Assessment of Groundwater Quality Using Entropy-We

Environment, Development and Sustainability (2024) 26:1615–1643
https://doi.org/10.1007/s10668-022-02776-8
Assessment of groundwater quality using Entropy‑Weighted

Quality Index (EWQI) and multivariate statistical techniques
in Central Ganga plain, India
Shamshaad Ahmad1 · Rashid Umar1 · Izrar Ahmad1
Received: 28 April 2022 / Accepted: 12 November 2022 / Published online: 27 November 2022
© The Author(s), under exclusive licence to Springer Nature B.V. 2022
Abstract
The present study aims to identify the quality of groundwater using integrated multivariate
statistical approach and Entropy-Weighted Quality Index (EWQI) in Mathura city of Uttar
Pradesh. A systematic sampling of a total of 96 samples was carried out in two consecu-
tive seasons and tested for major ions analysis using standard procedures. The groundwater
is falling in brackish category, alkaline and classified as hard to very hard type which is
somewhat unique for an area falling within Central Ganga Plains. The relationship between
electrical conductivity and Cl−/SO42− demonstrates an increase in salinity proportional to
the ratio confirming evaporitic dissolution as the dominant process controlling the ground-
water chemistry. The correlation coefficient revealed that TDS are strongly positive cor-
O4 and moderately positive correlated with Ca,
related with all salt including Na, Cl and S
hardness and K in both seasons. This suggested that the salinity is much more related to
geogenic environment consisting of halite (NaCl), Sylvite (KCl) and Gypsum (CaSO4)
mineral. The graphical presentation reveals that Na-K-Cl-SO4 is the dominant hydrochemi-
cal facies of groundwater. The results of various multivariate statistical techniques such
as principle component analysis, hierarchical cluster analysis and correlation coefficient
demonstrated groundwater quality to be controlled mainly by geogenic and to some extent
anthropogenic factors. The Entropy-Weighted Quality Index (EWQI) using entropy values
comprising numerous hydrochemical variables has been employed and proved to be more
feasible WQI method due to more extensive computation. According to the EWQI, major-
ity of samples displayed at rank 3 and medium groundwater quality in both the seasons.
The extreme northern, western and eastern parts of regions have elevated EWQI values.
These areas certainly require more attention for groundwater protection in future.
Keywords Salinity · Water quality index · Hierarchical cluster analysis (HCA) · Mathura ·
Uttar Pradesh
* Rashid Umar
[email protected]
1
Department of Geology, Aligarh Muslim University, Aligarh 202002, India
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Vol.:(0123456789)
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
1616 S. Ahmad et al.
1 Introduction
Groundwater is an important source of water in urban as well as rural areas of almost all
developed countries (Amiri et al.,et al. 2022; Khan et al.,et al. 2022; Wang et al.,et al.
2020). In India, approximately 80% and 50% of the rural and urban populations, respec-
tively, rely on groundwater for their household consumption (Biswas et al.,et al. 2014). A
quick urbanization has risked the quality of water resources in Indo-Gangetic plains. Dete-
rioration of water quality is caused by physical and chemical parameters. These parameters
are influenced by geological formations and human actions (He et al.,et al. 2022; Li et al.,et
al. 2017; Ren et al.,et al. 2021; Subramani et al.,et al. 2005). Water quality has deteriorated
most dramatically in heavily populated areas, major industrialized zones and areas with
shallow water tables (Sajjad, 2014; Su et al.,et al. 2020). It is crucial to study the hydro-
geochemical characteristics of the aquifer system in different seasons to explain the process
of groundwater growth in any aquifer system and to explain how groundwater quality var-
ies with time (Kadam et al.,et al. 2021; Saba & Umar, 2021; Uddin et al.,et al. 2011; Umar
& Alam, 2012; Umar et al.,et al. 2001, 2009).
Water quality degradation in the Central Ganga Plain (CGP) as a result of agricultural
practices, unplanned urbanization, rapid industrial and unscientific human activities has
resulted in a variety of geo-environmental risks (Ahmad et al. 2019; Ahmed et al. 2014;
Raju et al. 2011; Saba et al. 2018; Umar, 2006). Approximately 90% and 30% of rural and
urban Indian populations remain to depend on untreated surface or groundwater supplies,
respectively (Kumar et al. 2005). Increased contamination of surface water bodies has
put tremendous pressure on groundwater supplies (Singh et al. 2005). The lack of potable
and healthy drinking water was one of the most critical challenges that have been encoun-
tered in several states of India including West Bengal, Jharkhand, Andhra Pradesh, Orissa,
Rajasthan, Punjab and Western Uttar Pradesh. High concentrations of SO4, NO3 and K may
be attributable to anthropogenic impacts rather than natural mechanisms. Sewage pollution
and leachate percolation can both add sodium and chloride to the system (Umar & Alam,
2012; Umar et al. 2009). High groundwater salinity in parts of Mathura district is attributed
to the high concentrations of Na, Ca, H CO3 and Cl (Krishan et al. 2016; Misra & Mishra,
2006).
A groundwater quality variation is often presented with different statistical techniques.
Several researchers used various statistical approaches including correlation coefficient,
PCA, HCA, and factor analysis (FA) to analyze the quality of groundwater and surface
water (Kazi et al. 2009; Zhao et al. 2011; Ravikumar & Somashekar, 2017; Pande et al.
2020; Demir and Akyuz, 2021; Shukla et al. 2021). A different multivariate statistical tech-
nique includes CA and PCA/FA that aid in understanding complex data matrices and a
comprehensive understanding of the temporal and geographical variability of water quality
(Zhang et al. 2011). These technologies make it possible to determine the various influ-
ences on water aquifer systems.
In an earlier study, conventional Water Quality Index (WQI) was utilized to estimate
the groundwater quality (Ahmad et al. 2019; Gnanachandrasamy et al. 2020; Kumar et al.
2014; Vaiphei et al. 2020). This WQI technique is ineffective in revealing groundwater
quality because of the different hydrochemical factors (Zhang et al. 2021). The method-
ology for evaluating groundwater quality has gone through various stages from the con-
ventional WQI to EWQI. The EWQI using entropy values comprising numerous hydro-
chemical variables has been thought to be a more feasible method due to its more extensive
computation (Adimalla, 2021; Li et al. 2019; Wu et al. 2018). The Entropy-based WQI is a
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Assessment of groundwater quality using Entropy‑Weighted… 1617
comprehensive technique that is frequently used to quantify water quality for drinking uses
all over the world (Adimalla, 2021; Rao et al. 2020; Su et al. 2018; Wu et al. 2017; Zhang
et al. 2021; Zhou et al. 2016). The concentration of N CO3− is reportedly
a+, K+, Cl−, and H
higher in shallow aquifers in comparison with the deep aquifers in Mathura region which
is likely due to poor hydraulic conductivity between the shallow and deep zones. The study
also suggested that groundwater quality varies with depth and time in shallow and deep
aquifers (Misra & Mishra, 2006). The high deviation in groundwater salinity of Mathura
region is represented by TDS range 570 to 6692 mg/l (Rawat et al. 2012). High Salinity
along Yamuna river of Mathura district was also reported by Krishan et al. (2016), with
high salinity in terms of electrical conductivity of groundwater is 2000 to 3400 µS/cm. The
study demonstrated that the dominant ions are H CO3 and Cl among anions and Na among
cations. In an isotopic study, the impact of Yamuna river on groundwater was assessed.
The values of EC increase as the distance of groundwater increases from the river thereby,
indicating less influence of river water on groundwater with increasing distance (Krishan
et al. 2017). The groundwater salinity of the regions has been studied in relation to land-
use and hydrogeological constrains (Ahmad et al. 2019) and health-based index (Ahmad
et al. 2022).
The present study has been carried out to assess the quality of groundwater by employ-
ing integrated EWQI and multivariate statistical approaches. EWQI is the first time
attempted in the area to assess the quality of groundwater. The use of EWQI has been
demonstrated in presenting variations in groundwater index that arises due to a number of
variables. The outcomes of the study highlight the evolution of groundwater through spa-
tial and temporal domain, manmade and natural influences.
1.1 Location and climate
The study area, Mathura City, is situated between latitude 27°22′30″ to 27°32′30″N and
longitude77º37′30″ to 77º43′10″ E in state of Uttar Pradesh (Fig. 1). The study covered
a total area of approximately 229 k m2 which included Mathura city and its surround-
ing areas. It has arid to semiarid climatic conditions with cold winters dry summers and
monsoon season. The Yamuna River forms the principal drainage of the city. As per IMD
(2020), the area has received an average annual rainfall of 485 mm in the last 7 years.
1.2 Geology and hydrogeological framework
Major portion of the Mathura district is situated in a marginal alluvial plain, with some
parts lying in central alluvial plain of the Ganga basin, and is underlain by Quaternary allu-
vial deposits made up of older and younger alluviums (Ahmad et al.,et al. 2022; Misra &
Mishra, 2006). The quaternary alluvium comprises various grades of sand and clay associ-
ated with occasional inter-beds of calc. concretion. It is primarily made up of clayey sand,
clay with sand, and sandy clay (Fig. 1). There are essentially three types of soils viz. silty,
sandy and loamy soils, and clay with calc. concretion and Reh (saline efflorescence) in
the blocks of Chhataand Mathura. The depth of the shallow aquifer is 50 m bgl, whereas
deep aquifer lies between a depth of 135 and 185 m bgl. In the shallow aquifer group,
groundwater is found in unconfined to semi-confined, while in the deep aquifer, it is found
in semi-confined to confined conditions (Lal, 2013). Based on drilling data, it is inferred
groundwater below the depth of 40 m is saline. To ascertain the subsurface configuration
of the aquifer system, lithological logs of various boreholes were utilized to construct the
13
Fig. 1 Map showing location of sampling, borehole logs and fence diagram of the area
fence diagram. The fence diagram provides subsurface geology and geometry of aquifers.
The aquifer geometry is primarily controlled by depositional environment including the
changes that a river system develops during its formation and the deposition history of the
alluvial plain, and the configuration of the bedrock (Khanna, 1992).
The fence diagram (Fig. 1) demonstrates that the top clay with thickness range from 6 to
42 m is appearing across the whole area with inter-bedded calc. concretion. The thickness
of this layer is more in northwestern and central parts as compared to southern and eastern
parts of the area. In northern and eastern parts, the clay is dominant with the lenses of thin
sandy horizons. In the northern, central and southern parts of the area, thickness of clay
with calc. concretion is more as compared to the western and eastern parts of the area. An
alternate disposition of clay and thin sand layers occurs in the central part. The clay layer
is underlain by 21 m thick granular zone in the central part and comparatively thick in the
southern part with a thickness of 25 m. Aquifer material is constituted of fine to medium
grain sand. Due to preponderance of clay material, the transmissivity is relatively low in
study area as compared to other parts of Central Ganga Plain. Rao et al. (2000) carried
out a pumping test around Mathura oil refinery which is a part of the study area. The aver-
aged values of transmissivity and hydraulic conductivity are 8.84 m 2/day and 2.0 m/day,
respectively.
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2 Materials and detailed methodology
2.1 Sampling procedures and analytical techniques
A total of 96 groundwater samples were taken in June (Pre-monsoon) and November (Post-
monsoon) seasons of year 2018. All samples were collected in pre-cleaned polyethylene
bottles of 1 L volume after 10 min of purging. Samples were filtered by filter paper of
0.45 µm polycarbonate membrane. The electronic OTT dip meter was used to measure the
water level. The depth of sampling wells ranges from 7.2 to > 30 mbgl. The collected water
samples were tested for physico-chemical parameters using standard methods of APHA
(1992). The pH was determined by pH meter. A pre-calibrated portable conductivity meter
(Hachsens ION) has been used to determine electrical conductivity (EC) and total dis-
solved solids (TDS). The instrument was calibrated using buffer solutions with pH values
of 4, 7, and 10, as well as EC values of 147, 1413, and 12.88 mS/cm, respectively.
The concentration of calcium (Ca), magnesium (Mg), hardness, chloride (Cl) and bicar-
bonate (HCO3) was determined by the volumetric method. The EDTA titration analysis
was used to examine hardness and calcium using Eriochrome Black T and Murexide indi-
cators, respectively. The sodium and potassium concentrations were determined using
flame photometry. For bicarbonate (HCO3), methyl orange was used with 0.1 N HCl titra-
tion. Chloride (Cl) was determined by titrating with silver nitrate (AgNO3) solution using
potassium chromate ( K2CrO4). A spectrophotometer was used to determine the concentra-
tions of sulfate and fluoride. The colorimetric method was employed to quantify the con-
centration of nitrate using phenol disulfonic acid by spectrophotometer. Fluoride concen-
tration was determined by the spectrophotometer using SPADNS.
The ionic balance error was determined to confirm the analytical precision for accurate
ion measurement which is acceptable at ± 5% (Hounslow, 1995).
∑ ∑
( Cation − Anions)
Error of ion balance = ∑ ∑ ∗ 100 (1)
( Cation + Anions)
Except for a few samples in each season, the ionic balance error was within ± 5 in both
seasons.
2.2 Multivariate statistical analysis
The multivariate statistical analysis is widely used in the investigations of groundwater qual-
ity and identifies the factors which minimize the contamination (Nazzal et al.,et al. 2015; Rao
et al.,et al. 2020; Wu et al.,et al. 2014, 2020; Zhang et al.,et al. 2011). Kaiser–Meyer–Olkin
(KMO) and Bartlett’s sphericity test were used to check the data fitness for PCA. Various sta-
tistical techniques including box-whisker plot, correlation coefficient, PCA and HCA are used
to present our data in the most expressive way using SPSS 20 software. Correlation coefficient
is a very useful tool to measure the degree of dependencies between variables. Correlations
between water quality variables can identify many significant hydrochemical relationships
(Wu et al.,et al. 2014). If the correlation coefficient (r) is ± 1, it indicates a strongly positive
relationship between two variables, no relationship exists if the r value is around zero, and if
r > 0.75 and 0.5 < r < 0.75, it reflects a strong and moderate correlation, respectively (Helena
et al.,et al. 2000; Unmesh et al.,et al. 2006). The fundamental goal of PCA is to examine the
13
variance of large data set of inter-correlated variables with smaller number of independent
variables (Rao et al.,et al. 2020). This technique contains many functions like matrices of vari-
ance–covariance and correlation. PCs also give detailed information on the most important
aspects that explain the data set, thereby, reducing the data set with minimum loss of original
data (Helena et al.,et al. 2000; Wunderlin et al.,et al. 2001). HCA technique reduces the data
into a single cluster that contains all the individuals. HCA is the most frequent strategy that
begins with every instance in its cluster and gradually links the clusters together until only one
cluster remains, as shown by a dendrogram.
2.3 Entropy water quality index (EWQI)
EWQI results were calculated in five steps, as follows:

In step 1, the eigen value matrix X is created using groundwater quality data for “m” sam-
ples and the “n” parameter as Eq. 2.
⎡ x11 x12 ⋯ x1n ⎤

⎢x x ⋯ x ⎥
21 22 2n ⎥
X=⎢ (2)
⎢⋮ ⋮ ⋮ ⎥
⎢ ⎥
⎣ xm1 xm2 ⋯ xmn ⎦
In step 2, eigen value matrix X is converted into a standard-grade matrix Y by using Eq. 3.
Construction function of normalization is
Xij−
(Xij )max ⎫
Yij = Benefit type ⎪
(Xij )max −(Xij )min
(X ) −Xij ⎬ (3)
Yij = X ij max Cast type
( ij )max −(Xij )min
⎪
⎭
where (xij)min and (xij)max are minimum and maximum values of chemical parameters,
respectively, and “Yij” is the standardization process.
After transform, the standard-grade matrix Y can be expressed by using Eq. 4
⎡ y11 y12 ⋯ y1n ⎤

⎢y y ⋯ y ⎥
21 22 2n ⎥
Y=⎢ (4)
⎢⋮ ⋮ ⋮ ⎥
⎢ ⎥
⎣ ym1 ym2 ⋯ ymn ⎦
The probability of arising of the normalized value of the parameter j for sample i stated as
follows:
Yij
Pij = ∑m (5)
i=1
Yij
In step 3, the information entropy “ej” is computed by using Eq. 6.

m
1 ∑(
(6)
)
ej = − P × In Pij
In m i=1 ij
Afterward, the entropy weight “Wj” can be obtained as follows:
13
1 − ej
Wj = n
∑� � (7)
1 − ej
i=1
In step 4, the quality rating scale “qj” for every parameter is determined by Eq. 8
Ci
qj = (8)
Si
where Ci is the concentration in mg/l and Si permissible limit of BIS (2012) standard for
each chemical parameter.
In step 5, the EWQI is computed using Eq. 9
m
∑
EWQI = Wj × qj (9)
i=1
3 Results and discussion
3.1 General chemical characteristics
The results of chemical analysis data such as ranges, average and standard deviation val-
ues are compared with drinking water standards prescribed by BIS (2012) for June and
November 2018 seasons that are compiled in Table 1. The statistical variation in chemi-
cal data for 48 samples has been plotted using box–whisker plots to represent a temporal
variation in the major ion concentration such as Cl, HCO3, SO4, NO3, Ca, Mg, Na, K,
and F for both the seasons. Figure 2a and b provides a convenient way of viewing the
minimum, 25 percentile, median, 75 percentile and maximum values for a large group
of samples. The average concentration of Na, Mg, Ca, K is 491, 77, 57 and 21 mg/l
in June and 66, 140, 434 and 28 mg/l in November, respectively, whereas the average
values of Cl, H CO3, SO4, NO3 and F are 788, 424, 183, 15.4 and 0.68 mg/l and 816,
587, 202, 21.5 and 0.8 mg/l in November season, respectively. The order of relative
abundance of major ions is Cl > Na > HCO3 > SO4 > Mg > Ca > NO3 in June and Cl > H
CO3 > Na > SO4 > Mg > Ca > NO3 in November. In November, significant change in the
order of Na position was replaced by HCO3 which is possibly due to carbonate minerals
dissolution. It is also supported by fence diagram that showed calc. concretions locally
known as kankar (CaCO3) that are frequently associated with clay throughout the area.
The concentration of Na and SO4 showed the highest median and high scattered distri-
bution values in June and Ca, Na and S O4 in November seasons, whereas lowest median
and least scattered distribution were observed in Ca, Mg, NO3 and F in June and Mg, K,
NO3 and F in November 2018. The concentration of Cl showed the least median value
and highest scattered distribution. The major ion chemistry agrees of previous studies
carried out by Krishan et al. (2016), Misra and Mishra (2006) and Rawat et al. (2012).
A comparison of previous studies on groundwater quality of the area was done to see
the groundwater salinity trends including spatial and temporal variation (Table 2). The
present study results are close to the results given by Rawat et al. (2012) which is due to
similar geographical extents of the study and almost identical sampling site. Similarity
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Table 1 Statistical analysis of major ions for groundwater samples of the area
Water Maximum desir- Maximum Minimum Maximum Average Standard deviation
quality able limit (BIS, permissible limit
parameters 2012) (BIS, 2012)
June 2018
pH 6.5–8.5 7.21 8.17 7.58 0.20
EC 1180 12,090 3562 2347.4
TDS 500 2000 720 7370 2181 1481.4
Hardness 300 600 112 1296 459 240.3
Ca 75 200 8 417 57 67.23
Mg 30 100 17 214 77 38.6
Na – 200 192 2232 491 366.6
K – – 10 84 21 11.9
Cl 250 1000 241 3346 788 568.9
HCO3 200 600 182 793 424 146.1
SO4 200 400 39 615 183 126.2
NO3 45 No relaxation 0 85 15.4 18.0
F 1.0 1.5 0.17 1.66 0.68 0.4
November 2018
pH – – 7 8.7 7.5 0.27
EC – – 1017 13,020 3656 2392.4
TDS – – 621 7940 2223 1477.4
Hardness – – 144 2360 717 398.4
Ca – – 8 596 66 94.8
Mg – – 28 419 140 83.3
Na – – 108 1608 434 266.5
K – – 8 95 28 15.8
Cl – – 259 3195 816 546.7
HCO3 – – 247 923 587 168.2
SO4 – – 27 772 202 163.3
NO3 – – 0 68.1 21.5 21.9
F – – 0 2.0 0.8 0.46
is also applicable to large deviation in groundwater salinity. Although, the average TDS
value is seen in salinity decreased over a time from 2012 to 2018. Despite, the high TDS
levels were recorded in 2018 at specific locations. Misra and Mishra (2006) conducted
a study in close to the vicinity of the present study, and it was also reported moderate
salinity level in groundwater less than that of the present study. The sampling locations
in Krishan et al. (2016) study were mainly along the Yamuna river. For this reason, this
study reports lowest salinity of all studies. Another study carried out by Krishan et al.
(2017) found that the values of EC increase as the distance of groundwater increases
from the Yamuna river, thereby indicating less influence of river water on groundwater
with increasing distance. Overall, the results of chemical data demonstrate that the con-
centration of TDS, Cl−, HCO3−, SO42−, NO3− and F−, Na+ Ca2+, Mg2+ and K+ is excess
in groundwater.
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Fig. 2 Box-whisker plot of major ion (a, June; b, November)
13
1624
13
Table 2 Comparison of major previous studies on groundwater quality of the area
Major ions in mg/l Previous studies Present study
Misra and Mishra (2006) Rawat et al. (2012) Krishan et al. (2016) Pre-monsoon 18 Post-monsoon 18
Range Average Range Average Range Average Range Average Range Average
TDS 1200–4450 1813 570–6692 2697 669–2023 1179.8 720–7370 2181 621–7940 2223
Cl 210–810 462 22–2071 782 186–370 237.8 241–3346 788 259–3195 816
HCO3 310–940 715 259–1403 674 204–442 320.1 182–793 424 247–923 587
SO4 –* – – – 8.9–133 74.5 39–615 183 27–772 202
NO3 – – – – 1.9–70.7 38.04 0–85 15.4 0–68 21.5
F – – – – 1.12–1.64 1.17 0.17–1.66 0.68 0–2.0 0.8
Ca – – 24–268 141 37.3–118 84.4 8–417 57 8–596 66
Mg – – 16–570 144 16–83.7 50.8 17–214 77 28–419 140
Na 95–550 291 47–2000 592 144–274 189.6 192–2232 491 108–608 434
K 5–25 14.63 5–120 39 3.2–16.1 8.96 10.0–84 21 8.0–95 28
–*data not given

S. Ahmad et al.

3.2 Evolution of groundwater salinity
The groundwater classification has been made using EC, TDS and Hardness (Table 3).
Overall groundwater is slightly alkaline. The results of hardness revealed that the major-
ity of the samples are exceeding the desirable limit of 300 mg/l (BIS, 2012). Also, about
25% and 48% of samples of June and November seasons exceeded the permissible limit of
600 mg/l (BIS, 2012), respectively. Overall, the groundwater is hard to very hard type.
Electrical conductivity (EC) is one of the significant pollutants produced by irrigation in
arid and semi-arid regions (Barros et al. 2012) and increases salt concentration and loads
in groundwater due to the mineral weathering (Tanji & Aragues, 2007). From Table 3, it
is seen that about 52% and 48% of samples in June 2018 and 54% and 46% of samples
in November fall under medium conductivity (Class II) to high conductivity (Class III),
respectively. Overall the groundwater was found brackish to slightly saline type except five
samples of each season which show very high EC values greater than 6000 µS/cm. The
presence of significant values of Na, K, and Cl in groundwater is indicated by high EC
values.
The results of chemical data demonstrate that the concentration of S O42−, Cl−, Na+ and
EC is excess in groundwater. As a result, it is essential to check any potential relation-
ships between their ionic ratios. The C l−/SO42−vs EC ratio can be used to determine how
evaporite dissolution, such as halite and gypsum, evolved as a function of EC (Zereg et al.
2018). The ratio Cl−/SO42− vs EC has been made to identify the dissolution of halite and
gypsum depending on EC. The ratio also depicts the presence of salinity in the form of
residual salts. The trajectory of this ratio (Fig. 3a and b) demonstrates that salts are domi-
nant in both seasons. This ratio reveals that salinity increases in the proportion of the ratio.
Overall, it appears that the dissolution of evaporites is the dominant process influencing
groundwater chemistry. This view is also supported by the outcomes of saturation indices
of evaporite minerals including halite (NaCl) and gypsum which are highly undersaturated.
Table 3 Suitability of Parameters Water class Percentage of

groundwater for drinking samples
purposes based on EC, TDS and
hardness June November
Based on EC (µS/cm) after Sarma and Swamy (1981)

< 500 Low Conductivity NIL NIL
500–1000 Medium Conductivity (Class I) NIL NIL
1000–3000 Medium Conductivity (Class II) 52 54
> 3000 High Conductivity (Class III) 48 46
Based on Hardness (mg/l) after Sawyer and McCarty (1987)
< 150 Soft Water 4 2
150–300 Moderately hard 21 2
300–450 Hard 35 15
> 450 Very hard 40 85
Based on TDS (mg/l) after Freeze and Cherry (1979)
0–1000 Freshwater 8 11
1000–10,000 Brackish water 92 89
1000–100,0000 Saline water NIL NIL
> 100,0000 Brine water NIL NIL
13
l−/SO4.2− vs EC (a, June; b, November)

Fig. 3 Ionic ratio of C
This reveals that dissolution of halite and gypsum controls the groundwater chemistry of
the area (Ahmad et al. 2019).
Total dissolved solids (TDS) comprise inorganic salts such as Cl, S O4, HCO3, NO3,
Na, Mg, Ca and K as well as a small quantity of dissolved organic materials dissolved in
groundwater. The average TDS values are 2182 mg/l and 2223 mg/l in June and November
2018, respectively. All samples exceed the desirable limit of 500 mg/l. About 35% to 45%
of samples exceed the permissible limit of 2000 mg/l in June 2018 and 42% of samples in
November 2018 (BIS, 2012). Groundwater quality classification based on TDS is listed in
Table 3 (Freeze & Cherry, 1979). About 8% and 10% of samples in June and November
2018 have TDS values of < 1000 mg/l, respectively, categorized as freshwater. Therefore,
only a few samples are suitable for drinking. It is also observed that 92% and 90% of sam-
ples in June and November 2018 samples, respectively, fall in brackish water and are not
considered suitable for drinking purposes. High TDS values in groundwater to the area
are led by both anthropogenic activities like industrial, agricultural and domestic sewage
13
and geogenic process including arid to semiarid climatic conditions and the influence of
water–rock interaction (Misra and Misra 2007; Ahmad et al. 2019). The elevated concen-
tration of EC and TDS during monsoon season is most likely because of mineral leaching.
Box-whiskers plot showed that mean trends of cations and anions are Na > Mg > Ca > K
and Cl > HCO3 > SO4 > NO3 > F, respectively, in both the seasons, implying that meteoric
signatures are completely obliterated from groundwater of the study area. Excess of SO4
and NO3 is attributed to several factors. The prime sources of NO3 in groundwater are fer-
tilizers, septic tanks, densely dominated areas and industrial and municipal discharge (Liu
et al. 2005: Vystavna et al. 2015; Wang & Li, 2022).
3.3 Chemical classification of groundwater
The Chadha diagram has been used to classify the groundwater types in terms of major
ions. It is an updated version of Piper’s trilinear diagram (Piper, 1944) and Durov diagram
(Durov, 1948). A plot (Ca + Mg)—(Na + K) versus (CO3 + HCO3)—(Na + SO4) has been
made for June and November 2018 (Fig. 4a and b), respectively.
The Chadha diagram for June and November 2018 seasons is shown in Fig. 4a and b.
Figure 4a and 4b show that 41 samples (85%) in June and 34 samples (71%) in Novem-
ber fall in sub-field of zone 7. In this zone, alkali metals (Na + K) and strong acidic ions
(Cl + SO4) exceed over alkali earth (Ca + Mg) and weak acidic ions (CO3 + HCO3) respec-
tively. It is indicate that Na-K-Cl-SO4 exceed over the Ca-Mg-HCO3 demonstrate sodium
chloride coming from the dissolution halite minerals (NaCl) into groundwater. These types
of water have serious saline issues for domestic and agricultural purposes. Furthermore,
12 samples (25%) in June and three samples (6%) in November seasons 2018 fall in the
sub-field of 6 indicating that Ca-Mg-HCO3 exceeds over Na-Cl-SO4 and demonstrates
that permanent hardness is coming from the dissolution of gypsum. Few samples also fall
in the sub-field of zone 4 indicating that strong acidic ions exceed over the weak acidic
ions in both seasons. Thus, dominant hydrochemical facies are Na-Cl-SO4 and Ca-Mg-Cl-
SO4 types in both seasons. In two successive seasons, it is observed minor variation in the
chemical characteristics of groundwater.
3.4 Multivariate statistical analysis
3.4.1 Pearson’s correlation coefficient
Correlation matrix for 13 variables is prepared for June and November seasons and given
in Tables 4 and 5, respectively. TDS has a significant strong positive correlation with all
salts including Na, Cl andSO4 and moderately positive correlated with Ca, hardness and K
in both seasons. This suggested that the salinity is much more related to component salts of
halite (NaCl), Sylvite (KCl) and Gypsum (CaSO4) mineral. This also indicates that Na, Cl,
SO4, K and Ca are major contributors of TDS to the groundwater. Besides TDS, EWQI is
also strongly correlated with TDS, Na, Cl, K and SO4 in June and TDS, Ca, Hardness, Na,
Cl, K and SO4 in November season. This may be indicating that EWQI is mainly depend-
ent on TDS, Ca, H, Na, Cl, K and S O4. Hardness is moderately positive correlated with Ca,
Mg, K and Cl in June and Ca, Mg, Na, K, Cl and SO4 in November.
Furthermore, a strong positive correlation is also observed between Na and Cl and K is
moderately strong positive correlated with Na and Cl in both the seasons thereby indicat-
ing the same origin of that ion. This may also indicate that Na, Cl and K concentrations
13
Fig. 4 Chadha Diagram (a, Pre-monsoon; b, Post-monsoon)
in groundwater are driven by other chemical processes such as the dissolution of halite
of (NaCl) and sylvite (KCl). This is also corroborated by the Saturation Indices of hal-
ite and sylvite minerals (Table 6), which are substantially under saturated, i.e., less than
zero, implying that these minerals present in an aquifer would dissolve in groundwater and
increase Na, Cl, and K concentrations (Ahmad et al. 2019).
A moderately positive correlation of S O4 with Ca, Na, K and Cl is observed in both
seasons. This indicates that the ions are also dependent on each other. However, S O4, Na,
Ca, and Cl enrichment in groundwater mostly results from the dissolution of sodium sul-
fate and gypsum minerals. Besides positive correlation, pH is negatively correlated with
all ions except for F in both seasons thereby indicating pH is not much related to the ions.
Overall, it is concluded that the interrelationship of ions with a significant positive cor-
relation indicates that the concentration of ions in groundwater is attributed to lithological
13
Table 4 Correlation coefficient of chemical analysis data with EWQI in June 2018
pH EWQI TDS H Ca Mg Na K Cl HCO3 SO4 NO 3 F
pH 1 Light Blue Color: Strongly Correlation
EWQI –0.28 1 Purple Color: Moderately Correlation
TDS –0.35 0.87 1 Light Green Color: No correlation
H –0.32 0.68 0.55 1 Yellow Color: Negative correlation
Ca –0.24 0.68 0.51 0.74 1
Mg –0.24 0.30 0.28 0.71 0.08 1
Na –0.17 0.89 0.82 0.36 0.40 0.11 1
K –0.33 0.77 0.67 0.57 0.74 0.07 0.64 1
Cl –0.25 0.94 0.79 0.59 0.55 0.32 0.94 0.68 1
HCO3 0.32 0.10 0.06 –0.31 –0.21 –0.25 0.34 0.13 0.12 1
SO4 –0.29 0.76 0.79 0.41 0.55 0.03 0.69 0.70 0.63 0.13 1
NO3 –0.04 0.32 0.08 0.21 0.08 0.24 0.12 –0.09 0.22 –0.18 –0.10 1
F 0.25 –0.02 –0.08 0.10 0.12 0.03 –0.07 –0.01 –0.05 0.13 0.01 –0.17 1
Table 5 Correlation coefficient of chemical analysis data with EWQI in November 2018
pH EWQI TDS H Ca Mg Na K Cl HCO3 SO4 NO3 F
pH 1 Light Blue Color: Strongly Correlation
EWQI –0.43 1 Purple Color: Moderately Correlation
TDS –0.38 0.92 1 Light Green Color: No correlation
H –0.43 0.76 0.67 1 Yellow Color: Negative correlation
Ca –0.20 0.77 0.63 0.68 1
Mg –0.03 –0.04 –0.14 0.58 –0.10 1
Na –0.34 0.88 0.95 0.51 0.55 –0.09 1
K –0.45 0.88 0.74 0.65 0.73 –0.10 0.73 1
Cl –0.39 0.90 0.95 0.79 0.65 –0.15 0.87 0.77 1
HCO3 –0.19 0.20 0.19 0.01 –0.08 0.15 0.31 0.13 0.02 1
SO4 –0.33 0.81 0.86 0.54 0.53 –0.11 0.91 0.70 0.80 0.28 1
NO3 –0.29 0.41 0.16 0.25 0.17 –0.15 0.13 0.28 0.17 0.10 0.05 1
F 0.08 0.29 0.28 0.20 0.06 –0.15 0.34 0.19 0.29 0.29 0.31 0.09 1
Table 6 Range and average value of saturation indices of minerals

Mineral phase June 2018 November 2018
Range Average Range Average
Halite (NaCl) − 5.87 to − 3.87 − 5.19 − 5.11 to − 4.2 − 4.26

Sylvite (KCl) − 6.73 to − 4.84 − 6.09 − 5.75 to − 5.76 − 5.22
Gypsum (CaSO4.2H2O) − 3.11 to − 0.81 − 2.15 − 2.25 to − 1.15 − 1.61
Anhydrite (CaSO4) − 3.41 to − 1.11 − 2.45 − 2.25 to − 1.39 − 2.11
formations, and other land-use such as landfill leachate, waste disposal sites, industrial and
agricultural practices.
3.4.2 Principal component analysis (PCA)
PCA is performed for 13 chemical parameters viz. pH, EC, TDS, H, Ca, Mg, Na, K, Cl,
HCO3, SO4, NO3 and F to appraise the sources of contaminants for both seasons. These
parameters have obtained four major PCs depending upon the eigen value that is greater
13
than one. The total variation in the June and November seasons is 80.27 % and 79.09 %,
respectively. Rotated values of the component for June and November are given in Table 7.
In June, PC1 explained the 42.87% of total variance is exerted by strong positive load-
ing experience caused by EC, TDS, Ca, Na, K, Cl and SO4 concentrations. PCs 1 sig-
nifies the processes of rock–water interactions, ion exchange, dissolution of gypsum and
halite, irrigation return flows on groundwater system; Yidana, 2010; Selvam et al. 2016;
Bodrud-Doza et al. 2019). This view is also supported by the correlation coefficient. PCs
2 explained 14.47 % of the total variance, and in this component, positive loading is expe-
rienced due to pH and H CO3 concentrations which signifies the groundwater is alkaline in
nature and HCO3 may be attributed by carbonate weathering to groundwater (Selvam et al.
2016). PCs 3 explained 12.69% of the total variation and showed positive loading due to
Mg and N O3 concentrations which can be due to silicate weathering, NP-fertilizers and
domestic waste disposal to the groundwater system (Elango et al. 2003; Kraiem et al. 2014;
Kumar, 2014). The PCs 4 component shows 10.01 % of the total variation, and here, the
positive loading is experienced due to F.
Similarly, from Table 7, all the components can be easily explained for November sea-
sons. It is observed that about 70.26% variance is explained by first three components in
the June samples, while in November, 70.38% variance is contributed by first three com-
ponents. Figure 5a and b shows the plots of rotated loading for first three components in
June and November, respectively.A quick comparison of PCs analysis for the June and
November seasons is given in Table 8. It is revealed that PCs 1 is the same in both seasons,
while the remaining PCs are slightly different in groundwater chemistry between June and
November seasons. Mg that is loaded with PC 3 in the June samples has been shifted to
PC4 in November samples. Overall, the PCs and correlation coefficient suggest that the
Table 7 PCs of groundwater characteristics

Variables June 2018 November 2018
PC1 PC2 PC3 PC4 PC1 PC2 PC3 PC4
pH − .301 0.655 0.006 0.387 − 0.254 − 0.068 − 0.729 − 0.091

EC 0.930 − 0.084 0.153 − 0.082 0.933 0.210 0.105 − 0.067
TDS 0.915 − 0.093 0.157 − 0.074 0.948 0.195 0.114 − 0.062
H 0.522 − 0.564 0.459 0.373 0.761 − 0.148 0.257 − 0.016
Ca 0.629 − 0.482 − 0.044 0.348 0.787 − 0.298 0.013 − 0.053
Mg 0.126 − 0.345 0.741 0.198 − 0.063 0.069 − 0.138 0.892
Na 0.912 0.264 0.156 − 0.095 0.887 0.362 0.057 − 0.032
K 0.834 − 0.241 − 0.166 0.136 0.839 0.011 0.282 − 0.012
Cl 0.879 0.020 0.331 0.005 0.947 0.052 0.135 − 0.110
HCO3 0.237 0.805 − 0.208 0.071 0.043 0.832 0.178 0.252
SO4 0.857 − 0.062 − 0.204 − 0.004 0.855 0.331 0.003 − 0.031
NO3 0.006 0.026 0.768 − 0.217 0.062 0.019 0.772 − 0.219
F − 0.042 0.126 − 0.058 0.872 0.213 0.648 − 0.130 − 0.437
Eigenvalues 5.57 1.91 1.65 1.30 6.205 1.559 1.386 1.132
% of Variance 42.87 14.70 12.69 10.01 47.73 11.99 10.662 8.71
Cumulative % 42.87 57.57 70.26 80.27 47.73 59.72 70.38 79.09
Significant values is marked with bold
13
Fig. 5 Rotated loading plots of first three components (a, June; b, November)
Table 8 Comparison of PCs PCs June 2018 November 2018

during the June and November
seasons
PC1 EC, TDS, H, Ca, Na, K, Cl EC, TDS, H, Ca,
and SO4 Na, K, Cl and
SO4
PC2 pH, H and HCO3 HCO3 and F
PC3 Mg and NO3 pH and N
O3
PC4 F Mg
13
groundwater quality is mainly driven by geogenic factors, although, to a lesser extent,

human activity is also influencing the groundwater quality.
3.4.3 Hierarchical cluster analysis (HCA)
For HCA, Ward’s approach employing squared Euclidean distance is applied and gives
the most meaningful findings (Sharma et al.,et al. 2017; Vega et al.,et al. 1998). Several
researchers have also used Euclidean distance for cluster analysis (Behera & Das, 2018;
Fovell & Fovell, 1993; Magesh et al.,et al. 2017; Shrestha & Kazama, 2007). A dendro-
gram (tree-shaped structure) is used to display the results of cluster analysis. Several
common features are observed in this plot, and these are very similar to those examined
in PCA. Dendogram represents the divisions of the data at each stage for both seasons.
Figure 6a and b represents the dendogram for the June samples and November samples,
respectively. At distance 25, variables cluster is shown into two different groups in both
seasons. During June, cluster 1 is represented by hardness, pH, Ca, Mg, N O3 and K con-
centrations signifying their entry into groundwater system through processes of rock–water
interaction, NP-fertilizers and domestic waste disposal. Cluster 2 is contributed by the vari-
ables like Cl, Na, SO4 and HCO3. All these variables also exhibit higher loadings in PCs 1
indicating the same processes as explained by PCs 1 controlled the groundwater chemistry
of the area. Cluster 3 is a set of two variables that exhibit a resemblance between EC and
TDS concentrations and joins with the Group of cluster 1 and cluster to indicate that the
TDS and EC are mainly contributed by major ions, and groundwater chemistry is primar-
ily influenced by water-rock interaction (Subyani and Ahmadi 2010; Gopinath et al.,et al.
2018). Overall, it is observed that the variables of all three clusters in November are nearly
identical to those of the clusters present in the June season, implying that groundwater
hydrogeochemistry is impacted by similar variables.
3.5 Entropy water quality index (EWQI)
To assess the comprehensive effects of chemical parameters on the quality of water, EWQI
approach has been used by several researchers (Adimalla, 2021; Rao et al.,et al. 2020).
In this study, the values of TDS, hardness, N a+, Mg2+, Ca2+, K+, Cl−, HCO3−, SO42−
− −
NO3 and F have been taken in the estimation of the EWQI. The EWQI was obtained
according to information entropy (ej) and entropy weight (wi) of each parameter of both the
seasons given in Table 9. The EWQI > 100 indicates that the water is unsuitable for human
uses (Rao et al.,et al. 2020; Wu et al.,et al. 2018). The computed EWQI value ranges from
34 to 266 (average value = 79.8) in June and in 28.7 to 301.5 (average value = 91.57) in
November. The results of EWQI, rank and groundwater quality are given in Table 10.
Groundwater quality distribution and classification for both seasons are shown in Fig. 7.
EWQI classification standards of groundwater quality and rank of both seasons are listed
in Table 11. The results of EWQI indicate that about 69% of samples in June and 67% sam-
ples in November displayed the level of rank 3, i.e., medium groundwater quality. Only
a few groundwater samples exhibit good water quality in both seasons. The results also
indicate that two samples were collected from locations Salempur and Dahalwa in June
and four samples collected from the locations Salempur, Dahalwa, Rawal and Tyyapur are
extremely poor with EWQI > 150. Certainly, groundwater at these locations is not recom-
mended for drinking purposes. Authorities must look after the issue of groundwater protec-
tion and manage alternate sources of water supply. The extremely poor groundwater quality
13
Fig. 6 Dendogram (a, June; b, November)
13
Table 9 Information entropy Parameters June 2018 November 2018

(ej) and entropy weight (Wi) of
parameters ej Wi ej Wi
EC 0.957 0.080 0.951 0.091

TDS 0.955 0.084 0.955 0.084
H 0.967 0.060 0.957 0.080
Ca 0.882 0.220 0.759 0.447
Mg 0.968 0.059 0.935 0.121
Na 0.952 0.089 1.005 -0.010
K 0.970 0.056 0.961 0.073
Cl 0.953 0.087 0.956 0.082
HCO3 0.985 0.028 1.001 -0.002
SO4 0.952 0.089 0.889 0.205
NO3 0.877 0.228 0.925 0.139
F 0.970 0.056 0.969 0.058
at these locations is correlated primarily with the presence of thick clay. In addition, the
agricultural activities mainly by irrigation return flows which contribute to higher minerali-
zation of groundwater. Furthermore, about 15% and 21% of samples in June and November
season, respectively, are lower than permissible drinking standards and it is categorized as
poor water quality and not suitable for drinking purposes. Overall, it is observed that aver-
age EWQI value is high in November as compared to June. This may be due to the less
dilution effect because the thick top clay layer is persistent throughout the area. Further-
more, EWQI and concentration of TDS were correlated to find the possible relationship.
Figure 8 reveals a strong positive correlation between EWQI and TDS indicating that the
TDS is a major contributor to EWQI.
The EWQI was plotted to understand spatial distribution and possible relationship with
prevailing land-use patterns. Spatial distribution of EWQI for November (Fig. 9a) shows
that the high EWQI regions are present in extreme northern, western and eastern direc-
tion. The northern and eastern zones are located on the bank of Yamuna river, and these
zones are also covered with extensive agricultural and landfill sites. The western zones are
marked by a mixture of various industries such as chemical and metal industries, paint and
cloth factories, agricultural environments and landfill site. During November, almost iden-
tical pattern has been observed in November (Fig. 9b). Therefore, industrial, agricultural
sources and leaching of ions from landfill and industrial sites are responsible for contribut-
ing major ions corresponding to increases in the concentration of EWQI value to the area.
The spatial correlation of EWQI with the land-use pattern is more representative of the
impacts and solute acquisitions from land-use categories in comparison with the spatial
correlation of WQI with land-use pattern (Ahmad et al. 2019). This is all likely due to
more statistical computation within EWQI accounts with even minor variation in quality
parameters.
3.6 Factors influencing groundwater quality
Overall, it is observed that the concentration of Na, K, Ca, Mg, Cl, H

CO3, SO4 is high
in aquifer system of the area. This is borne out of the unique hydrogeological and
13
Table 10 Rank and quality of individual groundwater samples based on EWQI

Sample ID Sampling locations June 2018 November 2018
EWQI Rank Water Quality EWQI Rank Water Quality
1 Lakshmi Nagar 72.2 3 Medium 93.7 3 Medium

2 Sadar Bazar 55.9 3 Medium 64.5 3 Medium
3 Gopalpur 101.5 4 Poor 82.3 3 Medium
4 Ishapur 76.6 3 Medium 66.0 3 Medium
5 Jaisingpura 65.2 3 Medium 50.1 3 Medium
6 Krishna Janam Bhumi 67.2 3 Medium 56.7 3 Medium
7 Tayabpur 133.2 4 Poor 160.7 5 Extremely poor
8 Govindpur 62.3 3 Medium 95.6 3 Medium
9 Chandan Nagar 41.7 2 Good 64.9 3 Medium
10 Ahilyaganj 114.1 4 Poor 87.5 3 Medium
11 Ganeshra 103.7 4 Poor 112.8 4 Poor
12 Krishna Nagar 76.5 3 Medium 107.4 4 Poor
13 Gridharpur 54.2 3 Medium 71.1 3 Medium
14 Handpum Gate 60.2 3 Medium 60.8 3 Medium
15 Industrial Area 1 60.0 3 Medium 62.3 3 Medium
16 Industrial Area 2 56.8 3 Medium 84.5 3 Medium
17 BSE Collage 90.1 3 Medium 116.1 4 Poor
18 Moti Kunj 43.1 2 Good 58.8 3 Medium
19 Grudwara 35.9 2 Good 106.3 4 Poor
20 Madhapur 55.7 3 Medium 62.8 3 Medium
21 Rawal 119.5 4 Poor 205.5 5 Extremely poor
22 Gokul Brach 34.0 2 Good 60.1 3 Medium
23 Ajai Nagar 68.3 3 Medium 91.3 3 Medium
24 Nagla Shivji 50.0 2 Good 74.2 3 Medium
25 Satoya 77.9 3 Medium 75.2 3 Medium
26 Tanseb 92.8 3 Medium 102.8 4 Poor
27 Bajne 59.2 3 Medium 72.5 3 Medium
28 Salempur 266.5 5 Extremely poor 301.6 5 Extremely poor
29 Narholi 50.8 3 Medium 86.0 3 Medium
30 Virjapur 80.3 3 Medium 86.0 3 Medium
31 Damudarpura 85.0 3 Medium 101.9 4 Poor
32 Refinery 1 53.7 3 Medium 50.0 2 Good
33 Nawada 34.7 2 Good 28.7 2 Good
34 Aurangabad 104.8 4 Poor 110.3 4 Poor
35 Mubarakpur Banger 127.9 4 Poor 124.4 4 Poor
36 Dhannapur 69.9 3 Medium 120.5 4 Poor
37 Mokandpur 69.0 3 Medium 76.0 3 Medium
38 Lakshmi Nagar 70.4 3 Medium 71.5 3 Medium
39 Dahalwa 219.8 5 Extremely poor 204.8 5 Extremely poor
40 Birla Mandir 79.5 3 Medium 74.1 3 Medium
41 Court 73.7 3 Medium 69.4 3 Medium
42 Janakpuri 81.0 3 Medium 115.1 4 Poor
43 Gokul 82.5 3 Medium 55.1 3 Medium
13
Table 10 (continued)
Sample ID Sampling locations June 2018 November 2018
EWQI Rank Water Quality EWQI Rank Water Quality
44 Nagla Jand 80.2 3 Medium 84.7 3 Medium

45 Tarsi 87.3 3 Medium 77.5 3 Medium
46 Refinery 2 57.7 3 Medium 57.9 3 Medium
Fig. 7 Sample-wise EWQI values and its classification
Table 11 Classification standards EWQI Rank Water quality % of Samples

of groundwater quality and rank
based on EWQI June 2018 November 2018
< 25 1 Excellent – –
25–50 2 Good 6 (12%) 2 (4%)
50–100 3 Medium 33 (69%) 32 (67%)
100–150 4 Poor 7 (15%) 10 (21%)
> 150 5 Extremely poor 2 (4%) 4 (8%)
climatological conditions of the area. The unique hydrogeological setup is in the form of
thick clay layers with calc-concretion indicating a paleo-climate favoring deposition of clay
for a longer span of time. As discussed in Sect. 1.2, from fence diagram, it is observed that
the thick top clay layer is persistent throughout the area. At places, it also contains calc.
13
Fig. 8 Relationship between the index of EWQI and TDS
concretions. The presence of a thick clay layer in the subsurface geology enables the waters
to have a relatively longer residence and sluggish percolation time in the zone of aeration
which increases the concentration of Na, K, Cl, and H CO3 in the aquifer system. A similar
observation was made by Misra and Mishra (2006) in Saidabad sub-division of Mathura
district. The clay layer acts as a barrier to enable to recharge of the aquifer. Na, K, Ca, Cl,
HCO3, SO4 and NO3 are also added to the soil from several geogenic sources. Several geo-
genic processes including water–rock interaction, mixing of surface water to groundwater,
arid climatic conditions, low precipitation and high evaporation, dissolution of saline soil
patches and dissolution of carbonate minerals influence the quality of groundwater (Ahmad
et al.,et al. 2019).
Besides geogenic factors, various anthropogenic pollutants that contribute to ground-
water pollution are the toxic effluents that may be released from various industries, sew-
age discharge, septic tank leakages and landfill leachates. Groundwater pollution is also
caused due to agricultural activities in the peripheral region mainly by irrigation return
flows which contribute higher mineralization to groundwater.
4 Conclusion
The groundwater quality and geochemical behavior of the aquifer in Mathura city, West-
ern Uttar Pradesh, India, were assessed. Overall groundwater is alkaline brackish and
hard to very hard type. The relationship between electrical conductivity (EC) and C l −/
SO42− demonstrates an increase in salinity proportional to the ratio confirming evapo-
ritic dissolution as the dominant process to control the groundwater chemistry. Box-
whiskers plot showed that mean trends of cations and anions are Na > Mg > Ca > K and
Cl > HCO3 > SO4 > NO3 > F, respectively, in both the seasons. In all ions, majority of
samples exceed the desirable limit and a considerable number of samples also exceed the
maximum permissible limit. The Chadha diagram revealed that alkali metals (Na + K)
and strong acidic ions (Cl + SO4) exceed over alkali earth (Ca + Mg) and weak acidic ions
(CO3 + HCO3), respectively, depicting that Na-K-Cl-SO4 is a dominant hydrochemical
13
Fig. 9 Spatial distribution of

EWQI (a, June 2018; b, Novem-
ber 2018)
13
facies of groundwater. The results of EWQI indicate that majority of groundwater samples
displayed a level of rank 3, i.e., medium groundwater quality in both seasons. The extreme
northern, western and eastern parts of regions have higher EWQI values. Therefore, these
regions should be paid more attention for groundwater protection in future. Overall, it is
observed that the concentrations of EWQI are high in post-monsoon over pre-monsoon
season. This is rather a conspicuous trend which is likely due to the less dilution effect
because the thick top clay layer is persistent throughout the area and that excessive clay
layer restricted groundwater circulation. The EWQI application brings more clarity in pre-
senting water quality variation with reduced subjectivity in assigning weights and ratings
through multiple statistical operations. Interrelationship of ions with significant positive
correlation indicates that the concentration of ions in groundwater is attributed to lithologi-
cal formations and other land-use such as landfill leachate, waste disposal sites, effluents
released from industries and agricultural activities in the area. A total of four significant
principal components (PCs) were retrieved by principal component analysis, correspond-
ing to 80.27 and 79.09% of the total variation during two consecutive seasons. The results
of various multivariate statistical techniques such as PCs, HCA and correlation coefficient
are identified which reveals that geogenic and anthropogenic factors control the ground-
water quality. Overall, the quality of groundwater is poor, and it is crucial to find alternate
drinking water sources or treat the groundwater before consumption.
Acknowledgements The first author highly acknowledged the financial assistance received in the form
of Research fellowship (Non-NET) from UGC, New Delhi. The author is also obliged to Chairperson of
Department of Geology AMU, Aligarh for providing laboratory facilities in geochemical laboratory. The
authors gratefully acknowledge the Prof. Peiyue Li School of Water and Environment, Chang’an University
for his valuable suggestions. Valuable suggestions from anonymous reviewers are thankfully acknowledged.
Declarations
Conflict of interest We declare that there is no conflict of interest.
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Environment, Development and Sustainability (2024) 26:1615–1643

Assessment of groundwater quality using Entropy‑Weighted

Shamshaad Ahmad1 · Rashid Umar1 · Izrar Ahmad1

1.1 Location and climate

1.2 Geology and hydrogeological framework

2 Materials and detailed methodology

2.1 Sampling procedures and analytical techniques

2.2 Multivariate statistical analysis

2.3 Entropy water quality index (EWQI)

EWQI results were calculated in five steps, as follows:

⎡ x11 x12 ⋯ x1n ⎤

⎡ y11 y12 ⋯ y1n ⎤

In step 3, the information entropy “ej” is computed by using Eq. 6.

Afterward, the entropy weight “Wj” can be obtained as follows:

3 Results and discussion

3.1 General chemical characteristics

Fig. 2 Box-whisker plot of major ion (a, June; b, November)

–*data not given

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

3.2 Evolution of groundwater salinity

Table 3 Suitability of Parameters Water class Percentage of

Based on EC (µS/cm) after Sarma and Swamy (1981)

­ l−/SO4.2− vs EC (a, June; b, November)

3.3 Chemical classification of groundwater

3.4 Multivariate statistical analysis

3.4.1 Pearson’s correlation coefficient

Fig. 4 Chadha Diagram (a, Pre-monsoon; b, Post-monsoon)

Table 6 Range and average value of saturation indices of minerals

Halite (NaCl) − 5.87 to − 3.87 − 5.19 − 5.11 to − 4.2 − 4.26

3.4.2 Principal component analysis (PCA)

Table 7 PCs of groundwater characteristics

pH − .301 0.655 0.006 0.387 − 0.254 − 0.068 − 0.729 − 0.091

Significant values is marked with bold

Table 8 Comparison of PCs PCs June 2018 November 2018

groundwater quality is mainly driven by geogenic factors, although, to a lesser extent,

3.4.3 Hierarchical cluster analysis (HCA)

3.5 Entropy water quality index (EWQI)

Fig. 6 Dendogram (a, June; b, November)

Table 9 Information entropy Parameters June 2018 November 2018

EC 0.957 0.080 0.951 0.091

3.6 Factors influencing groundwater quality

Overall, it is observed that the concentration of Na, K, Ca, Mg, Cl, H

Table 10 Rank and quality of individual groundwater samples based on EWQI

1 Lakshmi Nagar 72.2 3 Medium 93.7 3 Medium

44 Nagla Jand 80.2 3 Medium 84.7 3 Medium

Fig. 7 Sample-wise EWQI values and its classification

Table 11 Classification standards EWQI Rank Water quality % of Samples

Fig. 8 Relationship between the index of EWQI and TDS

Fig. 9 Spatial distribution of

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1.1 Location and climate

1.2 Geology and hydrogeological framework

2 Materials and detailed methodology

2.1 Sampling procedures and analytical techniques

2.2 Multivariate statistical analysis

2.3 Entropy water quality index (EWQI)

3 Results and discussion

3.1 General chemical characteristics

3.2 Evolution of groundwater salinity

l−/SO4.2− vs EC (a, June; b, November)

3.3 Chemical classification of groundwater

3.4 Multivariate statistical analysis

3.4.1 Pearson’s correlation coefficient

3.4.2 Principal component analysis (PCA)

3.4.3 Hierarchical cluster analysis (HCA)

3.5 Entropy water quality index (EWQI)

3.6 Factors influencing groundwater quality