Acta Geochim (2023) 42:648–672
https://doi.org/10.1007/s11631-023-00610-0
ORIGINAL ARTICLE
Evaluation of hydro-chemistry in a phreatic aquifer
in the Vindhyan Region, India, using entropy weighted approach
and geochemical modelling
Ashutosh Mishra1 • Aman Rai1 • Prabuddh Kumar Mishra2
Received: 22 November 2022 / Revised: 27 February 2023 / Accepted: 11 April 2023 / Published online: 17 May 2023
 The Author(s), under exclusive licence to Science Press and Institute of Geochemistry, CAS and Springer-Verlag GmbH Germany, part of
Springer Nature 2023
Abstract Groundwater quality monitoring and geochemi-
cal characterization in the phreatic aquifer are critical for
ensuring universal and equitable access to clean, reliable,
and inexpensive drinking water for all. This research was
intended to investigate the hydrogeochemical attributes and
mechanisms regulating the chemistry of groundwater as
well as to assess spatial variation in groundwater quality in
Satna district, India. To accomplish this, the groundwater
data comprising 13 physio-chemical parameters from
thirty-eight phreatic aquifer locations were analysed for
May 2020 by combining entropy-weighted water quality
index (EWQI), multivariate statistics, geochemical mod-
elling, and geographical information system. The findings
revealed that the groundwater is fresh and slightly alkaline.
Hardness was a significant concern as 57.89% of samples
were beyond the permissible limit of the World Health
Organisation. The dominance of ions were in the order of
Ca2? [ Na? [ Mg2? [ K? and HCO3- [ SO42--
[ Cl- [ NO3- [ F-. Higher concentration of these ions
is mainly concentrated in the northeast and eastern regions.
& Prabuddh Kumar Mishra
prabuddh@shivaji.du.ac.in
Ashutosh Mishra
ashujubilian@gmail.com
Aman Rai
amanrai.ar29@gmail.com
Suresh Chand Rai
raisc1958du@gmail.com
1
Department of Geography, Delhi School of Economics,
University of Delhi, Delhi 110027, India
2 et al. 2021; Sinha and Rai 2021; Mondal et al. 2022). Its
Department of Geography, Shivaji College, University of
Delhi, Delhi 110027, India
123
• Suresh Chand Rai1
Pearson correlation analysis and principal component
analysis (PCA) demonstrated that both natural and human
factors regulate groundwater chemistry in the region. The
analysis of Q-mode agglomerative hierarchical clustering
highlighted three significant water clusters. Ca–HCO3 was
the most prevalent hydro-chemical facies in all three
clusters. Geochemical modelling through various conven-
tional plots indicated that groundwater chemistry in the
research region is influenced by the dissolution of cal-
cite/dolomite, reverse ion exchange, and by silicate and
halite weathering. EWQI data of the study area disclosed
that 73.69% of the samples were appropriate for drinking.
Due to high salinity, Magnesium (Mg2?), Nitrate (NO3-),
and Bicarbonate (HCO3-) concentrations, the north-central
and north-eastern regions are particularly susceptible. The
findings of the study may be accomplished by policy-
makers and groundwater managers to achieve sustainable
groundwater development at the regional scale.
Keywords Groundwater quality assessment  EWQI 
Multivariate statistical analysis  Geochemical modelling 
Hydrogeochemical processes  Saturation index
1 Introduction
Water is crucial for sustaining life, livelihood, and pro-
ductivity functions of any ecosystem, but the availability
and distribution of water is not uniform throughout the
planet. Groundwater is the foremost source of fresh water,
which provides a dependable supply for drinking along
with agricultural, industrial, and household usage (Gautam
ubiquity, reliability, and affordability throughout the year
Acta Geochim (2023) 42:648–672
have made it the primary safeguard against famine, playing
a critical role in food security. The importance of
groundwater as a precious natural resource increases
exponentially in arid and semi-arid regions with irregular
rainfall, low seasonal river flow, and drought-stricken
landscapes. Various studies indicate seasonal water scar-
city and conservation methods implemented in many
regions of the world (Mishra et al. 2019, 2020, 2021).
Depletion of surface water resources has led to the reliance
on groundwater as a sustainable supply of water. It has
resulted in its widespread and indiscriminate contamination
and depletion across the globe due to both natural and
human-related activities, without concern for the replen-
ishment of aquifers and other environmental issues (Ram
et al. 2021).
Hydrological, atmospheric, climatic, topographical, and
lithological factors are all natural influences on ground-
water quality (Panaskar et al. 2016; Islam et al. 2017a;
Uddin et al. 2021). The escalating groundwater contami-
nation and scarcity crisis is a global issue (McArthur et al.
2001; Macdonald et al. 2016). This scenario necessitates
the judicious management of groundwater resources to
guarantee their viability. Various studies are conducted all
over the world to assess the quality of groundwater using
various techniques (Guo and Wang 2004; Bhattacharya
et al. 2006; Islam et al. 2017b). These techniques include
the entropy method and the spatial autocorrelation index
(Gorgij et al. 2017; Alizadeh et al. 2018), multivariate
statistical techniques and geochemical modelling (Mar-
ghade et al. 2019; Liu et al. 2020), water quality index
(WQI) under GIS framework (Ram et al. 2021), Principal
component analysis and correlation for assessing ground-
water contamination (Kumari et al. 2019). While most
research has concentrated on developing better methods for
evaluating groundwater quality, some have also examined
the effects of geochemical processes on groundwater
chemistry and the health hazards it poses (Marghade et al.
2019; Shukla and Saxena. 2020; Karunanidhi et al. 2020).
Due to the groundwater’s unique biological and physio-
chemical characteristics, it is worth noting that protecting
groundwater resources and mitigating detrimental risks are
more practicable and cost-effective than remediating con-
taminated groundwater resources. At the same time, it is
also widely acknowledged that hydrogeochemical charac-
terisations of groundwater and their influencing factors are
the fundamental evidence for comprehending groundwater
quality and its evolution; as a result, these studies have
fascinated extensive popularity and acceptance among the
general public, academician and government organisations
(Stopelli et al. 2020; Liu et al. 2020). Therefore, to ensure
the long-term viability of valuable but diminishing
groundwater resources, evaluations of the groundwater
quality are essential. Numerous studies on the viability of
649
groundwater in India have been undertaken using the
conventional and novel geostatistical approach (Subrama-
nian et al. 1985; Batabyal and Chakraborty 2015; Singh
et al. 2017; Subba Rao et al. 2020).
Development ofi ndustry and population in mining re-
gions pollutes groundwater, resulting in a sharp de-
cline in its quality. In the Indian state of Madhya Pradesh,
the Satna district has serious water contamination issues.
Many industrial facilities, including cement, thermal
power, and fertiliser factories dump untreated or inade-
quately treated effluents into surrounding rivers and
streams. Other contaminants, including heavy metals,
nitrates, and fluorides, also impact the groundwater quality
in the Satna district. Several studies suggest that the
excessive use of fertilisers and pesticides in agriculture, in
conjunction with the discharge of untreated industrial
effluents, has contributed to the pollution of groundwater.
Singh et al. (2016) discovered that the groundwater in
Satna district is polluted with levels of fluoride that exceed
the World Health Organization’s acceptable threshold
(WHO). Jadhav and Singh (2016) reported in another study
that the groundwater in the Satna district is highly polluted
with heavy metals such as arsenic, iron, and manganese.
According to Verma et al. (2018), the groundwater in the
Satna district is polluted with nitrate levels that exceed the
permitted limit established by the Indian government.
Nestled between the fertile soils of the Son River basin
and the limestone belt of India, in the district of Satna, both
the mining industry and the agricultural sector are seeing
rapid expansion. In this socio-economic setting where
industry and agriculture both are well-represented, the
majority of the studies in the reason are focused on smaller
areas and have used single techniques to assess the impact
of industries or agriculture activities on groundwater, no
studies have been conducted on the groundwater quality
and appropriateness for human consumption at the district
level. Thus, there is a need for a comprehensive study to
assess the status of groundwater at the district level using
an integrated approach. The present study conducted a
comprehensive investigation of groundwater (GW) quality
evolution for drinking suitability along with comprehend-
ing the hydro-chemical characterisation of factors and
processes responsible for the geochemistry of shallow
groundwater in the foothill region of Northern Vindhyan
range (Satna district, Madhya Pradesh, India).
2 Study area
The study area is in the north-eastern part of Madhya
Pradesh, India, between latitudes 2305’N and 2512’N
and longitudes 8021’E and 8123’E, and encompasses an
area of 7502 km2 (Fig. 1). The region has a general
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650 Acta Geochim (2023) 42:648–672

Fig. 1 Location map depicting

the sampling sites

elevation ranging from 375 to 704 m above the mean sea
level with irregular relief.
The terrain is semi-arid due to the extended dry season.
The coldest month (January) has an average temperature of
16.4 C, while the hottest month (May) has an average
temperature of 34.2 C. The average annual precipitation is
1046 mm, with minor variations in rainy and dry years, and
around 90% of the total annual precipitation falls during
the commencement of the southwest monsoon. Land use
land cover of the study area contains 6 major classes, in
which agricultural area covers nearly 66% of the study area
followed by shrubs at 20.7%, and forest cover at 6.7%.
Built-up area in the region only covers 0.6% of the study
area however 4% of the area is classified as Barren land
and 2% area is covered by surface waterbodies (Fig. 2).

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Acta Geochim (2023) 42:648–672
Fig. 2 Land use land cover map of satna district 2020
2.1 Geology and hydrogeological setting
Dolomite, limestone, shales with quartzites, conglomerates,
sandstones, granite, and granitic-gneisses are among the
pre-Cambrian to Quaternary lithological formations that
dominate this area. From a hydro-geological standpoint,
groundwater generally occurs in jointed, fractured, and
weathered horizons of unconfined to semi-confined settings
and receives the majority of its replenishment from pre-
cipitation. Sedimentary rocks belonging to the Vindhyan
supergroup are the main bedrock of most aquifers, which
are severely fractured and weather-cracked, making them
ideal for groundwater retention (CGWB 2017). In addition,
the presence of secondary joints and cracks in hard rocks
and solution cavities in limestones also have a substantial
impact on the region’s groundwater availability and flow
(CGWB 2013; Mishra et al. 2013).
3 Materials and methods
3.1 Groundwater sampling and chemical analysis
Data from 38 locations in 2020 (May) were obtained from
the National Hydrograph Monitoring Stations (NHS) and
651
the Exploration wells established by the Central Ground
Water Board (CGWB) North Central Region, Bhopal,
Madhya Pradesh, India.
CGWB collected the samples as per guidelines of the
American Public Health Association (APHA 2012) from
38 different locations in the Satna district, which includes
23 from Hand Pumps (HP), 10 from Dug wells (DW), and
5 from Tube wells (TW). The pH, Electrical Conductivity
(EC), Total Hardness (TH), Total Dissolved Solid (TDS),
Na?, K?, Ca2?, Mg2?, HCO3-, F-, Cl-, NO3-, and SO42-
of these water samples were determined using established
procedures. A portable pH and EC metre were used to
determine the pH and EC values in-situ. On the other hand,
other contents were determined in the CGWB’s NABL-
accredited Chemical Laboratory in Bhopal, M.P., India.
Calculating TDS from water samples is more compli-
cated and time-consuming than that ofEC. It is thus com-
mon to utilise electrical conductivity (EC) to repre-
sent TDS (APHA 2012). The use of EC is based on
observing a linear relation between specific conductance
and ionic strength for fluids with conductance ranging from
10 to 10,000 S/cm (Lind 1970; Hem 1985). Electrical
conductivity (EC) is frequently used to determine TDS,
assuming that EC and TDS are correlated by the equation;
TDS (mg/L) = ke x EC (lS/cm), where ke is a propor-
tionality constant (Taylor et al. 2018). For most of the
natural waters with EC values ranging from 100 to 5000
S/cm at 25 C, TDS (mg/L) can be estimated with little
error assuming ke = 0.65 (Rusydi 2018; Hem 1985;
CGWBa, Bhu-Jal News 2012).
To assess the accuracy of ionic measurements, the
charge balance error was calculated (CBE). CBE may be
quantified as [(Tz?-Tz-/Tz? ? Tz-) 9 100], where Tz?
signifies the total number of cations, and Tz- denotes
anions represented in meq/l as a total. A range of ± 5% is
often recognised as an acceptable level of analysis (Appelo
and Postma 1993; Batabyal and Chakraborty 2015; Kant
et al. 2018). In the present study, the observed CBE for all
samples was well within the range of acceptability (± 5%),
except for three samples (S17, S22, S26 having CBE of
-8.99, -15.23, and -10.60 respectively). The geograph-
ical locations of sampling sites are given in Fig. 1. Fur-
thermore, to check that the data were processed correctly, a
graph between Tz? and Tz- was also constructed. The
results revealed a statistically significant degree of associ-
ation (R2 [ 0.99) (Fig. 3) The near-linear fit implies a high
degree of correlation and high precision in the data
analysis.
3.2 Entropy water quality index (EWQI)
There are several different water quality indices (WQIs)
that have been developed for assessing groundwater
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The eigenvalue matrix X is converted to the normalised

matrix Y to compare the parameters because each param-
eter has a unique concentration and measurement unit. In
this study, out of four types of normalisation techniques:
cost, fixed, interval, and efficiency, the efficiency kind of
normalisation was employed with the help of the following
Eq. (2):
 
xij  xij min
yij ¼     ð2Þ
xij max  xij min

where (xij)max and (xij)min represent the highest and lowest

values of the hydro-chemical variables, respectively.
After transformation, the normalised matrix Y was
obtained, which is shown as follows in Eq. (3):
y11 y21 y31
Y ¼ y12 y22 y32 ð3Þ
Fig. 3 Plot between total cationic versus total anionic concentration
y1m y2m y3m
quality; the selection of an appropriate index requires The likelihood of the standardised value Pij of the
consideration of both the groundwater input variables and examined parameter ’j’ occurring in the ’ith’ sample is
the intended outcomes (Bodrud-Doza et al. 2016; Singh provided by the following Eq. (4):
et al. 2017). The entropy water quality index (EWQI) has ð1 þ yij Þ
been used in several other studies (Pei-Yue et al. 2010; Pij ¼ Pm ð4Þ
i¼1 ð1 þ yij Þ
Alizadeh et al. 2018) to determine the appropriateness of
groundwater for drinking purposes. Contrary to classical The information entropy (ej) of each variable is derived
WQIs, instead of utilising actual values, this technique using Claude Shannon’s (1948) Eq. (5):
assigns weights to parameters based on their entropy.
1 X m
Entropy and probability of occurrence are inversely related. ej ¼  Pij lnPij ð5Þ
lnm i¼1
Low Shannon entropy suggests a high probability, imply-
ing an accurate forecast of an occurrence (Shannon 1948). (ii) Entropy weightage: The second critical step in cal-
Thus, lesser uncertainty or entropy means more exact culating the EWQI is determining the entropy weight (wj).
information (Pei-Yue et al. 2010; Gorgij et al. 2017; Subba The parameters with a lower degree of randomness will be
Rao et al. 2020). The most significant benefit of the entropy given a larger weighting (wj) according to the following
technique is that it produces accurate results owing to the Eq. (6):
absence of human involvement in assigning weights to
ð1  ej Þ
parameters. Although the EWQI method is widely used in wj ¼ Pn ð6Þ
groundwater quality assessment; yet, it has several evident j¼1 ð1  ej Þ
flaws, including the use of objective weights based on Finally, the quality rating scale (qj) for all other
entropy, a rigid framework, and insufficient input param- parameters except pH was computed using the following
eters; and the attempts to produce an enhanced WQI have equations:
persisted (Pei-Yue et al. 2010).
Cj
EWQI calculation was carried out in three major steps qj ¼ ð7Þ
(Pei-Yue et al. 2010):(i) Calculation of entropy: First, the Sj
eigenvalue matrix X was constructed using the physico- The concentration of hydro-chemical parameter j (mg/L)
chemical data for samples ‘‘m’’ and their parameter ‘‘n’’ as is denoted by Cj, and the parameter j permitted limits (mg/
given in Eq. (1) (Su et al. 2018). This matrix was created L) are denoted by Sj, as determined by WHO (2017)
using n = 13 parameters and 38 samples. standards (Table 2).
x11 x12 x13 Since pH does not have a unit, the quality rating scale
X ¼ x12 x22 x23 ð1Þ qpH for all samples was derived using the following
xm1 xm2 xmn Eq. (8): (Dashora et al. 2021):

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pH  7
qpH ¼  100 ð8Þ
SpH  7
Here, pH of the ’ith’ sample is represented by pH, while
SpH, i.e., 8.5, represents the highest permissible pH value.
(iii) EWQI: The EWQI value is then calculated in the
last stage by using Formula (9) as follows:
X n
EWQI ¼ w j qj ð9Þ
J¼1
After calculating the EWQI score, the samples were
classified into 5 different ranks and water quality classes
(Table 1) based on their EWQI score as per the classifi-
cation adopted by various studies (Subba Rao et al. 2020;
Dashora et al. 2021.)
3.3 Geographical information system (GIS) analysis
Due to its exceptional capacity to merge diverse informa-
tion, GIS has become a critical and indispensable feature of
many comprehensive environmental modelling systems.
To determine the variability throughout the study area, the
parameters are transformed to a raster format by interpo-
lating existing vector data using GIS technology.
The data were spatially interpolated, and values be-
tween measurements were estimated using an inverse
distance weighted (IDW) method.
3.4 Multivariate statistical analysis
The fundamental advantage of multivariate analysis is that
it examines the multiple independent (input) factors that
impact the dependent (output) variable to analyse several
variables at once and provide accuracy. It also provides
valuable implications by eliminating misleading variables.
To define hydro-chemical types and investigate the
origin of chemical components, we used multivariate sta-
tistical analysis, which included Pearson’s correlation
matrix, Principal Component Analysis (PCA), and
Agglomerative Hierarchical Cluster Analysis (AHCA).
Table 1 Criteria for water quality classification based on the EWQI
score
EWQI score Rank Water quality
\ 25 1 Excellent
25–50 2 Good
50–100 3 Medium
100–150 4 Poor
[ 150 5 Extremely poor
653
Additionally, the hydro-chemical facies were assessed
using a Piper trilinear diagram.
3.4.1 Pearson correlation matrix/Correlation analysis
Pearson’s correlation was used to assess the relationship
among the physicochemical parameters. In this investiga-
tion, a bivariate correlation was conducted. Pearson’s
coefficient of correlation quantifies the linear link between
two variables. It has a value between - 1 and 1, where 0
indicates no association, 1 indicates a perfect positive
relationship, and - 1 indicates a perfect negative
relationship.
3.4.2 Principal component analysis (PCA)
PCA is a statistical method for generating new results from
original data using varimax rotated R-mode to provide a
unique solution (Wu et al. 2018). The Kaiser criterion was
used with varimax rotation of loadings for a maximum
variance to extract the number of components in PCA. The
components with eigenvalues over 1 are considered
(Marghade et al. 2019). PCA was performed by using
Originlab 2022.
3.4.3 Agglomerative hierarchical clustering (AHC)
Agglomerative Hierarchical Clustering (AHC) is the most
frequently used hierarchical clustering. AHC divides the
dataset into clusters based on similarities and differences
between and within the datasets. The Q-mode of AHCA
divides the monitoring locations into clusters based on their
chemical and geochemical similarities. The AHCA was
performed using squared Euclidean distance and Ward’s
linkage, which is the most suitable combination for con-
ducting the AHCA analysis (Yidana et al. 2010). The
dendrogram is obtained and divided into clusters based on
the amount of dissimilarity. In order to conduct the AHC,
Microsoft Excel’s XL-STAT plugin was used.
3.5 Geochemical modelling
3.5.1 Saturation index
Geochemical modelling uses chemical thermodynamics,
chemical kinetics, or both to evaluate the chemical pro-
cesses that impact geologic systems, often with the help of
computer software. The saturation index (SI) can be used to
determine groundwater mineral concentration. As a result,
SI values can be used to determine the mineral phase in a
groundwater system, which is crucial for understanding
mineral dissolution and precipitation. The SI values were
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Table 2 Descriptive statistics of various physio-chemical parameters and their comparison with WHO (2017) standards
Variables Minimum Maximum Mean Median S.D WHO Standards (2017) Samples above WHO limits (in %)

pH at 25 C 7.20 8.53 7.66 7.63 0.31 8.50 Nil

EC at lS/cm 458 1915 922.50 855.5 368.17 1500 10.53
TH 124 800 343.26 335 147.52 300 57.89
TDS 297.70 1244.75 599.63 556.08 239.31 1000 10.53
Na? 3.00 112 44.34 36.50 28.87 200 Nil
K? 1.30 22.10 4.28 2.80 4.54 30.00 Nil
Ca2? 22.00 224 80.08 69.50 40.97 200 2.63
Mg2? 11.00 77.00 36.61 36.50 16.33 50.00 15.79
HCO3- 110 610 285.05 271.5 101.99 400 10.53
F- 0.11 1.15 0.56 0.54 0.26 1.50 Nil
Cl- 10.00 375 98.47 67.00 82.77 250 5.26
NO3- 3.00 157 24.58 14.00 29.96 50.00 10.53
SO42- 4.00 83.00 29.68 25.00 18.92 250 Nil
*Nil denotes that none of the samples are exceeding the permissible limit of WHO (2017)

calculated in this study using the PHREEQC program and
the following equation: (Parkhurst et al. 2013).
 
IAP
SI ¼ log ð10Þ
K
where IAP = ion activity products, K = corresponding
equilibrium constant, SI = 0, SI [ 0, and SI 0 represent
equilibrium, oversaturation, and undersaturation, respec-
tively, in Eq. (10). SI values between - 0.5 and ? 0.5
indicate an equilibrium condition between minerals and
groundwater, implying that the mineral is neither dissolv-
ing nor precipitating (Appelo and Postma 2005).
4 Results and discussion
4.1 Hydro-geochemistry
4.1.1 Physical parameters
Groundwater quality assessment studies rely heavily on a
statistical analysis of physicochemical characteristics,
which serve as valuable indicators of how groundwater
chemistry is evolving and the impact it has on the related
regulatory mechanisms besides the enhanced visualisation
of big data sets. Table 2 provides descriptive statistics of
the analysed physicochemical parameters of 2020.
Statistical analysis of the physical and chemical prop-
erties revealed that the pH of the study area varied from
7.20 to 8.53 (Fig. 4a), with an average of 7.66. This sug-
gests that the groundwater is neutral to mildly alkaline in
nature, mainly in the western and eastern parts of the dis-
trict in the form of some patches. The results portray that
Table 3 Groundwater classification based on Total Hardness (TH)
values (Sawyer et al. 2003)
Range Degree of hardness % Of samples
0–75 Soft Nil
75–150 Moderately Hard 05.26
150–300 Hard 36.84
[ 300 Very Hard 57.89
EC values varied widely from 458 to 1915 lS/cm, with an
average value of 922 lS/cm (Fig. 4b), which is a bit on the
higher side and demonstrates good to slightly saline
groundwater. High EC ([ 1500 lS/cm) is mostly found in
the central and eastern parts of the study area. TDS levels
ranged from 297.70 to 1244.75 mg/L, with an average
value of 599.63 mg/L.
Moreover, when it comes to Total Hardness (TH),
57.89% (Table 3) of the total samples during the studied
period surpassed the drinking criterion threshold of
300 mg/L recommended by the World Health Organization
(WHO 2017). The spatial distribution of TDS and TH are
depicted in Fig. 4c and d respectively.
4.1.2 Cations
Major cations were analysed and the analysis of ionic
content of Na?, K?, Ca2?, and Mg2? reported mean values
of 44.34, 4.28, 80.08, and 36.61 mg/L respectively. Thus,
the mean values of cations demonstrate the cation’s dom-
inance in the following order Ca2? [ Na? [ Mg2?
[ K?. Calcium is the more abundant cation in the region,

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Fig. 4 Spatial distribution of various physiochemical parameters a pH at 25 8C, b EC (S/cm), c Total hardness, d Total dissolved solid, e Sodium
(Na?), f Potassium (K?), g Calcium (Ca2?), h Magnesium (Mg2?), i Bicarbonate (HCO3-), j Fluoride (F-), k Chloride (Cl-), l Nitrate (NO3-),
m Sulphate (SO42-)

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Fig. 4 continued

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Fig. 4 continued

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Chloride had a range of concentration between 10 and

375 mg/L. Nitrate is less prevalent in comparison to
Chloride, with concentrations ranging from 1 to 157 mg/L.
However, around 21.05% of water samples contained
nitrate concentrations above the permissible limit of
45 mg/L as recommended by WHO. Fluoride concentra-
tions are modest, ranging from 0.11 to 1.15 mg/L. SO42-
may be contributed to groundwater by the dissolution of
gypsum and anhydrite, whereas NO3- may be contributed
to groundwater by fertilisers, leaching of municipal gar-
bage, and agricultural runoff (Singh et al. 2017). Cl-,
NO3- and SO42- concentrations are particularly high in the
north-eastern parts of the study area.
Moreover, the standard deviation values for K? and
NO3- (Table 2.) are more than the mean values, indicating
that the distributions are not homogenous (Singh et al.
2017). Thus, the wide variation in hydrogeochemical
parameters of the Satna district, as shown by descriptive
statistics with spatial distribution maps (Fig. 4), points to
the complexity of the hydrogeochemical processes taking
place in the research region.

4.2 Multivariate statistical result

4.2.1 Pearson correlation analysis

Hydrochemistry may be better understood by looking at the

Fig. 4 continued
correlation matrix in detail since it identifies each param-
eter’s function and effects explicitly (Helena et al. 2000).
varying from 22 to 224 mg/L. The highest Ca2? content is
In the present study, the relationship between the physic-
in the eastern region, where the lithological unit of lime-
ochemical parameters was determined using Pearson’s
stone is widespread. Values of Sodium vary from 3 to
bivariate correlation. The results are summarised in
112 mg/L. Due to ion exchange, Na? is stable in nature
Table 4.
and attaches to clay minerals (Subramanian et al. 1985).
A strong positive association (r [ 0.9) exists between
Magnesium has a range of concentration between 11 and
EC, TH, and TDS, while a very good positive correlation
77 mg/L. The concentration of Potassium is relatively
(r [ 0.7) exists between Na?, Ca2?, Mg2?, and Cl- in the
lower and it shows a range from 1.3 to 22.0 mg/L. The
studied period. These correlations demonstrate that these
spatial distribution of cations is depicted in Fig. 4e–h.
ions have a substantial effect on the conductivity of water.
TH demonstrated a high positive correlation with TDS and
4.1.3 Anions
a very good positive association with Ca2?, Mg2? and Cl-,
which suggests that Ca2? and Mg2? had greater contribu-
Anions show abundance in the order of HCO3- [ SO42--
tions toward hardness.
[ Cl- [ NO3- [ F-. The spatial distribution of anions is
The fact that Na? showed a strong and good positive
depicted in Fig. 4i–m. Bicarbonate is the dominant anion in
association with Mg2?, HCO3-, and Cl- shows that these
groundwater and it has a range of value between 110 to
ions may have come from the same source, such as sewage
610 mg/L, with an average of 285.05 mg/L. High HCO3
and/or mineral weathering (Sener et al. 2017). Again, Ca2?
concentration suggests the existence of carbonate-contain-
demonstrated a strong positive connection with Cl- only.
ing minerals, along with the decomposition of organic
A substantial correlation between Ca2? and Cl- shows that
matter (Rina et al. 2012). The sulphate content varied from
human activities, such as sewage disposal, are the primary
4 to 83 mg/L, with average values of 29.68 mg/L,
cause of groundwater pollution (Kumari et al. 2019).
respectively. Moreover, in all the samples, SO42- con-
Mg2? shows a significant positive connection with
centrations were well within the permitted range of
250 mg/L. HCO3- (r = 0.69), indicating that magnesium and bicar-
bonate may have come from the same source in the

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Table 4 Correlation Matrix of geochemical data

Parameters pH EC TH TDS Na? K? Ca2? Mg2? HCO3- F- Cl- NO3- SO42-

pH 1
EC - 0.44 1
TH - 0.47 0.90 1
TDS - 0.44 0.99 0.90 1
Na? - 0.02 0.72 0.47 0.72 1
K? 0.12 - 0.06 - 0.02 - 0.06 - 0.13 1
Ca2? - 0.66 0.83 0.82 0.83 0.34 - 0.08 1
Mg2? - 0.16 0.77 0.75 0.77 0.51 0.00 0.41 1
HCO3- - 0.21 0.61 0.55 0.61 0.50 - 0.21 0.34 0.69 1
-
F 0.23 0.15 0.17 0.15 0.19 - 0.13 - 0.01 0.28 0.36 1
Cl- - 0.48 0.87 0.82 0.87 0.54 - 0.04 0.86 0.55 0.22 - 0.05 1
NO3- - 0.28 0.38 0.33 0.38 0.35 0.08 0.38 0.13 - 0.02 - 0.04 0.27 1
SO42- - 0.19 0.45 0.31 0.45 0.31 0.36 0.34 0.38 - 0.04 0.04 0.41 0.41 1
Bold values denote strong positive correlation while Italic values denote strong negative correlation

groundwater. Furthermore, because NO3- and K? have a

poor relationship, fertiliser application is unlikely to be the
predominant source of nitrate in the groundwater in the
area (Shukla and Saxena 2020). Furthermore, HCO3- has a
strong positive association with TH and TDS.

4.2.2 Principal component analysis (PCA)

The findings of PCA show that the first three principal

components (PCs) with eigenvalues larger than 1 account
for 74.29 percent of the total variance in the hydrochem-
istry dataset (Fig. 5). Based on absolute loading levels
of [ 0.75, 0.75–0.5, and 0.50–0.30, respectively, Principal
Component (PC) loadings can be characterised as strong,
moderate, or weak (Liu et al. 2020).
Table 5 presents the principal component loadings and
explains the variance for three components of 2020, illus-
trating the significance of each variable for each compo-
nent. As indicated in Table 5, PC1 explained 49.19% of
total variances in 2020, with an eigenvalue of 6.395.
Additionally, PC1 had high positive loadings of Ca2?,
Mg2?, Cl-, EC, TH, and TDS (0.773, 0.764, 0.869, 0.993,
0.922 and 0.993 respectively) and moderate loadings on
Na? and HCO3- (0.675 and 0.597 respectively).
As shown in Fig. 5, regarding PC1, the loadings of the
variables described above were significantly longer, and
they were segregated by lower angles, which shows that
these variables are strongly correlated (Singh et al. 2017).
This suggests that EC, TH, and TDS in the study area are
primarily due to the combination of Ca2?, Mg2?, Cl-,
SO42- and NO3- ions, which mainly come from the min-
eralisation of geological components, silicate weathering,
cation exchange process, and dissolution of calcite,
Fig. 5 Scree Plot representing Eigenvalue for each Component
Number
dolomite, and halite (Guo and Wang 2004, Sajil Kumar
et al. 2016). Nonetheless, wastewater from domestic uses,
intensive use of unlimited gypsum and nitrogenous fer-
tilisers, and irrigation-returns-flows are also additional,
prominent sources of Na?, Mg2? and Cl- (Yidana et al.
2010). Therefore, PC1 represents an amalgamation of
geogenic and anthropogenic/human-induced occurrences.
PC1 can also be regarded as the salinity component of the
water, as Na?, Ca2?, Mg2?, Cl-, and HCO3- are the
important indices contributing to salinity.
With eigenvalues of 1.84, PC2 accounted for 14.21% of
the total variance (Table 5). No cations or anions exhibited
significant strong positive or negative loadings ([ 0.75)

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Table 5 Principal component loadings, eigenvalues, % variance, and (Subba et al. 2020). Thus, the PC3 represents the loading
cumulative variance matrix of the geochemical data factor of K? and SO42-.
Quality parameters Components In Fig. 6, the inverse relationship between pH and
HCO3- is noticeable, where both the loadings had longer
PC1 PC2 PC3
lengths with respect to PC3 and are separated through a
pH at 25 C - 0.507 0.425 0.537 larger angle ([ 90), possibly due to inverse ion exchange,
EC at lS/cm 0.993 0.038 0.018 which lowers alkalinity and produces positive pH loading.
TH 0.922 0.014 - 0.084 Similarly, substantial positive loading of Na? and negative
TDS 0.993 0.038 0.018 loading of Cl- was reported in PC3. Loadings of both the
Na? 0.675 0.259 0.255 ions in PC3 are longer and separated by a wider angle
K?
- 0.062 - 0.421 0.647 (more than 90) (Fig. 6), demonstrating a weak correlation
Ca2? 0.848 - 0.284 - 0.285 between the two ions (Table 5). It is conceivable because
Mg2? 0.773 0.343 0.212 the dissolution of halite is influenced by the mineral solu-
HCO3- 0.597 0.626 - 0.102 bility of halite, which is dependent on the saturation state
F- 0.156 0.653 0.303 of calcite minerals in groundwater. This indicates that an
Cl- 0.869 - 0.232 - 0.113 excess of Ca2? in groundwater might inhibit the break-
NO3- 0.421 - 0.424 0.22 down of halite in groundwater (Dashora et al. 2021).
SO42- 0.473 - 0.412 0.589
Eigenvalue 6.395 1.847 1.415 4.2.3 Agglomerative hierarchical clustering (AHC)
Cumulative eigenvalue 6.395 8.242 9.657
Total variance (%) 49.189 14.21 10.888
The dissimilarity was determined using Euclidean distance,
Cumulative total variation (%) 49.189 63.399 74.287
and the greatest measured level of dissimilarity was 152.
Agglomeration was accomplished using Ward’s approach.
Extraction method: principal component analysis Automatic truncation was performed depending on
Bold letters denote the high loadings [ 0.75 entropy. The phenol line bisects the dendrogram at dis-
similarity levels of 48 and it cuts across three dendrites,
resulting in three groups (Fig. 7). The agglomerative
with reference to PC2, while HCO3- and F- (0.626 and hierarchical cluster analysis (HCA) findings were shown on
0.653 respectively) showed a moderate positive loading dendrograms. The AHC analysis classified all 38 sampling
with reference to PC2, while no cations or anions exhibited locations into three clusters (highlighted in various colours)
significant strong positive or negative loadings. Whereas based on the closeness of their physicochemical properties
the K?, SO42- and NO3- had the high negative loading (Fig. 7). The complete list of samples inside clusters is
- 0.421, - 0.412, and - 0.424. The high positive loading shown in Table 6. Based on these clusters, further evalu-
of HCO3- & F- and high negative loading of K?, SO42 ations and interpretations were developed.
and NO3- suggested that they are derived from separate The most contaminated locations fall under cluster 1
sources, with HCO3- emerging mostly from the dissolution with high TDS, Cl-, Na?, and HCO3- concentrations,
of calcite and dolomite. Thus, the PC2 represents the dis- mainly caused by human factors such as agricultural
solution of bicarbonate and can be representative of a operations and inappropriate sewage disposal (Etikala et al.
natural process. Regarding PC2, the loadings, as mentioned 2019). Except for pH and Ca2?, all water quality indicators
earlier, had good length, and the angle between the positive were beyond the permissible limit in this cluster (WHO
loadings was also lesser (Fig. 7). The larger positive cor- 2017). The cluster 2 sites fall within the ‘‘moderate to
relation may be attributable to the presence of these ions as high’’ pollution category. Whereas cluster 3 reflects ‘‘ex-
important components in organic waste and fertilisers tremely low’’ polluted sites where all metrics were within
(Dashora et al. 2021). the WHO’s (2017) permissible limits (Table 7).
PC3 is characterised by accounting for 10.888% of the AHC revealed an interesting observation, SD values for
total variance, with an eigenvalue of 1.415 (Table 5). The parameters such as EC, TDS, TH, Cl, SO42-, and HCO3-
K? and SO42- demonstrated a moderate positive loading were quite high, as shown in Table 2. However, when the
(0.647 and 0.589 respectively), indicating that the presence sample sites were separated and clustered using AHC,
of K? and SO42- minerals (Sylvite, Anhydrite and Gyp- these SD values were lower, confirming the clustering.
sum) in the host rocks, which in turn affects water quality

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Table 6 AHC Results by Cluster

Total No. of cluster 03
Cluster 1 Cluster 2 Cluster 3

Total number of samples 04 20 14

by cluster
Samples within cluster S1 S10 S26 S2 S3 S4 S5 S6 S8 S9 S12 S15 S16 S18 S19 S21 S23 S25 S27 S7 S11 S13 S14 S17 S20 S22 S24 S28 S29 S31
S32 S30 S33 S35 S38 S34 S36 S37

Table 7 Descriptive statistics for groundwater as per clusters obtained through AHC
Statistics pH EC TH TDS Na? K? Ca2? Mg2? HCO3_ F_ Cl_ NO3- SO42_

Cluster 1
Mean 7.33 1752.00 676.67 1138.80 83.00 5.83 172.00 59.67 384.33 0.69 275.00 63.00 54.33
S.D 0.14 185.60 109.70 120.64 25.71 5.63 56.43 14.57 42.57 0.29 86.75 81.90 35.95
Min 7.20 1550.00 590.00 1007.50 63.00 1.50 112.00 46.00 354.00 0.46 220.00 7.00 14.00
Max 7.48 1915.00 800.00 1244.75 112.00 12.20 224.00 75.00 433.00 1.01 375.00 157.00 83.00
Cluster 2
Mean 7.66 967.45 345.45 628.84 51.45 3.07 77.40 40.45 310.60 0.60 102.85 19.75 30.90
S.D 0.19 198.03 82.16 128.72 27.90 1.53 21.29 12.91 105.17 0.27 51.38 20.27 14.33
Min 7.35 605.00 124.00 393.25 16.00 1.70 42.00 22.00 146.00 0.25 35.00 4.00 13.00
Max 8.00 1320.00 455.00 858.00 111.00 7.30 124.00 77.00 610.00 1.15 197.00 77.00 61.00
Cluster 3
Mean 7.78 592.54 228.85 385.15 24.69 4.51 54.38 22.62 214.23 0.48 39.31 19.15 18.54
S.D 0.42 84.59 52.29 54.99 15.08 4.98 18.57 10.26 76.86 0.27 19.69 23.04 13.90
Min 7.31 458.00 125.00 297.70 3.00 1.30 22.00 11.00 110.00 0.11 10.00 3.00 4.00
Max 8.53 715.00 320.00 464.75 53.00 20.00 72.00 44.00 372.00 0.95 75.00 89.00 59.00

4.3 Hydro-chemical facies
Piper trilinear plots (Piper 1944) were used to examine the
hydro-chemical facies, which successfully indicate the
chemical origin of groundwater and water type in the
research region (Bhattacharya et al. 2006; Chung et al.
2015). The general Hydro-chemical Facies of groundwater
are shown in Fig. 8. The results show that the cation tri-
angle is completely dominated by alkaline earth metal
(Ca2? type water) (57.89%), and only 5.26% of samples
had Na? as the dominant cation. The remaining 36.84% of
samples lacked dominating facies. Similarly, weak acids
(HCO3-) dominate strong acids (SO42- and Cl-) in the
anion triangle, with 92.10% of samples being HCO3– type
and just 7.90% having no dominating anion.
It is clear from Fig. 8 that the majority of samples fall
inside the field I (Ca2?–HCO3- type) of the central dia-
mond. Three samples are in field III (Mixed Ca–Mg–Cl
type), and only two data points are in field IV (mixed Ca-
Na-HCO3). No data points were plotted in fields II, V, or
VI, indicating the lack of further facies. Additionally, the
core component has been classified into seven subclasses
(1, 2, 3, 4, 5, 6, and 7) (Langguth 1966). Most of the data
points fall into the class ’4’ category, which is charac-
terised by alkaline earth water with an excess of alkalis
predominating in the form of bicarbonate. Additionally,
15.79% of samples fall into the ’1’ classification, defined as
normal earth alkaline water with a high concentration of
HCO3-. Only one data point falls inside the ’5’ class,
characterised by alkaline earth water with high SO42- and
Cl- concentrations.
The majority of the samples are calcium-bicarbonate
types. This indicates weathering of Ca2?-bearing minerals
(Limestone/ Dolomite/ Gypsum) could be a prominent
responsible factor for the dominance of calcium-type facies
(Singh et al. 2017) in the geo-hydro environment. Fur-
thermore, Ca-Na-HCO3 and Ca–Mg–Cl water types imply
mineral dissolution, recharge of freshwater, and probable
rock-water interaction. Additionally, agricultural activities
and extensive fertiliser application may account for this
result in the research area since the region is mostly rural.

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Fig. 6 Biplot of loading and

scores for the first three
components in a 3-dimensional
rotated space.
(where ? denotes the loading
and • represents score)

Fig. 7 Dendrogram of AHC,

indicating clusters of sampling
sites. Different colours indicate
the different clusters in the
dendrogram

4.4 Hydrogeochemical processes 4.4.1 Silicate weathering

A molar ratio bivariate plot of major ions can be used to A correlation diagram between Na? and Cl- (Fig. 9a)
determine how rock and water interact in groundwater reveals that the majority of samples from cluster 1 deviate
circulation. from the 1:1 line and fall into the Cl- zone (Na/Cl \ 1),

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Fig. 8 Piper trilinear diagram showing the water types in the groundwater during 2020
indicating that the Chloride ion concentration into the
groundwater is high in these sites due to some additional
processes such as weathering of Na-bearing silicate min-
erals (e.g., feldspar) (Meybeck 1987) and cation exchange
(Saha et al. 2020). A similar pattern was seen in many
clusters 2 samples.
However, the bulk of samples from cluster 3 follows a
1:1 trend line, indicating that halite minerals are dissolved
in groundwater containing equal amounts of Na and Cl.
Simultaneously, the Figure demonstrates that a consider-
able number of samples from Cluster 2 and 3 depart below
the 1:1 line and fall into the Na? zone, generating a Na/Cl
ratio greater than 1, which implies silicate weathering and
so acts as a source of high sodium ratios in groundwater at
the cost of deficiency of Ca2? and Mg2? (Chen et al. 2020).
The Total Cations vs (Ca2? ? Mg2?) (Fig. 9b) plot
demonstrates that alkaline earth elements (Na? ? K?)
predominate over alkali in the aggregate.
The source of Ca2? and Mg2? in groundwater can be
determined using a plot of HCO3- vs (Ca2? ? Mg2?)
(Fig. 9c). The ratio (Ca2? ? Mg2?)/HCO3- should be
close to 0.5 if carbonate weathering or silicate minerals
such as pyroxenes and amphiboles are the primary sources
663
of Ca2? and Mg2? in groundwater (Sami 1992). If the ratio
is less than 0.5, ion exchange or HCO3- enrichment may
occur at the expense of Ca2? and Mg2? depletion. All
samples are substantially above the slope of 0.5 (Fig. 9c) in
the present analysis, indicating that Ca2? and Mg2? in
groundwater are mostly derived through the reverse ion
exchange process.
4.4.2 Ion exchange processes
The scatter plot of (HCO3- ? SO42-) against (Ca2?
? Mg2?) (Fig. 9d) is useful for ion exchange analysis
(Fisher and Mullican 1997; Rajmohan and Elango 2004;
Dashora et al. 2021). The samples located far and above the
equiline showed a greater Ca2?/Mg2? ratio, indicating that
reverse ion exchange between cations is the cause of the
high Ca2?/Mg2? concentration. Whereas due to the ion
exchange mechanism between the anions, the sites far and
below the equiline had excess HCO3-/SO42- concentration
(Rina et al. 2012).
In Fig. 9d, the majority of the samples of Clusters 2 and
3 are along the equiline, demonstrating that calcite, dolo-
mite, anhydrite, and gypsum would be the primary
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b Fig. 9 Molar ratio bivariate plot of major ion concentrations between
groundwater samples a Na? against Cl- b (Na? ? K?) against
(Ca2? ? Mg2?) c HCO3- against (Ca2? ? Mg2?) d (HCO3-
? SO42-) against (Ca2? ? Mg2?) e (Na-Cl) against (Ca2?-
? Mg2?–HCO3--SO42-) f Ca2? against Mg2? g Ca2? and SO42-
h Na?/Cl- against EC
reactions in the system for the concern clusters (Fisher and
Mullican 1997). However, all the samples of cluster 1 are
plotted on the far left and above the equiline, this might be
the consequence of reverse ion exchange, implying that
excess Ca2? and Mg2? come from clay minerals, with
sodium ions exchanged for Ca2? and Mg2? at favourable
exchange sites (Jankowski and Acworth 1997; Fisher and
Mullican 1997). Rajmohan and Elango (2004) illustrate the
likely reactions to this process:
þ groundwater chemistry (Mayo et al. 1995; Dashora et al.
2Naþ þ Ca2 þ ðMgÞ  Clay
þ þ
! Na  Clay þ Ca2 þ Mg2
Again, to corroborate the preceding conclusion, A sec-
ond analysis of reverse ion exchange was carried out by
studying the reaction between (Na-Cl) vs (Ca2? ? Mg2?–
HCO3--SO42-) (Fig. 9e). If groundwater undergoes
reverse ion exchange, the slope of the trend line must be
- 1. Figure 11e displays a slope of -1.04, confirming the
link between Ca, Mg, and Na via the reverse ion exchange
mechanism (Fig. 11).
þ groundwater chemistry, most likely due to clay-induced
IonExchange : 2NaX þ Ca2 ! 2Naþ þ CaX 2
þ
ReverseIonExchange : CaX 2 þ 2Naþ ! Ca2 þ 2NaX
ð13Þ
4.4.3 Dissolution and deposition
The mineral–water system may be thought of as an
ensemble of ions dispersing between solid and watery
phases via dissolution and precipitation processes at the
crystal-water interface. Dissolution can be defined as how
mineral particles tend to dissolve in water. The common
minerals in these processes are calcite, dolomite, gypsum,
and halite, which are predominant in the study area.
The interionic bivariate graph between (HCO3--
? SO42-) versus (Ca2? ? Mg2?) (Fig. 9d) is also useful
for investigating the potential of dissolution processes.
HCO3- ? SO42- versus Ca2? ? Mg2? scatter plot shows
that 70% of sample points lie either on the or very close to
the 1:1 line with HCO3- ? SO42- \ 10 meq, suggesting
dissolution of carbonate (calcite, dolomite, and aragonite)
665
or SO42- rich minerals (gypsum and anhydrite) for the
presence of Ca2?, Mg2?, HCO3- and SO42-(Fisher and
Mullican 1997; Karunanidhi et al. 2020).
To confirm the dominance of dissolution, a plot of the
Ca /Mg2? molar ratio (Fig. 9f) is further constructed
2?
(Marghade et al. 2019). Ratios between Ca2? versus Mg2?
aid in identifying the mineral (calcite/dolomite) that causes
groundwater hardness by dissolving in it (Dashora et al.
2021). Figure 10f suggests that those points are on or
above the 1:1 ratio line, indicating the Ca2?/Mg2? ratio is
less than 1 causing dissolution of dolomite in the study
area. Conversely, those points below the 1:1 line reflect the
Ca2?/Mg2? molar ratios greater than 1 but less than 2,
indicating that calcite dissolution is more prevalent than
dolomite dissolution through reverse ion exchange Like-
wise, in the presence of samples with a Ca2?/Mg2? ratio
greater than 2, silicate weathering is the process governing
2021).
ð11Þ
CaCO3 ðCalciteÞ þ H2 CO3 ! Ca2þ þ 2HCO
3 ð14Þ
CaMgðCO3 Þ2 ðdolomiteÞ þ 2H 2 CO3
þ þ
! Ca2 þ Mg2 þ 4HCO 3 ð15Þ
Figure 9f reveals that the dissolution of calcite is the
predominant geo-chemical pathway, with 52.63% of sam-
ples having a ratio between 1 and 2. However, more than
26.32% of samples had a ratio greater than 2, implying that
non-carbonated mineral sources may play a role in the
ð12Þ
reverse cation exchange or gypsum dissolution (Mayo et al.
1995).
4.4.4 Dissolution of gypsum
Gypsum dissolution is a significant source of calcium and
sulphate in groundwater. A correlation diagram between
Ca2? and SO42- (Fig. 9g) was created in order to depict
the plausible sources of calcium and sulphate. Accord-
ing to Fig. 10 g, gypsum dissolution does not predomi-
nate in the study area. All the samples possessed excess
Ca2?, which would be originated through more preva-
lent and prominent processes of dissolution of calcite and
dolomite, rather than gypsum.
CaSO4 :2H2 OhiCa2þ þ SO2
4 þ 2H2 O ð16Þ
4.4.5 Dissolution of chloride
The chloride concentration does not have a notable corre-
lation with the pH (r = - 0.37 and 0.48). However, the
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trend to the EC Axis, suggesting that these locations are

more prone to evaporation in the foreseeable future.
Additionally, the Fig. illustrates in the present study that
when EC grows, the Na?/Cl- ratio decreases gradually,
which is mainly a result of Na? depletion due to reverse
ion exchange (Rajmohan and Elango 2004).

4.5 Saturation indices

The saturation states of eight different minerals (i.e.,

Fig. 10 shows the comparison of saturation indices of various
minerals
positive correlation between Cl- and Ca2? (r = 0.86)
demonstrates that calcite dissolution and chloride dissolu-
tion occurred concurrently. Alkaline groundwater enriched
with HCO3- enhanced the dissolution of CaCl2, ultimately
increasing the chloride concentrations (Marghade et al.
2019).
4.4.6 Evaporation
Plotting Na?/Cl- versus EC is a great approach to keeping
track of evaporation (Rajmohan and Elango 2004)
(Fig. 9h). A horizontal trend line will appear on the plot if
evaporation is the dominating mechanism with a constant
Na?/Cl- ratio and no mineral precipitation (Jankowski and
Acworth 1997).
The fact that samples from clusters 2 and 3 show a
declining trend indicates that evaporation is not a signifi-
cant factor in influencing the groundwater’s chemistry.
However, samples from cluster 1 reveal a modest parallel
Anhydrite, Gypsum, Aragonite, Calcite, Dolomite, Fluo-
rite, Halite, and Sylvite) were determined in all 38 samples.
Table 8 reveals a statistical summary of saturation
indices of minerals and from the table it is obvious that, SI
values for Carbonate minerals such as Aragonite, Calcite,
and Dolomite (Fig. 11c–e) were positive (Si [ 0), indi-
cating that these minerals are oversaturated in many loca-
tions, confirming that carbonate minerals may have
influenced the chemical composition of groundwater
extensively through precipitation pathways. Similarly, the
positive SI value of Fluorite in all the samples confirms the
tendency to precipitate. Whereas, SI of Halite and Sylvite
minerals (Fig. 11g, h) have negative values, reflecting the
undersaturated state and hence tending to dissolution. SI
values of gypsum were close to 0, indicating a relative
equilibrium status (Fig. 11b). SI values for another sul-
phur-bearing mineral i.e., Anhydrite was positive (SI [ 0)
in most of the cluster 1 sample (Fig. 11a). However,
majority of the cluster 2 and 3 samples shown the disso-
lution tendency, particularly in the district’s eastern
section.
Figure 11a, b & c demonstrates that evaporated minerals
(anhydrite, gypsum, and halite) in most samples are
undersaturated due to high evaporation of the surface water
caused by the study area’s low and erratic rainfall com-
bined with high water run-off and intense solar radiation.
The fact that evaporated minerals are undersaturated in
groundwater samples indicates that their soluble

Table 8 Statistical summaries of Saturation indices of minerals obtained through aqueous speciation modelling using PHREEQC
Minerals Descriptive statistics of saturation indices of minerals
Minimum Maximum Mean Standard deviation

Anhydrite (CaSO4) - 1.22 0.40 - 0.21 0.35

Aragonite (CaCO3) 2.29 0.93 2.82 0.18
Calcite (CaCO3) 2.43 3.36 2.96 0.18
Dolomite CaMg(CO3)2 4.56 6.95 5.74 0.49
Fluorite (CaF2) 0.20 2.23 1.37 0.46
Gypsum (CaSO4:2H2O) - 0.92 0.69 0.08 0.35
Halite (NaCl) - 5.99 - 3.56 - 4.53 0.62
Sylvite (KCl) - 5.82 - 3.87 - 4.90 0.44

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b Fig. 11 a Plots of (Ca2? ? SO42-) vs Saturation indices of Table 9 Description of Entropy and Relative Weight for physio-
2?
Anhydrite b Plots of (Ca ? SO42-) vs Saturation indices of chemical Parameters
Gypsum c Plots of Ca2? vs saturation indices of Aragonite d Plots of
Parameters Unit Entropy (ej) Relative Weight (Wj)
Ca2? vs saturation indices of Calcite e Plots of Mg2? vs saturation
indices of Dolomite f Plots of F- vs saturation indices of Fluorite pH at 25C mg/L 0.9961 0.0744
g Plots of (Na? ? Cl-) vs saturation indices of Halite h Plots of (K?
? Cl-) vs saturation indices of Sylvite EC lS/cm 0.9953 0.0901
TH mg/L 0.9965 0.0669
TDS mg/L 0.9953 0.0901
Na? mg/L 0.9952 0.0921
K? mg/L 0.9958 0.0815
components Na?, Cl-, Ca2?, and SO42- are not restricted
Ca2? mg/L 0.9969 0.0599
by mineral equilibrium (Barkat et al. 2021).
Mg2? mg/L 0.9958 0.0808
HCO3_ mg/L 0.9970 0.0579
4.6 Groundwater quality drinking suitability -
F mg/L 0.9959 0.0791
(EWQI) and its spatial distribution
Cl- mg/L 0.9959 0.0801
The water quality index for the 13 physio-chemical NO3- mg/L 0.9966 0.0666
parameters of all 38 locations is calculated using the SO42- mg/L 0.9958 0.0807
Shannon Entropy method (1948) described in Sect. 3.2.
The entropy value or entropy weight of a parameter is used
to assess its impact on drinking water quality (Table 9).
The physicochemical properties with the lowest entropy
and greatest entropy weight would have the greatest impact
on the quality of drinking water (Gorgij et al. 2017).
Table 9 shows that Na? had the greatest impact on drinking
water quality, followed by K? [ Mg2? [ SO42- [ Cl-.
HCO3- with the lowest relative weight had the least impact
on drinking water quality. The final EWQI map of the
study region is given in Fig. 12.
Table 10 depicts the classification of water quality in
terms of rankings and percentage of samples based on
their EWQI score. Furthermore, the location-wise sum-
mary of EWQI scores and their water quality statistics for
the studied period are reported in Table 11. As per the
adopted classification scheme, it is obvious that Rank 1 and
Rank 2 samples are suitable for drinking purposes. Hence,
the quality of groundwater at the district level is by and
large good, with some exceptionally polluted pockets.
According to Table 11, EWQI scores in the study region
vary from 21.79 to 110.95 and means EWQI was found to
be 47.12.
Several techniques used in the present study depict
groundwater quality in the study area. Using multiple
techniques helps to understand the geochemical properties
of groundwater in various ways. All the previous studies in
the study area were limited to smaller areas such as blocks,
using a single technique. The present study gives a detailed
analysis of groundwater quality and geochemical charac-
teristics on the district level using multiple techniques
Limitation of this study is the use of secondary data and a
limited number of samples used for analysis. However, Fig. 12 Groundwater quality map of study area based on entropy
further studies can be done using primary data with more weightage of physio-chemical parameters
samples to understand the spatial variation in groundwater

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Acta Geochim (2023) 42:648–672 669

Table 10 Description of (%) of samples within each rank and their water quality
EWQI Rank Water (%) of Sample
quality Samples

\ 25 1 Excellent 5.26 S22, S31

25–50 2 Good 68.42 S2, S3, S5, S7, S9, S11, S12, S13, S14, S15, S17, S18, S20, S21, S23, S24, S25, S27, S28, S29, S30, S34,
S35, S36, S37, S38
50–100 3 Medium 26.32 S1, S4, S6, S8, S10, S16, S19, S26, S32, S33
100–150 4 Poor 0 None
[ 150 5 Extremely 0 None
poor

quality better. Additionally, spatiotemporal analysis can
also be done to understand the rate of change in water
quality in different parts of the district over the years.
The introduction of sustainable farming practices, the
construction of suitable treatment systems, and local
community awareness campaigns can aid in the reduction
of groundwater contamination in the region. The State
Pollution Control Board has devised guidelines for estab-
lishing wastewater treatment plants and ensuring compli-
ance with discharge requirements. The government and
civic society must collaborate to address the issue of water
contamination in the Satna district and safeguard the
region’s water resources for future generations.
5 Conclusion
The techniques used in this study (agglomerative clustering
analysis, geostatistical modelling, and the EWQI) helped in
determining the current state of water quality for drinking
suitability as well as identifying the factors that influence
groundwater chemistry in the studied area. The current
investigation findings demonstrate that human and geo-
logical activities together have contributed to the
degradation of the groundwater quality in the hard rock
area of the Vindhyan region of Central India. A review of
agglomerative hierarchical clustering (AHC) defined three
major water-type clusters. In all the clusters of both peri-
ods, Ca2? and HCO3- were the dominant cations and
anions, respectively, and groundwater samples exhibited
alkaline affinity and elevated degrees of hardness. Hydro-
chemical facies, based on the Piper diagram and AHC,
indicate weathering of Ca2? bearing minerals (Calcite/
Limestone/Dolomite), especially in the far central and
southern reaches. Based on the EWQI assessment, it has
been concluded that the groundwater quality in the research
region varied substantially, from ‘‘Excellent’’ to ‘‘Moder-
ate’’ and the majority of groundwater samples in cluster 1
had ‘‘Moderate’’ quality, owing to the higher concentra-
tions of NO3-, SO42- and HCO3-. So, using the water for
drinking purposes from Cluster 1 requires careful consid-
eration. Largely, water–rock interaction is the primary
determinant of groundwater quality in the region. Even
though certain locations are severely impacted by human-
induced pollution. Untreated wastewater discharge, sand-
stone mining, and agricultural activities pose a substantial
danger to the quality of groundwater. Consequently,
essential preventive measures should be adopted

123
670 Acta Geochim (2023) 42:648–672

Table 11 Description of EWQI scores and associated water quality in Acknowledgements We would like to extend our gratitude to Head,
groundwater samples Department of Geography, University of Delhi, Delhi for providing
necessary support for the study. The authors would also like to thank
Sample ID Sample site EWQI score Water quality class CGWB, North Central Region, Bhopal for providing freely available
data. The authors are also grateful to anonymous reviewers and edi-
S1 Amarpatan1 83.33 Medium tors for their constructive comments.
S2 Kakra 48.19 Good
S3 Kemar 39.64 Good Author Contributions AM: methodology, software, mapping, for-
S4 Mauhari katra 71.21 Medium mal analysis, writing—review and editing, data collection, data
analysis, mapping, writing—original draft preparation, AR: method-
S5 Mukundpur 35.82 Good ology, software, formal analysis, writing—review and editing, data
S6 Amdara 64.57 Medium analysis, mapping, writing—review and editing, PKM: conceptual-
S7 Bhadanpur New 55.88 Good ization, supervision, formal analysis, data analysis, mapping,
methodology, writing—review and editing, SCR: conceptualization,
S8 Jhukehi 53.54 Medium
supervision, formal analysis Methodology, writing—review and
S9 Kusendi 42.22 Good editing, All authors have read and agreed to the published version of
S10 Maihar New 78.01 Medium the manuscript.
S11 Naraura 30.39 Good
Funding This research received no specific grant from any funding
S12 Rivara 43.63 Good
agency in the public, commercial, or not-for-profit sectors.
S13 Sabhaganj 27.07 Good
S14 Babupur 34.66 Good Data Availability The data presented in this study are available on
S15 Birsinghpur 42.06 Good request from the corresponding author. The data are not publicly
S16 Chitrakoot 53.57 Medium available.
S17 Chowraha 39.75 Good Declarations
S18 Jaitwara 50.85 Good
S19 Majhagawa 55.84 Medium Conflict of interest On behalf of all authors, the corresponding
S20 Nakaila 31.22 Good author states that there is no conflict of interest.
S21 Barethia 50.09 Good
S22 Dureha 24.52 Excellent
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