2ric.​org/​ref/​11/​10685.​pdf
org/​10.​1016/j.​desal.​2018.​02.​004 Fouad, S. F. (2015). Tectonic map of Iraq, scale 1: 1000 000,
Boosalik, Z., Jafari, H., Clark, I. D., & Bagheri, R. (2022). 3rd EDITION, 2012. Iraqi Bulletin of Geology and Min-
Chemo-isotopic tracing of the groundwater salinity in arid ing, 11(1), 1–7 http://​ibgm-​iq.​org/​ibgm/​index.​php/​ibgm/​
regions: An example of Shahrood aquifer (Iran). Journal artic​le/​view/​262
of Geochemical Exploration, 239, 107029. https://​doi.​org/​ Freeze, R. A., & Cherry, J. A. (1979). Groundwater. Pren-
10.​1016/j.​gexplo.​2022.​107029 tice-Hall Inc., Englewood Cliffs, Vol. 7632, 604.
Carol, E. S., Kruse, E. E., & Mas-Pla, J. (2009). Hydrochemi- Fu, C., Li, X., Ma, J., Liu, L., Gao, M., & Bai, Z. (2018).
cal and isotopical evidence of ground water salinization A hydrochemistry and multi-isotopic study of ground-
processes on the coastal plain of Samborombón Bay water origin and hydrochemical evolution in the middle
Argentina. Journal of Hydrology, 365(3–4), 335–345. reaches of the Kuye River basin. Applied Geochemistry,
https://​doi.​org/​10.​1016/j.​jhydr​ol.​2008.​11.​041 98, 82–93. https://​doi.​org/​10.​1016/j.​apgeo​chem.​2018.​
Chen, Y., Vigouroux, G., Bring, A., Cvetković, V., & Destouni, 08.​030
G. (2019). Dominant hydro-climatic drivers of water tem- Gat, J., & Carmi, I. (1970). Evolution of the isotopic composi-
perature, salinity, and flow variability for the large-scale tion of atmospheric waters in the Mediterranean Sea area.
system of the Baltic Coastal Wetlands. Water, 11(3), 552. Journal of Geophysical Research, 75(15), 3039–3048.
https://​doi.​org/​10.​3390/​w1103​0552 https://​doi.​org/​10.​1029/​jc075​i015p​03039
Chidambaram, S., Bhandary, H., & Al-Khalid, A. (2020). Trac- Giambastiani, B., Colombani, N., Mastrocicco, M., & Fideli-
ing the evolution of acidic hypersaline coastal groundwa- bus, M. D. (2013). Characterization of the lowland coastal
ter in Kuwait. Arabian Journal of Geosciences, 13(21). aquifer of Comacchio (Ferrara, Italy): Hydrology, hydro-
https://​doi.​org/​10.​1007/​s12517-​020-​06116-w chemistry and evolution of the system. Journal of Hydrol-
Chidambaram, S., Bhandary, H., & Hadi, K. (2021). CHIDAM ogy, 501, 35–44. https://​doi.​org/​10.​1016/j.​jhydr​ol.​2013.​
-A software for chemical interpretation of the dissolved 07.​037
ions in aqueous media. Groundwater for Sustainable Gibbs, R. J. (1970). Mechanisms controlling world water
Development, 13, 100496. https://​doi.​org/​10.​1016/j.​gsd.​ chemistry. Science, 170(3962), 1088–1090. https://​doi.​
2020.​100496 org/​10.​1126/​scien​ce.​170.​3962.​1088
Chidambaram, S., Prasanna, M. V., Karmegam, U., Singaraja, Guggenmos, M., Daughney, C. J., Jackson, B., & Morgenstern,
C., Pethaperumal, S., Manivannan, R., Anandhan, P., & U. (2011). Regional-scale identification of groundwa-
Tirumalesh, K. (2011). Significance of pCO2 values in ter-surface water interaction using hydrochemistry and
determining carbonate chemistry in groundwater of Pondi- multivariate statistical methods, Wairarapa Valley, New
cherry region India. Frontiers of Earth Science, 5(2), 197– Zealand. Hydrology and Earth System Sciences, 15(11),
206. https://​doi.​org/​10.​1007/​s11707-​011-​0170-5 3383–3398. https://​doi.​org/​10.​5194/​hess-​15-​3383-​2011
Chidambaram, S., Prasanna, M. V., Senapathi, V., Nepolian, Güler, C., Kurt, M. A., Alpaslan, M., & Akbulut, C. (2012).
M., Pradeep, K., Panda, B., Thivya, C., & Thilagavathi, Assessment of the impact of anthropogenic activities
R. (2022). Groundwater quality assessment for irrigation on the groundwater hydrology and chemistry in Tarsus
by adopting new suitability plot and spatial analysis based coastal plain (Mersin, SE Turkey) using fuzzy cluster-
on fuzzy logic technique. Environmental Research, 204, ing, multivariate statistics and GIS techniques. Journal of
111729. https://​doi.​org/​10.​1016/j.​envres.​2021.​111729 Hydrology, 414–415, 435–451. https://​doi.​org/​10.​1016/j.​
Clark, I. D., & Fritz, P. (2013). Environmental isotopes in jhydr​ol.​2011.​11.​021
hydrogeology. CRC Press eBooks. https://​doi.​org/​10.​ Han, D., & Currell, M. (2018). Delineating multiple saliniza-
1201/​97814​82242​911 tion processes in a coastal plain aquifer, northern China:
Dansgaard, W. (1964). Stable isotopes in precipitation. Tellus Hydrochemical and isotopic evidence. Hydrology and
B: Chemical and Physical Meteorology, 16(4), 436–468. Earth System Sciences, 22(6), 3473–3491. https://​doi.​org/​
https://​doi.​org/​10.​1111/j.​2153-​3490.​1964.​tb001​81.x 10.​5194/​hess-​22-​3473-​2018
Davis, S., & DeWiest, R. (1966). M (p. 463). Hydrogeology. Iraqi Meteorological Organization (IMO). (2020). Climatically
Del Pilar Álvarez, M., Carol, E. S., & Dapeña, C. (2015). The Data for Haditha meteorological station for the period
role of evapotranspiration in the groundwater hydrochem- (1988 - 2019), Baghdad, Iraq, Iraqi Meteorological
istry of an arid coastal wetland (Península Valdés, Argen- Organization (IMO).
tina). Science of the Total Environment, 506–507, 299– Jackson, R. E., Gorody, A. W., Mayer, B., Roy, J. W., Ryan, M.
307. https://​doi.​org/​10.​1016/j.​scito​tenv.​2014.​11.​028 C., & Van Stempvoort, D. R. (2013). Groundwater protec-
Drever, J. I. (1988). The Geochemistry of Natural Waters. 2nd tion and unconventional gas extraction: The critical need
Edition, Prentice-Hall, Englewood Cliffs, p. 437. https://​ for field-based hydrogeological research. Groundwater,
openl​ibrary.​org/​books/​OL238​8438M/​The_​geoch​emist​ry_​ 51(4), 488–510. https://​doi.​org/​10.​1111/​gwat.​12074
of_​natur​al_​waters Jassim, S. Z., & Goff, J. C. (2006). “Geology of Iraq” 1st
Durov, S. A. (1948). Classification of natural waters and graph- Edition, published by Dolin. Brno Printed in the Czech
ical representation of their composition. Doklady Aka- Republic.
demii Nauk SSSR, 59, 87–90. Kammoun, S., Trabelsi, R., Ré, V., Zouari, K., & Henchiri,
J. (2018). Groundwater quality assessment in semi-
arid regions using integrated approaches: The case of

Vol:. (1234567890)
13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
Environ Monit Assess (2024) 196:365 Page 17 of 18 365

Grombalia aquifer (NE Tunisia). Environmental Moni- Maskooni, E. K., Hashemi, H., Kompanizare, M., Arasteh, P.
toring and Assessment, 190(2). https://​doi.​org/​10.​1007/​ D., Vagharfard, H., & Berndtsson, R. (2021). Assessment
s10661-​018-​6469-x of hydro-geochemical properties of groundwater under the
Katerji, N., Van Hoorn, J., Hamdy, A., & Mastrorilli, M. effect of desalination wastewater discharge in an arid area.
(2003). Salinity effect on crop development and yield, Environmental Science and Pollution Research, 28(5),
analysis of salt tolerance according to several classifica- 6176–6194. https://​doi.​org/​10.​1007/​s11356-​020-​10787-z
tion methods. Agricultural Water Management, 62(1), Memon, M. A., Soomro, M. S., Akhtar, M. A., & Memon, K.
37–66. https://​doi.​org/​10.​1016/​s0378-​3774(03)​00005-2 S. (2010). Drinking water quality assessment in South-
Kharroubi, A., Tlahigue, F., Agoubi, B., Azri, C., & Bouri, ern Sindh (Pakistan). Environmental Monitoring and
S. (2012). Hydrochemical and statistical studies of the Assessment, 177(1–4), 39–50. https://​doi.​org/​10.​1007/​
groundwater salinization in Mediterranean arid zones: s10661-​010-​1616-z
Case of the Jerba coastal aquifer in southeast Tunisia. Meybeck, M. (1987). Global chemical weathering of surficial
Environmental Earth Sciences, 67(7), 2089–2100. https://​ rocks estimated from river dissolved loads. American
doi.​org/​10.​1007/​s12665-​012-​1648-5 Journal of Science, 287(5), 401–428. https://​doi.​org/​10.​
Khezzani, B., & Bouchemal, S. (2018). Variations in ground- 2475/​ajs.​287.5.​401
water levels and quality due to agricultural over-exploi- Nair, I. S., Brindha, K., & Elango, L. (2020). Assessing the
tation in an arid environment: the phreatic aquifer of the origin and processes controlling groundwater saliniza-
Souf oasis (Algerian Sahara). Environmental Earth Sci- tion in coastal aquifers through integrated hydrochemi-
ences, 77(4). https://​doi.​org/​10.​1007/​s12665-​018-​7329-2 cal, isotopic and hydrogeochemical modelling techniques.
Kim, J. H., Kim, R. H., Lee, J., & Chang, H. (2003). Hydro- Hydrological Sciences Journal-journal Des Sciences
geochemical characterization of major factors affecting Hydrologiques, 66(1), 152–164. https://​doi.​org/​10.​1080/​
the quality of shallow groundwater in the coastal area at 02626​667.​2020.​18264​90
Kimje in South Korea. Environmental Geology, 44(4), Najib, S., Fadili, A., Mehdi, K., Riss, J., & Makan, A.
478–489. https://​doi.​org/​10.​1007/​s00254-​003-​0782-5 (2017). Contribution of hydrochemical and geoelectrical
Kim, K. (2003). Long-Term disturbance of ground water chem- approaches to investigate salinization process and seawa-
istry following well installation. Groundwater, 41(6), ter intrusion in the coastal aquifers of Chaouia, Morocco.
780–789. https://​doi.​org/​10.​1111/j.​1745-​6584.​2003.​tb024​ Journal of Contaminant Hydrology, 198, 24–36. https://​
19.x doi.​org/​10.​1016/j.​jconh​yd.​2017.​01.​003
Li, C., Gao, X., Liu, Y., & Wang, Y. (2019). Impact of anthro- Nepolian, M., Chidambaram, S., Prasanna, M. V., Senapa-
pogenic activities on the enrichment of fluoride and salin- thi, V., Sekar, S., Devaraj, N. K., Gopalakrishnan, G., &
ity in groundwater in the Yuncheng Basin constrained by Mahalakshmi, M. (2022). Source, mobilization and dis-
Cl/Br ratio, δ18O, δ2H, δ13C and δ7Li isotopes. Journal of tribution of uranium in a complex aquifer system: A spa-
Hydrology, 579, 124211. https://​doi.​org/​10.​1016/j.​jhydr​ol.​ tial and temporal evaluation using geochemical, statistics
2019.​124211 and GIS approach. Environmental Earth Sciences, 81(7).
Liu, J., Chen, Z., Wang, L., Zhang, Y., Li, Z., Xu, J., & Peng, https://​doi.​org/​10.​1007/​s12665-​022-​10291-2
Y. (2016). Chemical and isotopic constrains on the ori- Panda, B., Chidambaram, S., Nagappan, G., Thilagavathi, R.,
gin of brine and saline groundwater in Hetao plain, & Kamaraj, P. (2020). Multiple thematic spatial integra-
Inner Mongolia. Environmental Science and Pollution tion technique to identify the groundwater recharge poten-
Research, 23(15), 15003–15014. https://​doi.​org/​10.​1007/​ tial zones—A case study along the Courtallam region,
s11356-​016-​6617-1 Tamil Nadu, India. Arabian Journal of Geosciences,
Liu, J., Gao, Z., Wang, Z., Xu, X., Su, Q., Shu, W., Qu, W., 13(24). https://​doi.​org/​10.​1007/​s12517-​020-​06223-8
& Xing, T. (2020). Hydrogeochemical processes and suit- Papatheodorou, G., Lambrakis, N., & Panagopoulos, G.
ability assessment of groundwater in the Jiaodong Penin- (2007). Application of multivariate statistical procedures
sula, China. Environmental Monitoring and Assessment, to the hydrochemical study of a coastal aquifer: An exam-
192(6). https://​doi.​org/​10.​1007/​s10661-​020-​08356-5 ple from Crete Greece. Hydrological Processes, 21(11),
Lü, C., Wang, G., Hu, F., Wang, Y., & Liang, L. (2013). 1482–1495. https://​doi.​org/​10.​1002/​hyp.​6322
Groundwater hydrochemistry and isotope geochemis- Pillai, A., Chidambaram, S., Keesari, T., Thivya, C., Thila-
try in the Turpan Basin, northwestern China. Journal gavathi, R., Senapathi, V., Prasanna, M. V., & Samay-
of Arid Land, 6(4), 378–388. https://​doi.​org/​10.​1007/​ amanthu, D. R. (2020). Seasonal changes in groundwater
s40333-​013-​0249-9 quality deterioration and chemometric analysis of pollu-
Martin, A. (2001). Late Permian to Holocene Paleofacies evo- tion source identification in South India. Environmental
lution of the Arabian Plate and its hydrocarbon occur- Science and Pollution Research, 27(16), 20037–20054.
rences. GeoArabia, 6(3), 445–504. https://​doi.​org/​10.​ https://​doi.​org/​10.​1007/​s11356-​020-​08258-6
2113/​geoar​abia0​603445 Piper, A. M. (1944). A graphic procedure in the geochemical
Mastrocicco, M., Gervasio, M. P., Busico, G., & Colombani, interpretation of water-analyses. Transactions, 25(6), 914.
N. (2021). Natural and anthropogenic factors driving https://​doi.​org/​10.​1029/​tr025​i006p​00914
groundwater resources salinization for agriculture use in Polemio, M. (2020). Review of utilization management of
the Campania plains (Southern Italy). Science of the Total groundwater at risk of salinization. Journal of Water
Environment, 758, 144033. https://​doi.​org/​10.​1016/j.​scito​ Resources Planning and Management, 146(9). https://​doi.​
tenv.​2020.​144033 org/​10.​1061/​(asce)​wr.​1943-​5452.​00012​78

Vol.: (0123456789)
13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 365 Page 18 of 18 Environ Monit Assess (2024) 196:365

Prasanna, M. V., Chidambaram, S., Kumar, G., Ramanathan, Jordan. HydroResearch, 2, 129–145. https://​doi.​org/​10.​
A., & Nainwal, H. C. (2010). Hydrogeochemical assess- 1016/j.​hydres.​2020.​02.​001
ment of groundwater in Neyveli Basin, Cuddalore District Thilagavathi, R., Chidambaram, S., Thivya, C., Prasanna, M.
South India Arabian. Journal of Geosciences, 4(1–2), V., Keesari, T., & Pethaperumal, S. (2017). Assessment
319–330. https://​doi.​org/​10.​1007/​s12517-​010-​0191-5 of groundwater chemistry in layered coastal aquifers
Pulido-Bosch, A., Rigol-Sánchez, J., Vallejos, Á., Andreu, J. using multivariate statistical analysis. Sustainable Water
M., Cerón, J. C., Molina-Sánchez, L., & Sola, F. (2018). Resources Management, 3(1), 55–69. https://​doi.​org/​10.​
Impacts of agricultural irrigation on groundwater salinity. 1007/​s40899-​017-​0078-7
Environmental Earth Sciences, 77(5). https://​doi.​org/​10.​ Thilagavathi, R., Chidambaram, S., Thivya, C., Prasanna, M.
1007/​s12665-​018-​7386-6 V., Singaraja, C., Tirumalesh, K., & Pethaperumal, S.
Rao, N. S. (2005). Seasonal variation of groundwater quality in (2014). Delineation of natural and anthropogenic pro-
a part of Guntur District, Andhra Pradesh India. Environ- cess controlling hydrogeochemistry of layered aquifer
mental Geology, 49(3), 413–429. https://​doi.​org/​10.​1007/​ sequence. Proceedings of the National Academy of Sci-
s00254-​005-​0089-9 ences, India Section A: Physical Sciences, 84(1), 95–108.
Rashid, T., Chidambaram, S., Al-Qallaf, H., Bhandary, H., Al- https://​doi.​org/​10.​1007/​s40010-​013-​0114-4
Jomaa, M., Shishter, A., & Al-Salman, B. (2022). Evo- Tomaz, A., Palma, P., Fialho, S., Lima, A., Alvarenga, P.,
lution of hydrogeochemistry in groundwater production Potes, M., Costa, M. J., & Salgado, R. (2020). Risk assess-
fields of Kuwait–Inferences from long-term data. Chem- ment of irrigation-related soil salinization and sodification
osphere, 307, 135734. https://​doi.​org/​10.​1016/j.​chemo​ in Mediterranean areas. Water, 12(12), 3569. https://​doi.​
sphere.​2022.​135734 org/​10.​3390/​w1212​3569
Rasouli, F., Pouya, A. K., & Cheraghi, S. M. (2011). Hydro- USSL Staff. (1954). Diagnosis and improvement of saline and
geochemistry and water quality assessment of the Kor– alkali soils. USDA Agr. Handbook No.60.
Sivand Basin, Fars province Iran. Environmental Monitor- WHO. (2004). Guidelines for Drinking Water Quality, Volume
ing and Assessment, 184(8), 4861–4877. https://​doi.​org/​ 1: Recommendations. 3rd Edition, WHO, Geneva.
10.​1007/​s10661-​011-​2308-z Wilcox, L. V. (1955). Classification and Use of Irrigation
Samayamanthula, D. R., Chidambaram, S., Alayyadhi, N. A., Water. US Department of Agriculture, Circular 969,
Al-Ajeel, F. K., Al-Qallaf, H., & Akber, A. (2022). Spatial Washington DC.
and temporal variation of dissolved C ­ O2 in rainwater from Xu, F., Li, P., Wang, Y., & Du, Q. (2023). Integration of hydro-
an arid region with special focus on its association with chemistry and stable isotopes for assessing groundwater
DIC and p­CO2. Environmental Earth Sciences, 81(4). recharge and evaporation in pre- and post-rainy seasons
https://​doi.​org/​10.​1007/​s12665-​022-​10176-4 in Hua County China. Natural Resources Research, 32(5),
Schoeller, H. (1967). Qualitative evaluation of ground water 2023.
resources. In H. Schoeller (Ed.), Methods and Techniques Xu, F., Li, P., Du, Q., et al. (2023). Seasonal hydrochemi-
of Groundwater Investigation and Development Water cal characteristics, geochemical evolution, and pollu-
Resource Series (Vol. 33, pp. 44–52). UNESCO. tion sources of Lake Sha in an arid and semiarid region
Singh, A. K., Mondal, G. C., Kumar, S., Singh, T. V., Tewary, of northwest China. Exposure and Health, 15, 231–244.
B. K., & Sinha, A. (2007). Major ion chemistry, weath- https://​doi.​org/​10.​1007/​s12403-​022-​00488-y
ering processes and water quality assessment in upper Zhang, Y., Xu, M., Li, X., Qi, J., Qiang, Z., Guo, J., Yu, L., &
catchment of Damodar River basin India. Environmen- Zhao, R. (2018). Hydrochemical characteristics and multi-
tal Geology, 54(4), 745–758. https://​doi.​org/​10.​1007/​ variate statistical analysis of natural water system: a case
s00254-​007-​0860-1 study in Kangding County, southwestern China. Water,
Sissakian, V., & Mahmud, B. (2007). Stratigraphy of the Iraqi 10(1), 80. https://​doi.​org/​10.​3390/​w1001​0080
Western Desert. IBGM, SCGSM, 51–125.
Stuyfzand, P. J. (1993). Hydrochemistry and hydrology of Publisher’s Note Springer Nature remains neutral with regard
coastal dune area of the Western Netherlands. Thesis, Free to jurisdictional claims in published maps and institutional
University of Amsterdam. affiliations.
Subramani, T., Rajmohan, N., & Elango, L. (2010). Groundwa-
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https://​doi.​org/​10.​1007/​s10661-​009-​0781-4
self-archiving of the accepted manuscript version of this article
Tarawneh, M. S. M., Janardhana, M. R., & Ahmed, M. M.
is solely governed by the terms of such publishing agreement
(2019). Hydrochemical processes and groundwater qual-
and applicable law.
ity assessment in Northeastern region of Jordan valley,

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