Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

https://doi.org/10.1007/s00477-023-02537-7(0123456789().,-volV)(0123456789().
,- volV)

ORIGINAL PAPER

Study of hydrogeochemical factors affecting groundwater quality used

for land reclamation: application of multivariate statistical analysis
Othman Fallatah1 • Mahmoud R. Khattab2

Accepted: 31 July 2023 / Published online: 10 August 2023

Ó The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
Saudi Arabia struggles to supply its population with enough clean water as being one of the biggest and fastest-growing
nations outside its own continent. For this study 49 groundwater samples were collected between June and December of
2021. Different analytical techniques were used for determinations of anions and cations concentration. Using World
Health Organization’s recommended safe limits to compare results that were collected. Groundwater is affected by aquifer
matrix disintegration, water infiltration from irrigation systems, and water–rock interactions, according to the results of the
hydrogeochemical study. The anions HCO3-, CO32-, Cl-, NO32-, and F-, as well as the cations Na?, K?, Ca2?, and
Mg2?, were also presented in the collected groundwater samples in acceptable concentrations. Using physical charac-
teristics and hydrochemical characterizations is also a commendable approach to regulating the quality of groundwater
samples collected for crop agriculture and irrigation. Most of the collected groundwater samples are desired and fit for
human and industrial consumption. In addition, application of the statistical analysis concluded that in some locations
contaminated surface water may recharge the groundwater. A variety of physical characteristics, including as EC, SAR,
RSC, KR, MH, CR, PI, and PS, are widely used to regulate the quality of groundwater samples collected for crops
agriculture and irrigation. Piper and Gibbs diagrams for groundwater hydrochemical characterizations were used. The
obtained results indicated that the collected groundwater samples are acceptable for crops drinking, agriculture and
irrigation.

Keywords Geochemical processes  Anions  Cations  Groundwater  Irrigation  Statistical analysis

1 Introduction Saudi Arabia lacks any permanent bodies of water due

to harsh temperature, a high rate of evaporation, and little
Use of groundwater depends on its quality, and measuring rainfall. As a result, deep aquifers and water desalination
that quality is a crucial part of groundwater studies. Vari- are the primary sources of water in Saudi Arabia. The
ations in groundwater quality between regions are largely majority of runoff water recharges shallow aquifers
caused by geological factors; geology, amount of rainfall, beneath alluvial fans and grasslands, along river valleys,
hydraulic gradient, as well as anthropogenic activities; and in various geographic locations. Typically unconfined,
agricultural, domestic, or industrial pollution (Subba Rao these aquifers are small in area, and their water tables react
et al. 2022). quickly to local precipitation. Al-Khaf, Tawil, Al-Urma,
Al-Jawf, Sakaka, Al-Jala, and Al-Jubaila are a few of the
shallow reservoirs. A total of 2.8 billion cm3/year of
groundwater is thought to be sustainable. The deep sedi-
& Othman Fallatah mentary rocky aquifers cover thousands of square kilo-
ofallatah@kau.edu.sa
metres with only a feeble natural recharge and are typically
1
Department of Nuclear Engineering, Faculty of Engineering, made of sandstone and limestone. About 72% of Saudi
King Abdulaziz University, P.O. Box 80204, 21589 Jeddah, Arabia’s total water consumption is in the agricultural
Saudi Arabia industry. 90% of the water used in agriculture is sourced
2
Geochemical Exploration Department, Nuclear Materials
Authority (NMA), El-Maadi, P.O. Box 530, Cairo, Egypt

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4720 Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

from underground reservoirs (Chowdhury and Al-Zahrani chemical changes that take place during groundwater
2015). migration from recharge to discharge regions (Rao et al.
Over the past century, study on agriculture and land 2021a, b; Ali et al. 2018).
reclamation got more attention, greatly influencing our way Liu et al. 2021 evaluated the potential negative health
of life and quality of living. An important component of impacts of manganese and fluoride contamination in the
these developments is the use of agricultural chemicals. groundwater in the Chinese Weining Plain using Monte
They significantly contribute to both the productivity and Carlo simulation. According to their study, these pollutants
effectiveness of agriculture as well as the prosperity of both may be bad for people’s health in general and kids in
rural and metropolitan areas. But many people are worried particular. To determine groundwater risk, Zhang et al.
about the potential impacts that using these chemicals 2021 created a model. They used the updated DRATICL
might have on environmental safety, water purity, and model in their study to take into account pollutant loading.
human health. Water availability and quality are therefore This research provides a method for evaluating the vul-
significant global concerns, but are particularly acute in nerability of groundwater in major river basins.
arid and semiarid regions (Al Suhaimi et al. 2016). Due to the limited water resources in the Najran area
Groundwater makes up 98 % of the water that is readily and the ongoing urban extension of Najran city, the Min-
available. Water is provided by this essential natural istry of Environment, Water, and Agriculture decided in
resource to billions of people, and its development has 2011 to drill 22 deep groundwater wells to supply the
been essential for the expansion of the global farming Najran urban area with water needs. In addition, the dis-
industry, which supplies about one-fifth of the world’s food charge of sewage into surface junkyards has caused a
(Hu et al. 2018). For domestic, industrial, and agricultural number of environmental issues in nearby water resources,
uses, groundwater is a significant source of water (Amiri posing a threat to local residents and the environment as a
et al., 2021a).The primary causes of regional variations in whole by spreading dangerous diseases.
groundwater quality are typically anthropogenic activities This study looks for investigating the Najran area’s
like household, industrial, or agricultural contamination as groundwater quality in order to aid in the management and
well as geological variables like geology, rainfall, and protection of groundwater resources. According to the
hydraulic gradient. Researchers from around the world hydrochemical data, the types of the gathered groundwater
have looked into different scenarios to determine how to show how they are categorized and whether they are suit-
evaluate the quality of groundwater (Subba Rao et al. 2022; able for different uses like irrigation, drinking, and indus-
Ravindra et al. 2022; Belkhiri et al. 2010). Population trial ones. We want to (i) understand the chemical
expansion, less precipitation, and climate change all con- interactions between the minerals in the aquifer and how
tribute to an increase the need for groundwater (Li et al. they affect groundwater chemistry; and (ii) use hydro-
2013). chemical analysis to support groundwater chemistry, which
Hydrochemistry has also contributed significantly to our is affected by its source, climate, and geology. TDS, pH,
understanding of groundwater evolution (Dar et al. 2014). EC, and major ions are used to measure the purity of
Groundwater contains chemical indicators from anthro- groundwater and pinpoint hydrogeochemical processes. In
pogenic activities as well as interactions between recharge the study area, groundwater is the most important main
water and minerals and sediments that form aquifers along source of water for drinking, agriculture, and industries
flow pathways (Voutsis et al. 2015). With the use of the purposes. The primary goals of this research were to assess
interactive Phreeqc program and an ionic ratio map, the the potential risk to human health and evaluate the quality
processes controlling hydrochemistry can be identified of groundwater using physicochemical parameters.
(Bouzourra et al. 2014).
Aquifer minerals and their chemical processes influence
the chemistry of the groundwater. The hydrochemical 2 Materials and methods
analysis also supports the groundwater’s chemistry in terms
of its relationship to the water supply, climate, and geol- 2.1 Geological settings
ogy. For evaluating groundwater quality and identifying
hydrogeochemical mechanisms, the detection of water The research area lies in southern Saudi Arabia in the
physicochemical parameters (major ions, TDS, pH, and Najran region between latitudes 19°010 and 19°50 3000 and
EC) is crucial (Ravindra et al. 2022). longitudes 45°10 1500 and 45°090 E. Najran City, which can
Because of pollution, the main problem that might arise be found along Wadi Najran, serves as the region’s main
is decreased groundwater use (He et al. 2019; Gu et al. governmental center. Sediments carried by the breeze from
2017; Liu et al. 2017). The groundwater would not be fit Ar Rub Alkhali cover the eastern part of Najran. Two
for irrigation or consumption because of the physical and important irrigation systems, Wadi Habawnah and Wadi

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Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735 4721

Najran, enter Ar Rub Al Khali from the east. Najran is also 3.8 9 10–4. The expected specific output is between 3 and
situated between 950 and 2432 m above sea level. The 10%. Within the study region, the groundwater level of the
terrain is also rough, with a plateau that is heavily divided upper Wajid aquifer ranges between 118.72 and 132 m.
among other features (Fig. 1). From north to south, the study area’s groundwater depth
On the southern border of the Arabian Shield, there are gradually rises. Using ArcGIS, the research area’s water-
rocks from the Proterozoic period, Cambro-Ordovician shed was located. Except for wells 18 and 22, all of the
Wajid sandstone, and Quaternary surface deposits (Fig. 1). other wells are outside the deep south basin. It has a 144.6
In the study region, the Proterozoic basement is made up of km2 territory. The primary stream of this watershed flows
sedimentary rocks, rocks from the Halaban group, and from north to south. On the eastern edge of the watershed,
mafic to intermediate volcanic rocks. According to a the highest elevations range between 827 and 1027 m
hypothesis made by Greenwood et al. (1982), the layered above sea level (Alfaifi et al. 2021).
rocks were the record of a Late-Proterozoic volcanic region
based on the lithology of the earliest layers and the sup- 2.3 Sample collections and analytical methods
posed depositional conditions. Along a zone of plate con-
vergence that dipped southwest, andesitic and basaltic Soil and plants are affected by the mineral concentration in
volcanic rocks most likely developed by melting sub- groundwater. Mineral concentrations in groundwater,
ducted, mostly ensimatic crust (Alfaifi et al. 2021). which directly impact agricultural plants and soils, are the
source of the drop in yield (Alfaifi et al. 2021). Numerous
2.2 Hydrogeology of study area variables, including water sources, regional geological
changes, and meteorological factors have an impact on the
The western part of Wadi Ad Dawasir contains the Upper chemistry of groundwater. For instance, too salty ground-
Wajid aquifer, which is 100 m deep. It is roughly 1500 m water can gravely harm plants by modifying their meta-
thick in the Rub Al Khali basin’s center. About 200 m of bolism and lowering their capacity to absorb water.
thickness are present in the study region. The Upper Wajid In the Najran area, 49 groundwater samples were col-
groundwater is one of the unconfined aquifers. Except for lected between June and December of 2021. Each well
outcrop zones, the upper and lower Wajid aquifers have provided two liters of water, which was stored in plastic
been combined into a single reservoir. The transmissivity bottles. A small field instrument calibrated with deionized
of the upper Wajid groundwater varies between 7.1 9 104 water was used to instantly measure the pH and TDS of the
and 4 9 102 m2s-1. Typically, the storage number is groundwater. TDS was used to detect EC. We also

Fig. 1 a Geological map of Saudi Arabia and the study area; Najran area, b and c Map showing the collected samples locations

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recorded the latitude and longitude of each sampling The TDS values varied between 71 and 783 mg/L, with
location using a portable GPS device. The cations K?, a mean value of 478 ± 22.7 mg/L. According to ground-
Na?, Ca2?, and Mg2?, as well as the anions HCO3-, water conductivities, the collected groundwater samples
SO42-, Cl-, NO32- and F- were determined. By utilizing were highly ion-bearing. Ca2?, Mg2?, Na?, and K?
flame atomic absorption spectrophotometry, the concen- amounts ranged between 19–94 mg/L, 0–34 mg/L, 0–110
trations of K? and Na? were determined. EDTA titration mg/L, and 0–6 mg/L, respectively. The median readings
method was used to measure the concentrations of Ca2? were 67, 21, 62, and 4 mg/L, and the mean values were 64,
and Mg2?. The measurements of SO42-, Cl-, CO32- and 17.7, 58.9, and 3.3 mg/L. The collected groundwater
HCO3- were achieved using ion chromatography. While samples had concentrations of dissolved anions like
other ions; NO32-, and F- were measured by alkaline HCO3-, Cl-, SO42-, NO32-, and F- that varied between
titration. 322–450 mg/L, 1–16 mg/L, 0–168 mg/L, 0–21 mg/L, and
0.08–0.1 mg/L, respectively. With a mean value of
2.4 Hydrochemical parameters 378.6 ± 4.18, 109 ± 7.2, 60 ± 3.7, 10.3 ± 0.7, and
0.02 ± 0.003 mg/L respectively, and a median value of
Hydrogeochemical parameters such as Total Harkness; TH, 389, 121, 62, 10 and 0.01 mg/L respectively (Table 2).
Permeability Index; PI, Magnesium Hazard; MH, Salt The concentrations of major ions in groundwater and the
Absorption Rate; SAR, Residual Sodium Carbonate; RSC, mineralogy of different rocks have been used to determine
Sodium Ratio; Na %, Kelly Ratio; KR, Magnesium Ratio; the sources of the main ions to the groundwater and their
MR and Corrosion Ratio; CR were used for identification links to regional geology and weathering processes.
of quality assessment of the collected groundwater and Because it promotes the development of bones and teeth,
shown in Table 1. the Ca2? cation concentration in groundwater has a sig-
nificant impact on its composition. For the permissible
limit of Ca2? concentration, suggestions were clarified by
3 Results and discussion WHO (2017) and BIS (2012). Groundwater is frequently
loaded with calcium because of the calcium-bearing rocks
3.1 Hydrochemical characteristics and minerals like plagioclase, amphibole, and pyroxene
(Rao 2021).
Table 2 included minimum, maximum, mean, and standard Ion exchange and the presence of carbon dioxide in the
deviation values for the physicochemical parameters of soil zone are two additional methods by which calcium
these groundwater samples that were statistically analyzed. reaches groundwater. Ledesma-Ruiz et al. 2015 noted that
The groundwater samples’ pH levels varied from slightly the anions’ and cations’ standard deviations in the
acidic to alkaline, with a mean value of 7.61 ± 0.09 and a groundwater samples they obtained were lower than their
range of 7 and 9. Electric conductivity, with EC values mean values, indicating that the study area’s geochemistry
ranged between 98 and 1443 S.cm-1 and a mean of is homogeneous, which presumably indicates the
825.9 ± 41.2 S.cm-1 (Table 2). enhancement of solute load in the aquifer. The main
cations in the collected groundwater samples were Na?,

Table 1 Equations used for calculating irrigation quality parameters

Parameters Equations References

Total Hardness (TH) TH ¼ 2:497Ca2þ þ 4:115 Mg2þ Todd (1980)

 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  
Permeability Index (PI) PI ¼ Naþ þ HCO3 = Ca2þ þ Mg2þ þ Naþ  100 Falowo et al. (2017)
 
Magnesium Hazard (MH) MH ¼ ðMg2þ  100Þ= Ca2þ þ Mg2þ Abdulhussain (2018)
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  ffi
Salt Absorption Rate (SAR) SAR ¼ Naþ = Ca2þ þ Mg2þ =2 Abdulhussain (2018)
 2þ 
Residual Sodium Carbonate (RSC) RSC ¼ ðHCO 2
3 þ CO3 Þ  Ca þ Mg2þ Gupta and Gupta (1987)
Sodium Ratio (Na %) þ þ 2þ 2þ þ þ Gao et al. (2016)
Na % ¼ ðNa þ K Þ=ðCa þ Mg þ Na þ K Þ  100
Kelly Ratio (KR) þ 2þ 2þ Kelly (1963)
KR ¼ Na =ðCa þ Mg Þ

 2 
Corrosion Ratio (CR) Cl =35:5þ2 SO4 =96 Aravindan et al. (2004)
CR ¼   2
  100
2 HCO3 þ CO3 =100Þ

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 Table 2 Statistical analyses of the collected groundwater results, cations and anions concentration (mg/L)
Variables pH TDS EC TH Na? K? Ca2? Mg2? Cl- SO42- HCO3- CO32- NO32- F-

Mean 7.6 ± 0.09 477.6 ± 22.7 825.9 ± 41.2 230.7 ± 10.8 58.9 ± 3.3 3.7 ± 0.2 64 ± 2.5 17.7 ± 1.12 109 ± 7.2 60 ± 3.7 378.6 ± 4.2 374.1 ± 7.6 10.3 ± 0.7 0.02 ± 0.0
95% 7.43–7.78 432–523.1 743.2–908.7 209–252.3 52.2–65.6 3.4–4 58–68 15.4–19.9 94.6–126.4 52.6–67.5 370.6–387 358.8–389.4 8.8–11.8 0.02–0.3
Confidence
interval
5% Trimmed 7.57 486.2 842 234.3 59.7 3.8 64 17.9 110.1 60 378.6 377.4 10.3 0.02
Mean
Median 8 504 939 252 62 4 67 21 121 62 389 387 10 0.01
Variance 0.367 25,166.1 83,067.5 5686.8 543.7 1.3 314 62 2507.6 673.3 835 2842.5 26.8 0.0
Std. Deviation 0.61 158.6 288.2 75.4 23.3 1.14 17.7 7.9 50.1 26 29.2 53.3 5.2 0.02
Minimum 7 71 98 47 0 0 19 0 1 0 322 88 0 0.1
Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

Maximum 9 783 1443 361 110 6 94 34 216 168 450 492 21 0.09
Range 2 712 1345 314 110 6 75 34 215 168 128 404 21 0.08
Interquartile 1 254 456.5 127 35 1 28.5 14 92 25 50 50 3 0.02
range
Skewness 0.43 - 0.91 - 0.93 - 0.92 - 0.67 - 1.91 - 0.86 - 0.76 - 0.531 0.67 - 0.118 - 3.1 0.29 1.74
Kurtosis - 0.62 0.70 0.65 58.9 0.7 5.2 0.25 0.14 - 0.28 6.33 - 0.88 17.2 0.39 1.55
Desirable limit 6.5–8.5 500 500 200 200 10 75 50 250 200 200 200 25 1
(WHO 2017)
Permissible – 1500 1500 500 600 12 200 100 500 250 600 600 45 1.5
limit (WHO
2017)
4723

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Ca2?, Mg2?, and K?, while the most common anions were adequacy, which has to be higher than 0.5 and determines
HCO3-, CO32-, Cl-, and SO42-. In contrast to WHO whether a component is significant. The overall KMO
(2017), Table 2 showed that cations and anions concen- sampling adequacy is 0.783 (Liu et al. 2003). The collected
trations in the groundwater samples were reduced. groundwater passes the Bartlett test of sphericity; v2 with p
(Sig.) \ 0.0001 and a result of zero. These results
3.2 Application of multi-statistics analysis demonstrated that PCA could be used and that the data was
sound (Aguirre et al. 2019). According to Table 4, just
3.2.1 Pearson correlation analysis three significant components with eigenvalues [ 1 repre-
sented 82.47% of the total variation in the collected
The coefficient correlation matrix; r) is one of the impor- groundwater results, as illustrated in Fig. 2.
tant analyses that demonstrates the relationships between The component loading values above 0.5 are significant
two different water-related factors. The Pearson correlation and useful, but factor loading values above 0.75 are cate-
coefficient matrix is the most well-known indicator of how gorized as strong, 0.75–0.50 are moderate, and 0.50–0.30
two water parameters are influenced by one another. It are weak (Wu et al. 2020). PC1 was the most significant in
serves as a measure of how well one variable may be used the results as shown in Table 4. It also exhibited positive
to predict another (Howlader et al. 2014). The correlation loading with TDS, TH, EC, Mg2?, Ca2?, Cl-, Na?, SO42-,
coefficient ranged between -0.005 and 1. The relationship K?, CO32-, F- and HCO3-. Naturally, due to water–rock
is defined as being anti-correlated or having a negative interaction, these groupings could have their roots in the
slope when the value of r is close to 1. aquifer matrix. Cl- and SO42- ions are frequently associ-
The correlation coefficient was shown in Table 3 as a ated with sedimentary rocks and are common markers of
result of PCMA’s recognition of the links between water pollution (Battistel et al. 2016). According to Nigro et al.
quality metrics. Variable interdependence was assessed 2017, Na?, Mg2?, and Ca2? are naturally occurring in
using the PCMA. A linear connection was found between groundwater because they are leached from rocks, and they
every two pairings of constituents in the groundwater also exist in landfill leachate.
dataset, showing strong; r = 0.01 and significant; r = 0.05 Geological weathering conditions and geogenic hydro-
relationships. EC displayed a significant connection with geochemical development of groundwater are indicated by
Na?; r = 0.939 and virtually comparable liner correlation high ionic concentrations (Bodrud-Doza et al. 2016). These
with TDS; r = 0.98 and 98% confidence level. circumstances may be related to large anthropogenic
The increase in TDS and Na? ions concentrations in the activity involving cations and anions exchange. The key
collected groundwater samples is as a result of rock factors causing the greatest variation in electrical conduc-
weathering, which also increases ionic strength and salin- tance and dissolved solids are matrix erosion in aquifers
ity. Moreover, Ca2? showed strong positive correlation
with Mg2? (r = 0.905) and Cl- (r = 0.912), and SO42-
(r = 0.861). In addition, Mg2? showed a strong positive Table 4 The main three principal components extracted form
correlation with Cl- (r = 0.903) and SO42- (r = 0.877). groundwater samples
These connections showed the lithologic impact of the
Parameters PC1 PC2 PC3
dissolution of aquifer minerals and water–rock interactions.
TDS 0.994 – –
3.2.2 Principal component analysis TH 0.983 – –
EC 0.977 – –
Bartlett’s test of normality was used to calculate the cor- Mg2? 0.962 – - 0.178
relation matrix, and Kaiser–Meyer–Olkin KMO sampling Ca2? 0.959 – –
Cl- 0.953 – –
Table 3 The main principal component analysis of the collected Na? 0.953 – –
groundwater samples SO42- 0.911 – 0.110
?
Component Initial eigenvalues K 0.900 - 0.151 0.113
pH 0.631 0.204 –
Total % Variance Cumulative %
CO32- 0.107 0.738 0.463
1 8.769 62.639 62.639 HCO3- 0.377 0.659 0.400
2 1.489 10.632 73.271 NO32- – - 0.452 0.721
3 1.288 9.2 82.47 F- – 0.476 - 0.553

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According to Mollema et al. (2015), redox reactions and

CaCO3 dissolution were the main causes of high HCO3-
concentrations; up to 680 mg/L. Cluster 3 is made up of
K?, NO32-, pH, and F-. When the pH increase, HCO3- is
produced in groundwater. According to Omo-Irabor et al.
2008, the presence of K? showed that fertilizers and bio-
genic vegetation degradation may be the sources of the
leaching from K-feldspar rocks in the aquifer media.

3.3 Hydrogeochemical characterization

Using a Piper diagram (Piper 1944), the hydrochemical

parameters of the collected groundwater samples were
shown in Fig. 4. Knowing the main cations and anions that
have a big impact on the local hydrochemistry is crucial to
understanding the hydrogeochemical properties of
Fig. 2 Principal component analysis plot PC1, PC2, and PC3 of groundwater. Two cones were visible. Anion was sym-
groundwater bolized by one, and cation by the other. The areas of the
cation and anion fields were combined to depict a single
and ion input. Additionally, the ions Ca2?, Na?, and SO42- point in the rhombus field using the idea of the hydro-
may come from fertilizers (Bodrud-Doza et al. 2016). chemical plane. These three-line plots were more effective
PC2 showed positive loading with pH, CO32-, HCO3-, than earlier graphical techniques at revealing the precise
and F- and negative loading with K? and NO32-, chemical correlations between groundwater samples. The
accounting for 10.63% of the overall variation (Table 5). idea of comparing various locations according to categories
This component demonstrates the crucial role that pH plays of cation and anion concentrations hydro-geochemically
in the aquifer’s impact on the dissolution of minerals. The made it easier to comprehend the composition of water and
PC3 in the datasets accounted for 9.2% of the total varia- classify it into multiple groups. The chemical information
tion and has positive loading for SO42-, K?, CO32-, obtained from the collected groundwater samples were
HCO3-, and NO32- but negative loading for Mg2? and F- displayed as a three-line plotted in Fig. 4.
(Table 5). It might be related to the leaching and dissolu- Piper diagram indicates that most of the groundwater
tion of sediments as well as geochemical changes in samples fall within the Ca-Mg cation type in the cations
groundwater. On the other hand, K? loading may indicate plot field and of the Cl plot type in the anion plot field
agricultural waterways, especially those that have infil- (Piper 1944). The Ca–Mg–Cl water type, which is preva-
trated waste effluent and the nitrogenous fertilizer KNO3. lent in the groundwater samples that were collected, was
found in the subareas (1) of the diamond-shaped region,
3.2.3 Hierarchical cluster analysis (HCA) suggesting that surface water and irrigation canals were the
source of the recharge. The results showed that ground-
This method generates a dendrogram, or tree diagram, as water’s hydrochemistry is dominated by alkaline earth
illustrated in Fig. 3, which depicts three major clusters for metals like Ca2?. Carbonate rocks, such as limestones and
the characteristics relating to groundwater quality. The dolomites, which are dissolved by carbonic acid in
elements EC, Na?, Cl-, and SO42- were found in Cluster groundwater, are the primary sources of calcium. Calcium
1, and they may have formed as a result of water–rock in the groundwater may be caused through the chemical
interactions that caused the aquifer matrix to dissolve, breakdown of calcic-plagioclase feldspars and pyroxenes
especially carbonates weathering in alkaline conditions. (Ganyaglo et al. 2010). Lime is another form of calcium
Most of collected groundwater samples have low acidity that can be found in agricultural fertilizers. Dolomite,
and relatively high alkalinity, which may be a result of ferromagnesian minerals like olivine, pyroxene, amphi-
carbonates weathering. Fertilizers containing calcium sul- boles, and dark-colored micas are the main sources of
phate; CaSO4 may be the source of Ca2? and SO42-. Ca2?, magnesium in groundwater. Magnesium is found in the
Mg2?, TH, HCO3-, and CO32- were the ions that make up composition of serpentine, montmorillonite, and chlorite in
Cluster 2, and they can be found in groundwater naturally metamorphic rocks (Nag 2009). The amount of dissolved
as a result of water–rock interactions or as a result of CO2 in the groundwater affects the reaction involving the
domestic sewage and agricultural contamination (Masoud magnesium solution.
and Abu El-Magd 2022).

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Table 5 Pearson correlation coefficient matrix among physicochemical parameters in the collected groundwater
pH TDS EC TH Na K Ca Mg Cl SO4 HCO3 CO3 NO3 F

pH 1 - 0.573** - 0.580** - 0.578** - 0.508** - 0.688** - 0.512** - 0.638** - 0.483** - 0.541** - 0.108 0.028 - 0.118 - 0.043
TDS 1 0.975** 0.987** 0.963** 0.872** 0.973** 0.952** 0.965** 0.895** 0.350* 0.082 0.019 - 0.085
EC 1 0.966** 0.939** 0.849** 0.937** 0.949** 0.950** 0.885** 0.308* 0.083 - 0.020 0.007
TH 1 0.911** 0.864** 0.982** 0.968** 0.930** 0.888** 0.322* 0.084 - 0.006 - 0.047
Na 1 0.820** 0.898** 0.880** 0.984** 0.845** 0.382** 0.071 - 0.010 - 0.131
K 1 0.832** 0.864** 0.788** 0.783** 0.292* 0.062 0.190 - 0.156
Ca 1 0.905** 0.912** 0.861** 0.344* 0.126 0.069 - 0.086
Mg 1 0.903** 0.877** 0.272 0.030 - 0.103 0.004
Cl 1 0.834** 0.370** 0.085 - 0.121 - 0.074
SO4 1 0.305* 0.078 0.204 - 0.108
HCO3 1 0.486** - 0.005 0.054
CO3 1 - 0.014 0.079
NO3 1 - 0.267
F 1
**
Correlation is significant at the 0.01 level (P \ 0.01)
*
Correlation is significant at the 0.05 level (P \ 0.05)
Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735
Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735 4727

Fig. 3 Dendrogram with an

imaginary vertical line showing
the clustering behavior of the
groundwater quality parameters

Cluster 1

Cluster 3

Cluster 2

Fig. 4 Piper diagram for the collected groundwater samples

In groundwater, 74.1% of the Ca2? and 40.2% of the regions, salty ocean water intrusion into fresh groundwater
Mg2? are attributed to the dissolution of carbonate rocks, sources. Chloride; Cl- concentrations in groundwater may
according to Holland (1978) and Ali et al. (2021). Chloride be caused by a variety of factors, including the existence of
can infiltrate groundwater through a number of different chlorides in rocks, evaporates, seawater intrusion, connate
channels, including soil weathering, salt-bearing geological and juvenile water, industrial refuse pollution, or domestic
formations, salt spray deposition, salt used for de-icing sewage pollution. Concentrations of Cl- in groundwater
roads, contributions from waste fluids, and in coastal are lower than 30 mg/L, while arid locations frequently

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4728 Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

have levels of 1000 mg/L or higher (Nag 2009). The low hydrochemistry of the research region, which comprises a
value of chloride ions is an indication of low salinity of the range of geological units.
groundwater of the study area. Figure 7 was plotted to understand the source of the
To better comprehend the connections between water major ion constituents in groundwater, weathering and
chemistry, aquifer lithologies and explain the mechanisms dissolution processes. Figure 7 indicated that groundwater
and processes that regulate water chemistry Gibbs diagram chemistry is largely controlled by evaporation dissolution.
is used. Additionally, Gibbs 1970 contended that the There is a weak correlation between Ca2?/Na? versus
chemistry of the world’s groundwater is substantially Mg2?/Na? as (r = 0.3447). From the bivariate plot, it was
controlled by processes like as atmospheric precipitation, clear that carbonate and Silicate dissolutions didn’t play
rock weathering, and evaporation crystallization. The three any significant role in the aquifer system of the study area.
fields in Gibbs’ diagram-precipitation dominance, rock The relation of (Ca2? ? Mg2?)-(SO42- ? HCO3-) vs.
dominance, and evaporation dominance-are therefore (Na?-Cl-) (Fig. 7) confirmed the existence an ionic
included to help identify the process regulating the chem- exchange process. This showed a trend of increase of Na?
istry of the water. Gibbs diagram displayed the ratios I content and decrease of Ca2? content, confirming an anion
represents; Na? ? K?/Na? ? K? ? Ca2? for cations and exchange process which is one of the hydrochemistry
the ratio II represents; Cl-/(Cl- ? HCO3-) for anions, processes in the study area (Farid et al. 2015).
where the ion concentration was expressed in mg/L. Ratio Using Sulin’s graphic, it was determined whether the
II demonstrated that the main anion ratio of the collected groundwater came from a marine or meteoric source (Sulin
groundwater samples was plotted, while ratio I depicts the 1946). There are two equal squares in this diagram. The
ratio of major cations. upper-right one, which represents MgCl2 and CaCl2 gen-
The samples used to calculate the amount of evaporation erating marine water, has rNa/rCl = 1. NaHCO3 and Na2-
are all obtained from wells that have been drilled next to SO4 come from meteoric water when rNa/rCl [ 1. Two
the ocean. Evaporation increases salinity by increasing triangles are formed by the division of two squares (Fig. 8).
Na? and Cl- proportionally to the increase in TDS. Na2SO4 and CaCl2 were two forms of recognized water.
Additionally, human activities like agricultural fertilizers Most of the collected groundwater samples were of old
and irrigation return flows affect the evaporation of marine (CaCl2) and old meteoric (Na2SO4) provenance.
increasing Na? and Cl- and, subsequently, TDS (Fig. 5). It The Na2SO4 groundwater type was related to deep mete-
is imperative to emphasize that samples of groundwater oric water percolation, and it exhibited a steady drop in
were decreasing in the silicate weathering area (Fig. 6). bicarbonate ion concentration with depth as a result of
Finally, it was determined that rock dominance is the most carbonate precipitation, increase in sulphate component
effective controlling mechanism for evaluating the solubility with groundwater temperature, and substantial

Fig. 5 Gibbs diagram showing rock water interaction

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Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735 4729

Fig. 6 Scatter plot between 140

Ca2? ? Mg2? and
HCO3- ? SO42- ionic 120
concentrations of the Carbonate Weathering
groundwater samples
100

Ca2+ + Mg2+ (mg/L)

80

60

40
Silicate Weathering
20

0
0 100 200 300 400 500 600
HCO3- + SO42- (mg/L)

12.0 200

Carbonate Carbonate
10.0
150
8.0 Silicate
HCO3-/Na+

Silicate
Mg2+/Na+

6.0 100

4.0
Evaporation 50
2.0 Evaporation

0.0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0 2 4 6 8 10 12
Ca2+/Na+ Ca2+/Na+

120
Release of Ca2+ and
70 Adsorption of Na+
(Ca2++Na+)-Cl-

20

0 -100 -200 -300 -400 -500

-30

Release of Na+ and

-80
Adsorption of Ca2+

-130
(Ca2++Mg2+)-(HCO3+SO42-)

Fig. 7 Ca2?/Na? vs Mg2?/Na? and Ca2?/Na? vs HCO3-/Na? and (Na? ? K?)-Cl- and (Ca2? ? Mg2?)-(HCO3–SO42-) relationships

fertilizer application (El-Sabbagh 2000). Using Chadha’s Sub-field 6, which showed reversed ion exchange activi-
figure, the hydrochemical facies of groundwater were cal- ties, represented a Ca–Mg–Cl water type.
culated (Chadha 1999). The collected groundwater samples
were plotted in sub-field 6 on Chadha’s figure (Fig. 9).

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4730 Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

Fig. 8 Sulin diagram of the collected groundwater samples

Fig. 9 Chadha diagram 100

classification of the studied
water samples
80
3
60 5
8
40
(HCO3-) - (Cl- + SO42-)

20

2 0 1
-100 -80 -60 -40 -20 0 20 40 60 80 100
-20
4

-40
7 6
-60

-80

-100
(Ca2++Mg2+) - (Na++K+)

3.4 Water quality assessment groundwater samples’ pH values ranged between 7 and 9.
The collected groundwater samples were lower than the
3.4.1 Drinking water quality permissible limit according to World Health Organization.
The groundwater samples’ TDS levels ranged from fresh to
Physicochemical parameters of the collected groundwater marginally saline, between 71 and 783 mg/L. TDS levels
samples and the approved guidelines from the World in the groundwater samples were lower than 1000 mg/L,
Health Organization (WHO 2017) were contrasted. The making them safe to drink (Table 6). The maximum TH

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Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735 4731

Table 6 Classification of
Parameter and range Water Classification according to Davis and Dewiest (1966) Groundwater %
drinking water samples based
on different parameters TDS
\ 500 Desirable for drinking 11.7%
500–1000 Permissible for drinking 88.24%
[ 1000 Unfit for drinking –
Hardness Sawyer and McMcartly (1967)
\ 75 Soft –
7–150 Moderately high –
150–300 Hard 80.9%
[ 300 Very Hard 19.1%

Table 7 Classification of the

Parameter Water Classification Groundwater %
collected groundwater samples
based on different parameter Sodium adsorption Ratio (SAR) Wilcox (1955)
0–10 Low sodic hazard 20.4%
10–18 Medium sodic hazard 71.4%
18–26 High sodic hazard 8.2%
[ 26 Very hard sodic hazard –
Electric Conductivity (EC) WHO (2017)
\ 250 Excellent 6.12%
250–750 Good 20.4%
750–2000 Permissible 71.4%
2000–3000 Doubtful –
[ 3000 Unsuitable –
Sodium Percent (Na %) Gao et al. (2016)
\ 20 Excellent 6.12%
20–40 Good 91.8%
40–60 Permissible 2.08%
60–80 Doubtful –
[ 80 Unsuitable –
Residual Sodium Carbonate (RSC) Gupta and Gupta 1987
\ 1.25 Good –
1.25 – 2.5 Doubtful –
[ 2.5 Unsuitable 100%
Kelley Ratio (KR) Kelly, 1963
\1 Good quality water 97.96%
[1 Unsuitable water 2.04%
Magnesium Hazard (MH) Abdulhussain (2018)
\ 50 Suitable water 100%
[ 50 Unsuitable water –
Permeability Index (PI) Falowo et al. (2017)
[ 75 Good 100%
25–75 Doubtful –
\ 25 Unsuitable –
Corrosion Ratio (CR) Aravindan et al. (2004)
\1 Suitable 97.96%
[1 Unsuitable 2.04%

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4732 Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735

concentration that can be used for drinking is 500 mg/L collected groundwater samples were excellent for irriga-
(WHO 2017). All of the collected groundwater samples are tion, 20.4% were suitable for irrigation, and 71.4% were
acceptable for drinking as they have TH lower than the permissible for irrigation.
permissible limit; 500 mg/L (Table 6). Residual Sodium Carbonate, or RSC, is another indi-
cation that groundwater is suitable for irrigation (Raju et al.
3.4.2 Irrigation water quality 2015). The groundwater can be used for irrigation if the
RSC value is lower than 2.5 meq/L. All of the collected
Different hydrogeochemical parameters such as Electrical groundwater samples couldn’t be used for irrigation
Conductivity; EC, Residual Sodium Carbonate; RSC, (Table 7). When dissolved salt levels in groundwater are
Kelley’s Ratio; KR, Magnesium Hazard; MH, Permeability higher than dissolved calcium and magnesium levels, clay
Index; PI, and Potential Salinity; PS, Soluble Sodium soil expands or undergoes dispersion, which drastically
Percentage; SSP, Sodium Adsorption Ratio; SAR; Mag- reduces the soil’s capacity for infiltration (Gupta and Gupta
nesium Hazard; MH were commonly used to control the 1987).
quality of collected groundwater samples for agricultural Kelley’s ratio, which compares the amount of sodium to
purposes (Table 7). the amounts of calcium and magnesium, is the basis for
Sodium adsorption ratio SAR, is a measurement of the rating irrigation waters (Kelley 1963). 97.96% of the col-
irrigation suitability of groundwater. Higher SAR irrigation lected groundwater samples were classified as good quality
water damages soil aggregates and structure by increasing water and 2.04% were classified as unsuitable water
the soil’s salt (Singh and Singh 2018). 20.4% of the col- (Table 7). By displaying the ratio of Mg2? to Ca2?, mag-
lected groundwater samples had low sodic hazard, 71.4% nesium hazard; MH can be used to determine the suitability
had medium sodic hazard, and 8.2% had high sodic hazard. of groundwater for irrigation. Due to the high Mg2? con-
The measurement of sodium percent; Na% is important centrations in irrigation water, the soil quality is negatively
for the management of groundwater for irrigation because impacted, becoming alkaline and resulting in a decrease in
high sodium concentrations in water and soil reduce soil crop yield (Gao et al. 2016; Kumar et al. 2007). For irri-
permeability, which slows plant growth. By comparing gation water, 50 is the permissible limit for magnesium
Na% and EC, Gao et al. (2016) classified groundwater for hazard. According to Table 7, all of the collected ground-
irrigation (Fig. 10). Since 99% of the collected ground- water samples were suitable for agriculture and irrigation
water samples fall into excellent to good and good to in every instance. When mineral-rich water is used for a
allowed categories, the collected groundwater samples can long period of time, it diminishes the soil’s permeability,
be used for irrigation of crops and for agriculture. which has an indirect impact on crop yield. Due to its
The ability of crops to absorb water and nutrients from permeability index being below the allowable limit, all of
the soil is decreased by salt, which has a high electrical the collected groundwater samples were excellent and
conductivity value. Based on EC in groundwater, four suitable for irrigation (Table 7). Corrosivity ratio; CR is in
categories were created: excellent, good, permissible, and term describes how vulnerable groundwater is to corrosion.
doubtful (WHO 2017). According to Table 7, 6.12% of the Table 7 showed that 97.96% of the collected groundwater
samples were appropriate for agriculture uses and crop
irrigations whereas only 2.04% were not suitable.
100

90

80 4 Conclusion
Sodium Percent (Na %)

Doubtful to Unsuitable

70
Unsuitable

60 For irrigation and drinking purposes in the research area,

groundwater is a crucial source. Agribusiness operations
Excellent to Good

50
Good to Permissible

have a significant impact on groundwater quality. For

40
irrigation and drinking purposes, groundwater has been
30
assessed. Quality of the collected groundwater samples for
20 irrigation purposes is controlled by using different hydro-
10 geochemical Parameters. The groundwater samples’ pH
0 levels varied from slightly acidic to alkaline. Electric
0 500 1000 1500 2000 2500 3000 3500 4000 conductivity, with EC values ranged between 98 and 1443
S.cm-1 and a mean of 825.9 ± 41.2 S.cm-1. The TDS
Fig. 10 Plot of Sodium Percent (Na%) versus Electric Conductivity
(EC) values varied between 71 and 783 mg/L, with a mean value
of 478 ± 22.7 mg/L. According to groundwater

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Stochastic Environmental Research and Risk Assessment (2023) 37:4719–4735 4733

conductivities, the collected groundwater samples were Data availability Not applicable.
highly ion-bearing. Ca2?, Mg2?, Na?, and K? concentra-
tions. The collected groundwater samples had concentra- Declarations
tions of dissolved anions like HCO3-, Cl-, SO42-, NO32-,
and F- that varied between 322 and 450 mg/L, 1–16 mg/L, Conflict of interest The authors declare no conflicts of interest.
0–168 mg/L, 0–21 mg/L, and 0.08–0.1 mg/L, respectively.
The main cations in the collected groundwater samples
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