Environment, Development and Sustainability (2020) 22:2591–2624

https://doi.org/10.1007/s10668-019-00312-9

Geochemical mobility of ions in groundwater

from the tropical western coast of Maharashtra, India:
implication to groundwater quality

Satyajit Gaikwad1 · Suryakant Gaikwad1 · Dhananjay Meshram1 · Vasant Wagh2 ·

Avinash Kandekar3 · Ajaykumar Kadam4

Received: 2 August 2018 / Accepted: 8 January 2019 / Published online: 16 January 2019
© Springer Nature B.V. 2019

Abstract
Groundwater quantity and quality are equally important for the sustainable management
of water resources in coastal parts of the world. Therefore, it is essential to study the geo-
chemical mobility of ions in groundwater and their spatial variation in western coastal part
of Maharashtra, India. A total of sixty-five (65) groundwater samples were collected from
different dug and bore wells and spring samples and subjected to physicochemical analy-
sis using standard methods of APHA. The analytical results inferred that groundwater is
acidic to alkaline in nature. The order of abundance of ions in the groundwater samples
is ­Ca2+ > Na+ > Mg2+ > K+ and ­HCO3− > Cl− > SO−2 − −
4 >NO3 > F . The piper trilinear dia-
gram reveals that the ground water is of Ca-HCO3 and mixed Ca–Cl-HCO3 types. Gibbs
diagrams indicate rock and precipitation dominance which is controlling the groundwater
chemistry. As compared with World Health Organization drinking standards, groundwater
is good for drinking; however, a few samples surpass the desirable limit of pH, ­HCO3 and
F. Similarly, suitability of groundwater for irrigation purpose is also studied using USSL
diagram, SAR and %Na and it was found that all groundwater samples are suitable for irri-
gation purpose, showing good to excellent quality. Conversely, Kelley’s ratio suggests that
78.47% of water samples are unsuitable for irrigation. Multiple linear regressions model
is used for predicting the fluoride content and confirming the efficiency of the proposed
model based on R (0.72) and RMSE (0.035) values. Furthermore, correlation analysis,
cluster and principal component analysis were performed to find the significant parameters
that influence groundwater chemistry. The cluster analysis explored that all the parameters
are associated with EC and PCA which shows four factors are found to be significant which
influenced groundwater chemistry.

Keywords Spatial variation · Geochemical mobility · Groundwater · Drinking · Irrigation ·

Terekhol River basin

* Satyajit Gaikwad
satyajit.gaikwad@gmail.com
* Ajaykumar Kadam
kadamajaykumar1@gmail.com
Extended author information available on the last page of the article

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2592 S. Gaikwad et al.

1 Introduction

The groundwater quality is crucial to human health due to declining freshwater resources
due to population pressure, industrial growth and intense agriculture. Persistently, ground-
water quality is not given as important as quantity, especially in developing and underde-
veloped countries due to scientific inadequacy (Kammoun et al. 2018). The groundwater
quality is affected by many sources of pollutions including natural and anthropogenic (Sin-
garaja et al. 2016; Wagh et al. 2016a, b). Generally, in the coastal area, groundwater is
polluted due to intrusion of seawater as well as overexploitation of groundwater (Kaliraj
et al. 2015). The coastal aquifers are fragile in nature, and due to overexploitation, depleted
easily (Chidambaram et al. 2008). In coastal regions of India, groundwater is one of the
important and reliable sources for drinking and irrigation; therefore, its qualitative assess-
ment becomes crucial as concerned with public health (Gaikwad 2012). Therefore, many
studies advocate that hydrochemical characteristics are vital to study the quality of ground-
water by measuring the concentration of different ions and their effects on human health
(Shanmugasundharam et al. 2017; Vasant et al. 2016; Wagh et al. 2017a). The chemical
composition of groundwater varies due to local lithology, velocity of groundwater flow,
residence time and rock–water interactions (Todd 1980). In addition to these factors, cli-
mate, soil characteristics and terrain topography also modify the composition of groundwa-
ter (Raghunath 1987). Anthropogenic activities may also help in modification of ground-
water chemistry and its quality (Mukate et al. 2017; Varade et al. 2018; Zhu et al. 2017).
The spatial distribution maps of the major ionic concentrations help to locate the suitable
groundwater sources for drinking as well as for irrigation purpose. Hence, study of spa-
tial variation of these major ions gives clues about the processes that control groundwater
chemistry and spatial extent of pollution and helps to understand characteristics of an aqui-
fer (Wagh et al. 2017b; Panaskar et al. 2016).
The absolute consideration of groundwater suitability for irrigation is mainly based
on electrical conductivity (EC), sodium adsorption ratio (SAR), percent sodium (%Na)
and Kelley’s ratio (Kelley 1951; Richards 1954; Wagh et al. 2018a; Ghalib 2017). Also,
it depends on total salt contents, sodium content, availability of nutrients alkalinity, acid-
ity and hardness of irrigated water leading to loss in soil fertility and crop yield (Kirda
1997). The poor water quality may influence the crop productivity, physical state of soil
and amount of dissolved ions in irrigation water which will cause stunted plant growth
and crop productivity (Ayers and Westcot 1994). Thus, addressing the irrigational water
quality with its suitability-related problems is vital to explore at confined to large scale.
The increased concentration of fluoride in groundwater is reported from coastal parts of
the India which may lead to health implications like fluorosis and associated health risk
(Selvam 2015; Adimalla and Li 2018; Brindha and Elango 2013). Rao (2006) has studied
potability of water and nitrate contamination of shallow aquifers along the coastal region
of Andhra Pradesh. Hydrogeochemical study of coastal lowlands of Kerala suggests the
unsafe characteristics of groundwater for drinking purpose (Prasanth et al. 2012). Arslan
(2017) studied the spatiotemporal variation in groundwater quality along the coastal aqui-
fer of Turkey. Many researchers reported the hydrochemical characteristics of groundwa-
ter along the coastal tracks of India (Kumar and James 2013; Gopinath et al. 2018; Gna-
nachandrasamy et al. 2018; Kanagaraj et al. 2018). In addition, multivariate statistical
techniques like correlation, multiple linear regressions, bivariate ionic plots, cluster and
principal component analysis (PCA) have been employed by many researchers to find out
the significant factors, viz. geogenic and anthropogenic inputs, affecting water chemistry.

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Geochemical mobility of ions in groundwater from the tropical… 2593

Recently, GIS-based techniques have been commonly used to characterize the spatiotem-
poral variations in ions, hydrogeology, hydrochemistry, geomorphology, rainwater harvest-
ing structure and green growth (Kadam et al. 2012; Kadam et al. 2017; Sahu et al. 2018;
Kadam et al. 2018). According to the Das and Nag (2015), multivariate statistical meth-
ods indirectly tell us in detail about the factors that control hydrogeochemical processes.
Recently, Li et al. (2013) have studied the hydrogeochemistry of shallow groundwater from
China using multivariate analysis. Multivariate statistical methods have been used by many
researchers to evaluate and interpret the surface-water and groundwater quality coupled
with hydrochemical processes (Zheng et al. 2016; Bhuiyan et al. 2016; Hassen et al. 2016;
Machiwal and Jha 2015; Singh et al. 2017).
In case of the Terekhol River basin, the hydrogeological and hydrochemical studies are
carried out by federal government agencies like Groundwater Survey and Development
Agency (GSDA 1984) and Central Ground Water Board (CGWB 1992, 2009, 2014). Also,
Gaikwad and Pawar (2012) have studied the groundwater chemistry of Terekhol River
basin on minor scale. Yet, the work related to groundwater suitability for different pur-
poses and spatial variation of ions in groundwater is found inadequate. Therefore, system-
atic studies are required for the evaluation of hydrogeochemistry, influencing factors and
quality of water for drinking and irrigation. Thus, the present study is initiated with main
objectives of (1) studying major ion chemistry and hydrochemical process controlling the
groundwater quality and its suitability for drinking and irrigation purpose, (2) using inter-
polation technique to know the spatial extent of groundwater quality in the basin and (3)
using geo-statistical techniques to recognize the significant association among water qual-
ity variables and their influence on groundwater quality. The findings of this study may be
helpful to know the quality of groundwater problems in the Terekhol River basin.

2 Study area

The Terekhol River basin is located in a southern part of Sindhudurg district of Coastal
Maharashtra, India (Fig. 1). Terekhol River originates in the Western Ghats, flows for
around 69 km and further meets the Arabian Sea near Terekhol Fort. The area is bounded
by longitudes 73°61′–74°90′E and latitudes 15°70′–16°60′N and included in the Survey
of India’s toposheets numbers 47 I/1, 47 H/16, 47 L/4, 48 E/5, 48 E/9 and 48 E/10 on
1:50,000 scale. It covers an area of about 687.5 km2 with elevation difference around
929 m, and physiographically the area comprises mountains, ridges and hills forming gen-
tly rolling topography and alluvial plains along the river courses with undulating topog-
raphy and meandering streams (CGWB 2014). The study area receives an annual average
rainfall of 3642 mm from southwest monsoon (CGWB 2009). A variety of rock types are
exposed in the Terekhol River basin from the Precambrian to Recent in age (Fig. 2). The
area under investigation is also known as Konkan, western part of Maharashtra, and has a
geological setup similar to the Western Dharwar Craton of Karnataka, India (Sarkar and
Soman 1986). According to Deshpande (1998), major stratigraphic units represented in the
area are Dharwarian meta-sediments of Archean age, Kaladgi Formation of Precambrian
age, while Deccan Trap basaltic flows are of Upper Cretaceous to Lower Eocene in age.
This basaltic flow is overlain by laterite which is of Pleistocene in age. The Recent- to sub-
Recent-deposited alluvium is seen along the lower part of the river course (CGWB 2009).
On the basis of field characteristics and petrography, within the Archean complex, three
units, namely Sargur Group, Peninsular Gneiss and Bababudan Group, are recognized

13
2594 S. Gaikwad et al.

Fig. 1  Study area map with groundwater sample locations

(Sarkar and Soman 1986). According to the Geological Survey of India, granite gneiss,
quartzite/quartz sericite schist and quartz chlorite amphibolite schist/ferruginous phyllites
which are Archean in age are reported in the basin (GSI 2006; Prasanna et al. 2011).

3 Material and methodology

The sites for sampling are selected to cover most of the area of the Terekhol River basin;
hence, representative sixty-five (65) groundwater samples including dug wells (DW), bore
wells (BW) and springs samples (SP) were collected for major ions analysis in December
2014 (i.e., post-monsoon 2014). Groundwater samples were collected in pretreated poly-
ethylene bottles (1 l) after pumping the water for 2–3 min to avoid contamination. During
field investigation, details about type of well, its location, water level were recorded prior
to collection of samples. Prior to analytical procedure, groundwater sample was filtered
through 0.45 mm Millipore filter paper on Millipore filtration unit. Out of this, 150 ml
of sample stored separately in polyethylene bottles (120 ml) was acidified with 3–4 ml
ultrapure nitric acid and stored below 4 °C in icebox for analysis of cations. The pH and
electrical conductivity (EC) were recorded in situ by using portable pH (eco Tester pH1)
and EC meter (Hanna Instruments Model number-CD-98303). Anions like ­Cl−, ­HCO3,
­F−, ­SO42−, ­NO3− were analyzed on Dionex make DX-600 HPIC (high-performance ion
chromatography) systems, while major cations like ­Na+, ­K+, ­Ca2+ and M ­ g2+ were meas-
ured on the inductively coupled plasma atomic emission spectrometer (ICP-AES-9000,

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Geochemical mobility of ions in groundwater from the tropical… 2595

Fig. 2  Geology of the study area (after GSI 2006)

Shimadzu, Japan) in the Department of Geology, Savitribai Phule Pune University, using
standard procedures given by APHA (2005). Multi-element standard solution (Merk, made
in Germany) has been used for preparations of standards for ICP-AES. The quality of the
analysis data was confirmed by standardization using blank samples, prepared standards
and running of duplicate samples. The accuracy of the chemical ion data was calculated
using DOS-based stiff software. These data showing charge balance error (CBE) between

13
2596 S. Gaikwad et al.

cation–anion is ± 05% considered (Hounslow 1995). The physicochemical data of major

elements of water samples in study area are given in Table 1. Spatial distribution maps of
pH, EC, anions and cations were plotted using Arc GIS 9.2 software. The statistical analy-
sis of the data was performed by using MS Excel and R software.

4 Result and discussion

The physicochemical data of groundwater samples are presented in Table 1. To know the
spatial extent of ions in groundwater, spatial variation maps were prepared.

4.1 Spatial variation in pH and EC

The pH values range from 5.25 to 8.23, indicating groundwater is acidic to alkaline in
nature. The high pH is recorded in the northern and central part of the basin, while low pH
is seen in the eastern as well as in southern parts (Fig. 3). Most of the groundwater samples
(58.5%) show acidic pH (pH < 7), whereas 41.5% of groundwater samples show slightly
alkaline pH (pH > 7) which is due to loss of ­CO2 as well as precipitation of mineral (Pawar
and Kale 2006). Groundwater consumption with lower pH values (especially in BW-31;
BW-43; BW-44; DW-51; DW-52; DW-53; DW-56; DW-57; and DW-58) will cause gastro-
intestinal disorder in human being so this consumption of lower pH water is harmful. Elec-
trical conductivity (EC) values range from 31 μS/cm (in BW-31) to 514 μS/cm (in BW-20).
High values are seen in the western side of the basin, while low EC values are seen in the
eastern side (Fig. 4). The average values of EC (189 μS/cm) is pinpointing to low minerali-
zation of groundwater (Pawar et al. 2008).

4.2 Spatial variation in cations

Calcium ­(Ca2+), magnesium ­(Mg2+), sodium ­(Na+) and potassium ­(K+) are the major cat-
ionic constituents in all types of water. The order of abundance of cations in the water
samples is ­Ca2+ > Na+ > Mg2+ > K+. The Na concentration ranges from 6.27 to 36.93 mg/l
(Table 1). The calcium is a dominant cation with average concentration of 21.07 mg/l in
groundwater. Elevated Ca values (Fig. 5) in the central and southwestern parts of basin
indicating feldspar, pyroxene and amphibole present in the country rocks mainly contribute
­Ca2+ to the groundwater (Hem 1991). The Na concentration increases from northeast to
southwest (Fig. 6), which may be due to the directional flow of groundwater plus residence
time (Jebastina and Arulraj 2016). The magnesium (Mg) in groundwater ranges from 0.42
to 27.60 mg/l (Fig. 7). It is a one of the major constituents of ferromagnesian minerals,
which contribute major source of Mg in groundwater (Singaraja et al. 2016). Concentration
of potassium (K) varies from 0.8 to 22 mg/l. Its less concentration is due to non-appearance
of K-bearing minerals. The highest value of K (22.7 mg/l) is reported at DW-59 (Fig. 8)
which may be due to use of potassium-rich fertilizers (Pawar et al. 2008).

4.3 Spatial variation in anions

In the study area, bicarbonate is the principal anion followed by chloride, sulfate, nitrate
and fluoride. The ­HCO3 values range from 40.0 to 190 mg/l. Higher values of ­HCO3

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 Table 1  Physicochemical data of major elements of water samples in study area (post-monsoon 2014)
Type pH EC TDS Na+ K+ Ca2+ Mg2+ Cl− HCO3− SO42− NO3− F− CBE

BW-01 8.05 292 186.88 20.8 3.29 14.9 6.21 29.68 80 11.2 5.1 1.42 − 4.6
BW-02 7.1 236 151.04 11.45 2.89 12.91 8.55 26.48 90 4.2 9.7 0.69 − 3.47
BW-03 8.23 303 193.92 7.96 1.93 9.89 27.6 20.12 150 9.5 6.2 0.16 − 2.54
BW-04 7.47 380 243.2 6.27 1.42 41.5 8.37 30.6 120 35.9 7.5 0.42 − 2.31
BW-05 7.89 375 240 10.22 2.51 36.5 9.87 24.48 130 21.23 9.1 0.41 − 3.67
BW-06 6.37 193 123.52 8.09 2.41 6.72 7.03 32.96 90 26.5 6.9 0.21 − 4.39
DW-07 6.81 100 64 7.79 2.11 10.47 6.37 21.96 50 3.5 2.5 0.18 − 3.77
BW-08 6.71 167 106.88 6.89 0.8 9.04 5.22 22.6 70 2.1 6.2 0.33 − 0.07
BW-09 7.39 236 151.04 7.27 2.69 19.82 6.93 23.16 80 20.42 6.9 0.38 − 4.64
BW-10 7.59 297 190.08 19.1 2.94 16.93 6.42 26.46 90 6.7 12.2 0.74 − 3.74
BW-11 6.8 233 149.12 8.43 3.69 15.6 5.51 24.28 80 7.9 5.2 0.31 − 3.81
BW-12 6.28 115 73.6 8.26 2.92 5.86 5.93 22.39 50 8.2 5.1 0.17 − 2.74
BW-13 6.44 164 104.96 8.53 2.17 3.89 3.52 29.73 80 22.3 4.2 0.15 − 4.26
BW-14 6.57 208 133.12 10.58 3.89 8.27 6.43 31.27 90 1.2 7.4 0.21 − 1.42
Geochemical mobility of ions in groundwater from the tropical…

BW-15 7.24 194 124.16 9.55 2.15 13.82 8.75 21.76 70 13.7 6.2 0.29 − 1.62
BW-16 7.52 369 236.16 9.94 2.1 21.78 9.77 28.64 80 23.9 7.2 0.56 − 4.34
BW-17 8 238 152.32 14.2 3.83 12.89 8.72 20.12 80 16.2 2.6 0.17 − 4.2
BW-18 7.86 196 125.44 6.84 2.91 16.9 5.31 18.4 60 6.2 6.9 0.23 − 2.67
SP-19 7.77 165 105.6 7.21 2.61 15.32 8.95 21.34 60 17.24 6.2 0.17 − 4.16
BW-20 7.39 514 328.96 26 1.24 37.1 0.42 42.8 80 16.26 9.3 0.83 0.68
BW-21 7.14 216 138.24 6.82 2.41 9.85 18.7 21.28 80 25.6 9.7 0.14 − 4.27
DW-22 6.7 80 51.2 8.92 2.62 7.81 7.6 19.6 50 6.3 5.9 0.19 − 4.2
BW-23 7.77 272 174.08 7.67 1.84 22.82 10.7 24.55 90 26.3 4.2 0.18 − 3.72
BW-24 6.39 111 71.04 9.75 2.56 11.83 6.31 18.79 40 21.4 3.8 0.17 − 2.84
DW-25 6.8 174 111.36 9.41 2.92 13.76 5.61 20.34 40 22.72 2.3 0.22 − 3.19
SP-26 6.99 60 38.4 12.51 2.42 13.76 4.73 23.12 40 20.5 5.7 0.14 − 4.13
BW-27 6.47 99 63.36 14.92 1.85 14.86 3.43 28.3 60 26.5 9.8 0.22 − 3.47
2597

13
 Table 1  (continued)
2598

Type pH EC TDS Na+ K+ Ca2+ Mg2+ Cl− HCO3− SO42− NO3− F− CBE

13
SP-28 7.19 77 49.28 15.62 1.76 16.7 4.34 29.8 40 21.41 6.9 0.10 − 3.49
BW-29 7.29 272 174.08 10.32 1.51 12.55 23.9 32.64 110 26.1 4.7 0.17 − 4.1
BW-30 6.47 139 88.96 13.87 2.41 18.23 6.91 31.75 90 36.7 14.8 0.21 − 1.85
BW-31 5.25 31 19.84 14.1 1.58 13.93 4.23 41.12 40 0.92 0.5 0.10 − 4.12
BW-32 7.9 271 173.44 14.74 1.15 28.7 7.33 36.8 140 0.45 9.5 0.19 − 4.08
DW-33 6.6 71 45.44 19.52 1.42 20.78 7.42 45.52 40 31.8 9.7 0.15 − 4.26
SP-34 6.69 131 83.84 17.75 0.86 21.98 6.71 37.21 90 0.31 6.8 0.17 − 3.9
BW-35 7.77 314 200.96 21.65 2.56 36.54 16.2 39.45 180 34.2 14.22 0.27 − 4.48
BW-36 7.04 353 225.92 18.25 2.85 28.67 10.42 58.52 130 18.9 11.6 0.42 − 3.69
DW-37 6.64 95 60.8 17.52 1.78 20.87 2.89 28.8 60 13.5 8.7 0.20 − 3.03
DW-38 6.74 279 178.56 26.41 4.34 24.52 5.34 70.81 60 0.3 11.4 0.21 − 4.08
BW-39 6.44 115 73.6 14.75 1.79 15.65 4.98 38.28 90 28.9 7.5 0.24 − 1.97
DW-40 6.39 44 28.16 25.87 1.54 22.37 1.92 36.54 70 14.3 6.5 0.18 − 2.82
DW-41 6.07 54 34.56 20.45 1.34 18.73 1.82 34.12 50 8.7 9.5 0.11 − 2.62
BW-42 6.93 206 131.84 24.76 3.54 26.4 5.49 32.49 110 28.7 6.7 0.24 − 3.98
BW-43 5.68 57 36.48 19.42 1.42 17.71 2.41 42.8 40 19.8 7.2 0.10 − 3.51
DW-44 5.59 55 35.2 18.89 1.87 20.24 1.78 46.3 40 3.9 5.1 0.00 − 2.39
DW-45 6.03 49 31.36 17.45 1.12 19.29 1.29 38.2 50 0.5 6.3 0.08 − 3.95
DW-46 6.41 85 54.4 21.59 1.72 27.79 1.15 40.9 60 21.4 7.1 0.15 − 4.51
BW-47 7.49 340 217.6 25.51 1.92 32.21 14.4 84.52 120 18.3 5.7 0.21 − 4.52
BW-48 7.53 308 197.12 23.75 3.51 35.6 8.82 41.23 180 2.7 5.2 0.28 − 4.49
DW-49 6.49 201 128.64 16.83 1.52 21.38 3.69 36.8 50 15.5 8.1 0.17 − 3.81
BW-50 8.04 277 177.28 22.76 6.83 37.81 4.62 42.26 160 0.52 6.8 0.28 − 2.79
DW-51 5.47 57 36.48 25.18 2.23 26.32 1.74 47.64 60 16.23 11.4 0.09 − 4.4
BW-52 5.6 31 19.84 16.49 0.81 15.82 0.42 54.48 70 0.3 13.7 0.09 0.53
DW-53 5.73 69 44.16 24.76 1.51 28.51 1.06 48.64 80 4.7 6.4 0.09 − 4.7
BW-54 7.29 356 227.84 28.97 1.76 34.54 14.9 73.48 140 13.5 5.3 0.20 − 4.75
S. Gaikwad et al.
 Table 1  (continued)
Type pH EC TDS Na+ K+ Ca2+ Mg2+ Cl− HCO3− SO42− NO3− F− CBE

DW-55 5.43 56 35.84 26.15 1.88 24.19 0.97 45.7 50 23.5 6.1 0.09 − 4.33
DW-56 5.99 48 30.72 25.28 0.87 24.11 1.67 41.8 60 20.7 7.3 0.14 − 4.81
DW-57 5.7 31 19.84 28.48 0.96 26.7 1.24 48.91 70 14.7 6.5 0.09 − 4.18
DW-58 5.62 45 28.8 25.87 1.13 23.63 1.78 39.8 50 22.5 6.2 0.16 − 0.62
DW-59 7.6 457 292.48 36.93 22.7 34.12 10.79 59.63 190 14.7 5.9 0.19 − 4.21
DW-60 6.41 92 58.88 23.41 0.93 25.76 6.51 53.12 60 25.2 6.7 0.10 − 4.21
BW-61 7.11 187 119.68 25.91 2.27 31.86 7.28 44.63 140 21.5 4.7 0.22 − 2.13
BW-62 6.84 260 166.4 29.76 2.83 26.89 6.78 55.37 140 0.67 5.3 0.26 − 3.95
BW-63 6.9 207 132.48 25.82 3.26 24.52 4.31 35.79 130 0.52 9.5 0.25 − 2.07
BW-64 6.61 304 194.56 31.87 2.73 28.11 6.09 61.84 110 34.7 9.8 1.40 − 4.42
DW-65 7.7 302 193.28 33.49 2.56 31.12 9.86 63.68 110 23.9 10.9 0.22 − 4.74
Min. 5.25 31 19.84 6.27 0.80 3.89 0.42 18.40 40 0.30 0.50 0.00 − 4.81
Max. 8.23 514 328.96 36.93 22.70 41.50 27.60 84.52 190 36.70 14.80 1.42 0.68
Mean 6.84 189.43 121.24 17.47 2.55 21.07 6.71 37.18 85.23 15.52 7.23 0.26 − 3.43
Geochemical mobility of ions in groundwater from the tropical…

All the above values are in mg/l except pH in scale and EC in μS/cm
DW dug well, BW bore well, SP spring sample
2599

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2600 S. Gaikwad et al.

Fig. 3  Spatial variation of pH

(Fig. 9) are observed in central and western parts of the basin, while low values are
in the eastern and southern sides. High values of ­HCO3 in groundwater at few places
are due to plentiful supply of ­CO2 by rainwater seepage and dissolution of the gases
present in the pedologic horizons (Hem 1985; Pawar et al. 2008; Kale et al. 2010; Kale
and Pawar 2017). Chloride (Cl) concentration ranges in groundwater from 18.4 to
84.52 mg/l. Spatial distribution map depicts that the high values of chloride concentra-
tions are predominant in the central part of the study area (Fig. 10). The anomalous high
Cl is found at major localities in the study area such as Sawantwadi (DW-65) and Banda
(54), which is possibly due to the anthropogenic sources such as domestic effluents, fer-
tilizers and septic tanks or from natural sources (Jiang et al. 2015; Mukate et al. 2015).
The concentration of sulfate ­(SO4) ranges from 0.3 to 36.7 mg/l. It is observed that the
high values of sulfate ­(SO4) concentrations (Fig. 11) are predominant in the central and
upper parts of Terekhol Basin. High concentration in central part may be due to the use
of fertilizers along with other human influences. Nitrate (­NO3) concentration (Fig. 12)
ranges from 0.5 to 14.8 mg/l. The higher values at few locations are observed indicating
local anthropogenic source like nitrogenous inorganic fertilizers used in agriculture in
addition to human and animal waste (Brindha et al. 2010; Wagh et al. 2017b, 2018b).
The fluoride (F) in groundwater ranges from 0 to 1.42 mg/l. High values are reported
in northwestern part of the study area (Fig. 13). High values of fluoride in BW-01 and
BW-64 (deep bore well) indicate the prolonging time of rock–water interaction (Gaik-
wad 2012; Gaikwad and Pawar 2012).

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Geochemical mobility of ions in groundwater from the tropical… 2601

Fig. 4  Spatial variation of electrical conductivity (EC)

5 Groundwater quality for drinking purposes

The water to be used for drinking purposes must be free from undesirable physical
properties like cloudiness, objectionable odor and taste (Nikumbh 1997). It is evident
that these values of physicochemical parameters are within desirable limits except pH
(66.16%), ­HCO3 (18.47%) and fluoride (3.07%) but all the parameters are below the per-
missible values prescribed by WHO (2011). It is confirmed that the groundwater quality
is good for drinking.

6 Geo‑statistical analysis

In this study, geo-statistical analysis was used to reduce and organize the data with simi-
lar hydrochemical characteristics. Therefore, a total of 11 water quality variables were
considered for the construction of correlation analysis. Cluster analysis and principle
component analysis and their results are demonstrated in Tables 2 and 3.

6.1 Correlation analysis

The correlation analysis is used to know the degree of relationship among various physico-
chemical parameters which influence groundwater quality (Table 2). It involves statistical

13
2602 S. Gaikwad et al.

Fig. 5  Spatial variation of calcium (Ca)

calculations and gives a measure of how one variable predicts the value of another vari-
able (Pearson 1896). If the variables are showing correlation coefficient (r) > 0.7, between
0.5–0.7 and < 0.3, indicating strong, moderate and weak correlation, respectively. A pos-
itive correlation indicates the same sources of specific ions which can be influenced by
natural or anthropogenic origin; however, weak correlation infers the sources of ions are
independent from each other (Islam et al. 2017). Positive correlation between pH with EC
(r = 0.76), Mg (r = 0.62) and ­HCO3 (r = 0.59) suggests dissolution and alkalinity process
are dominant in the study area. A correlation of EC with ­HCO3 (r = 0.71), Mg (r = 0.53)
and F (r = 0.51) is due to the dissolution of salts, which leads to rises in the electrical con-
ductivity (Wagh et al. 2016a). Sodium (Na) positively correlates with calcium (r = 0.65)
and chloride (r = 0.79) that inferred the affinity (Touhari et al. 2015). Calcium moderately
correlates with chloride (r = 0.59) and bicarbonate (r = 0.57). The correlation of fluoride
with Ca (r = 0.13) and Mg (r = 0.04) indicates the low solubility of fluoride in natural
groundwater (Handa 1975). Magnesium moderately correlates with bicarbonate (r = 0.53)
indicating temporary hardness.

6.2 Cluster analysis

The cluster analysis technique is performed to find the similarity among the water variables
using Ward linkage method. The cluster analysis indicates that the samples are classified

13
Geochemical mobility of ions in groundwater from the tropical… 2603

Fig. 6  Spatial variation of sodium (Na)

into three groups represented in dendrogram (Fig. 14). It is observed that pH, N
­ O3, Mg, K,
Na, Ca, ­SO4 and Cl are closely associated with each other. Further, this group is associated
with ­HCO3 and these two groups are jointly associated with EC.

6.3 Principal component analysis

In hydrochemical studies, it is imperative to correlate the significant association among

various physicochemical parameters and attempt to find out their possible sources of con-
tamination due to complexities in local hydrogeology and hydrochemical processes that
take place in aquifer which are complex to elucidate. Therefore, in order to recognize the
utmost influencing physicochemical parameters on groundwater quality, R-mode factor
analysis using SPSS 22.0 v was applied to the groundwater data to classify the different
groups based on inherent qualities of physicochemical parameters. R-mode factor analysis
is used to observe the association between water quality variables by exploring a matrix
of simple correlation coefficients for all pairs of variables considered (Saager and Sinclair
1974). Also, factor analysis is performed to differentiate the factors without altering the
data structure which helps to reduce the contribution of less significant parameters distress-
ing groundwater quality (Mertler and Vannatta 2005; Aryafar and Ardejani 2013). Table 3
presents the rotated component matrix of four factors with eigenvalues, % of variance and

13
2604 S. Gaikwad et al.

Fig. 7  Spatial variation of magnesium (Mg)

cumulative % of each factor. The selection of optimal number of factors in R-mode fac-
tor analysis requires amount of the cumulative variance, eigenvalues > 1 and scree plot
(Fig. 15). The component plot in rotated space is presented in Fig. 16. An eigenvalue gives
a measure of the significance of the factor and the factor with highest eigenvalue as the
most significant. The factor loading is characterized as strong (> 0.7), moderate (0.5–0.7)
and weak (0.3–0.5), respectively (Kwon et al. 2016). It is observed that the first factor (Fac-
tor 1) accounts for 27.931% of the total variance and is positively loaded with pH (0.851),
EC (0.822), K (0.465), Mg (0.825), ­HCO3 (0.793). The high loading of EC is led to dis-
solution of salts. Positive loading of ­HCO3 indicates groundwater is recharged with fresh-
water and C ­ O2 dissolution during precipitation. Also, positive loadings of Mg indicate oli-
vine and pyroxene minerals from weathering of basalt. Factor 2 accounts for Na (0.922),
Ca (0.793) and Cl (0.885) with 24.985%. The Na and Cl show high PC loadings due to
their high solubility behavior (Rao 2014). The third factor is with high loadings of F (0.91)
owed to geogenic origin. The fourth factor is dominated by ­SO4 (0.80) and ­NO3 (0.533)
suggesting the leaching of agricultural and animal wastes, fertilizers into aquifer which
turn to reflect anthropogenic origin.

13
Geochemical mobility of ions in groundwater from the tropical… 2605

Fig. 8  Spatial variation of potassium (K)

7 Hydrogeochemical evaluation

To understand the hydrogeochemical processes within a river basin, groundwater is chemi-

cally and biologically reacts with and altered through the naturally occurring rock–water
interactions such as physical, chemical and biological reactions prevailing in soil and
groundwater, types of weathering and anthropogenic activities (Todd 1980). Thus, it is
vital to comprehend the geochemistry of groundwater to identify the contributing sources
through hydrochemical facies, rock–water interactions and dissolution and precipitation
reactions.

7.1 Hydrochemical facies

Piper diagram (1944) is useful for exhibiting the results of analysis in a multi-coordinate
field. The piper diagram is drawn by plotting the proportions (in equivalents) of the major
cations ­(Na++K+, ­Ca2+, ­Mg2+) on one triangular diagram and the proportions of the major
anions ­(HCO3− + CO3, ­Cl− and S ­ O42−) on the other. The combined information from the
two triangle diagrams is plotted on a quadrilateral diagram. The piper trilinear diagram
shows chemical relationship of groundwater constituents from study area (Fig. 17). In the
study area, Ca-HCO3 and mixed Ca–Cl-HCO3 are the two major types reported which indi-
cate rainfall recharge and evaporation are the processes responsible for this type.

13
2606 S. Gaikwad et al.

Fig. 9  Spatial variation of bicarbonate ­(HCO3)

7.2 Gibbs plots

Gibbs (1970) has pointed out that the rate of evaporation, chemical compositions of rocks
and rainwater influence generally control the groundwater chemistry. In order to evaluate
the sources of various ions in the water, the chemical data were plotted in Gibbs diagram
for cations and anions separately (Fig. 18). The Gibbs diagrams suggest that the rock domi-
nance and the precipitation dominance control the groundwater chemistry of the study
area.

7.3 Geochemical plots

The Na versus Cl scatter diagram (Fig. 19) shows positive correlation (r = 0.70) indicat-
ing combined influence of anthropogenic and lithogenic sources (Gaikwad and Pawar
2008). Alike, the cross-plot of Ca + Mg versus ­HCO3 (Fig. 20) depicts a positive correla-
tion (r = 0.78), demonstrating addition of more Ca and Mg over H­ CO3 (Singh et al. 2014).
The cross-plot Na + K versus H ­ CO3 (Fig. 21) also shows positive correlation (r = 0.36),
suggesting that there is also less contribution of ions from felsic lithologies in the area
(Singh et al. 2014). The scatter plots of Ca + Mg versus Cl + SO4 (Fig. 22) and Ca + Mg
versus ­SO4 + HCO3 (Fig. 23) represented positive association (r = 0.47 and 0.23, respec-
tively), signifying that these are preferred ion pairs forming in the groundwater (Pawar
et al. 2008). The correlation between Ca + Mg versus Na + K is weak (r = 0.33), suggesting

13
Geochemical mobility of ions in groundwater from the tropical… 2607

Fig. 10  Spatial variation of chloride (Cl)

additions of ion from carbonate weathering than silicate weathering. It is observed that
there is no significant correlation found between Ca and Mg (r = 0.0312), confirming less
role of mafic minerals in the groundwater geochemistry (Fig. 24). In the Ca + Mg versus
­SO4 + HCO3 (Fig. 23) scatter diagram, the ionic concentrations in meq/l fall in both the
sides of equiline indicating silicate weathering and carbonate weathering that are main pro-
cesses responsible for altering groundwater chemistry (Tiwari et al. 2016). If ­Ca2+/Mg2+
molar ratio (Fig. 25) is >2, then it is indicative of dissolution of silicate minerals (Kanaga-
raj and Elango 2016). It is confirmed that about 46% of water samples show this ratio to
be more than two. Moreover, remaining 20% samples have molar ratio of ≤ 1, which is
indicative of dolomite dissolution (Mayo and Loucks 1995). Also, about 33% of samples
have ­Ca2+/Mg2+ molar ratio of > 1 but < 2, indicating dissolution of calcite is the dominant
geochemical processes in groundwater (Subramani et al. 2010).

8 Multiple linear regression analysis

Multiple linear regressions are used to know relationship among various explanatory vari-
ables and a response variable by fitting a linear equation to observed data (Rasouli et al.
2012). In this study, to articulate the best fit for fluoride content of the groundwater, the
following processes are performed. First, correlation analysis is performed to identify the
association between various parameters. Table 2 shows that pH, EC, Na, K, Ca, Mg, Cl,

13
2608 S. Gaikwad et al.

Fig. 11  Spatial variation of sulfate ­(SO4)

­HCO3 and F positively correlate with each other. Hence, for further formulation of multiple
regression analysis, pH, EC, Na, K, Ca, Mg, Cl and ­HCO3 parameters were considered
as independent variables and F as regressed variable. Then, the multiple regressions are
authenticated with assumptions of multiple R, R ­ 2, adjusted R
­ 2, standard error and observa-
tions. Finally, we compare the observed values of fluoride of the groundwater with the pre-
dicted values obtained from the best fitted multiple regression equation. Table 5 shows the
statistics about the regression. Figure 26 corroborates the observed and predicted results of
the F concentration. The regression equation is as follows.

F = 0.0751 ∗ Constant + 0.0216 ∗ pH + 0.0023 ∗ EC + 0.0196 ∗ Na

− 0.0314 ∗ K − 0.0137 ∗ Ca − 0.0179 ∗ Mg − 0.0056 ∗ Cl
− 0.0005 ∗ HCO3

From Table 5, it is confirmed that regression equation can give better results, i.e.,
R = 0.72 and RMSE (0.035), which clearly show the efficiency of the proposed model.

13
Geochemical mobility of ions in groundwater from the tropical… 2609

Fig. 12  Spatial variation of nitrate ­(NO3)

8.1 Groundwater quality for irrigation purposes

The comprehensive consideration of groundwater suitability for irrigation is expressively

based on total ionic content of the water such as EC, SAR, %Na, Ca, MAR, Cl, Na and
RSC. Also, it depends on amount of salt concentration, sodium content, nutrients rate,
alkalinity, acidity and hardness of water which lead to loss of soil fertility and crop yield
(Kirda 1997). If groundwater quality is not protected well in time, then the impact of using
such contaminated water may lead to descent of plant growth and crop yield (Wagh et al.
2018a). As a result, the suitability of groundwater for irrigation has been attempted on the
basis of SAR, USSL, %Na and KR and their classification is represented (Table 6).

8.2 Sodium adsorption ratio (SAR)

SAR is an important ratio used for determining the suitability of groundwater for irrigation
because sodium concentration reduces soil permeability and affects soil structure (Saleh
et al. 2017). SAR ratio measures alkali/sodium hazard to the crop which results in damage
to the soil productivity in the long term (Wagh et al. 2018b). SAR is calculated with the
help of the following equation:
/ {[( ) ]1∕2 }
SAR = Na+ Ca2+ + Mg2+ ∕2

13
2610 S. Gaikwad et al.

Fig. 13  Spatial variation of fluoride (F)

Table 2  Correlation analysis of physicochemical parameters

pH EC Na K Ca Mg Cl HCO3 SO4 NO3 F

Ph 1.00
EC 0.76 1.00
Na − 0.17 0.08 1.00
K 0.27 0.39 0.28 1.00
Ca 0.22 0.45 0.65 0.18 1.00
Mg 0.62 0.53 − 0.24 0.14 − 0.03 1.00
Cl − 0.20 0.17 0.79 0.14 0.59 − 0.05 1.00
HCO3 0.59 0.71 0.31 0.44 0.57 0.53 0.30 1.00
SO4 0.06 0.10 − 0.01 − 0.07 0.15 0.20 − 0.01 0.00 1.00
NO3 0.02 0.14 0.21 − 0.06 0.26 − 0.02 0.23 0.18 0.18 1.00
F 0.37 0.51 0.10 0.05 0.13 0.04 0.00 0.20 0.11 0.17 1.00

Bold values show significant correlations among physicochemical parameters

where all ion concentrations are expressed in meq/l.

If SAR values (< 10) is considered as excellent; 10–18 as good; 18–26 as fair; and above
26 are unsuitable for irrigation use (Richards1954). The SAR values in water samples
range from 0.23 to 1.46 with an average value of 0.86. It is confirmed that all the water
samples are excellent for irrigation use.

13
Geochemical mobility of ions in groundwater from the tropical… 2611

Table 3  Principal component Parameters Factors

analysis of groundwater
1 2 3 4

pH 0.851 − 0.156 0.300 − 0.010

EC 0.822 0.190 0.416 − 0.001
Na − 0.87 0.922 0.061 − 0.080
K 0.465 0.299 − 0.040 − 0.475
Ca 0.280 0.793 0.129 0.138
Mg 0.825 − .197 − 0.209 0.217
Cl − 0.018 0.885 − 0.074 0.037
HCO3 0.793 0.429 0.069 − 0.048
SO4 0.150 0.008 − 0.066 0.808
NO3 − 0.34 0.335 0.339 0.533
F 0.190 0.009 0.913 0.045
Eigenvalues 3.072 2.748 1.293 1.241
% of variance 27.931 24.985 11.750 11.285
Cumulative % 27.931 52.916 64.666 75.952

Bold values indicate the high positive loading

Rotation method: Varimax with Kaiser normalization
Rotation converged in five iterations

Fig. 14  Dendrogram

13
2612 S. Gaikwad et al.

Fig. 15  Scree plot

Fig. 16  Component plot

13
Geochemical mobility of ions in groundwater from the tropical… 2613

Fig. 17  Classification of hydrochemical facies of groundwater on piper trilinear diagram

Fig. 18  Gibb’s plots

8.3 USSL diagram

The US salinity laboratory diagram (Fig. 27) is used for rating the irrigation water suitabil-
ity (Richards 1954). These values of SAR are plotted against electrical conductivity. It is
observed that EC values less than 100 are reported in 19 samples, while more than 100 but
less than <250 EC values are conveyed in 25 samples and remaining 21 samples show EC

13
2614 S. Gaikwad et al.

Fig. 19  A scatter plot of Na

versus Cl

Fig. 20  A scatter plot of Ca + Mg

versus ­HCO3

Fig. 21  A scatter plot of Na + K

versus ­HCO3

more than 250 (Table 6). It is found that 67.70% of groundwater samples fall in the ­C1S1
and while 32.3% of samples fall in C ­ 2S1 fields, indicating low to medium salinity and low
alkalinity, which are suitable for irrigation of most crops (Ağca 2014).

13
Geochemical mobility of ions in groundwater from the tropical… 2615

Fig. 22  A scatter plot of Ca + Mg

versus Cl + SO4

Fig. 23  A scatter plot of Ca + Mg

versus ­SO4 + HCO3

Fig. 24  A scatter plot of Ca + Mg

versus Na + K

13
2616 S. Gaikwad et al.

Fig. 25  A scatter plot of Ca

versus Mg

Table 5  Regression statistics Regression statistics

Multiple R 0.72
R square 0.52
Adjusted R square 0.45
Standard error 0.19
Observations 65

1.5 F Predicted F
F Concentraon(mg/L)

0.5

0
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64
Sample Numbers

Fig. 26  Line graph of observed and predicted value of fluoride

8.4 Percent sodium (%Na)

The percent sodium (%Na) is a parameter used to identify the soluble sodium in water and
sodium hazard (Raghunath 1987). The percent sodium (%Na) is calculated using the equa-
tion is as follows:
%Na = Na+ + K+ × 100∕ Ca2+ + Mg2+ + Na+ + K+
( ) ( )

where all the concentrations are expressed in meq/l.

13
 Table 6  Suitability of groundwater for irrigation based on EC, SAR, Na% and Kelley’s ratio
Parameter Range Classification Sample numbers Numbers of % of samples
samples

EC (μS/cm) Raghunath < 250 Excellent 2, 6–9, 11–15, 17–19, 21, 22, 24–28, 30, 31, 33, 34, 37, 39–46, 44 67.7
(1987) 49, 51–53, 55–58, 60, 61, 63
250–750 Good 1, 3, 4, 5, 10, 16, 20, 23, 29, 32, 35, 36, 38, 47, 48, 50, 54, 59, 21 32.3
62, 64, 65
750–2000 Permissible – – –
2000–3000 Doubtful – – –
> 3000 Unsuitable – – –
SAR Richards (1954) < 10 Excellent 1–65 65 100
10–18 Good – – –
18–26 Doubtful – – –
Geochemical mobility of ions in groundwater from the tropical…

> 26 Unsuitable – – –
Na% Raghunath (1987) < 20 Excellent 1–11, 15–58, 60–65 61 93.85
20–40 Good 12, 13, 14, 59 04 6.15
40–60 Permissible – – –
60–80 Doubtful – – –
> 80 Unsuitable – – –
KR Kelley (1951) <1 Suitable 4, 9, 11, 18, 20, 37, 44–46, 49–53, 14 21.53
>1 Unsuitable 1–3, 5–8, 10, 12–17, 19, 21–36, 38–43, 47, 48, 54–65 51 78.47
2617

13
2618 S. Gaikwad et al.

Fig. 27  USSL diagram for classification of irrigation water (Richards 1954) (color coding = yellow spring
samples (n = 04); black borewell (n = 40); and blue dugwell (n = 21))

The percent sodium content ranges from 3.2 to 38.8% with an average value of 9.69%
suggesting that the groundwater in the basin falls under good to excellent for irrigation
(Table 6). The high sodium content is absorbed by clay particles in the exchange of Ca and
Mg which reduces the permeability of soil (Chitsazan et al. 2017).

8.5 Kelley’s ratio (KR)

This ratio is used to measure the sodium content against calcium and magnesium contents.
Generally, if the ratio is (> 1) proposes the excessive concentration of sodium which can
pose to adverse effects on soil properties and also reduced soil permeability. Subsequently,
if water with ratio (> 1) is unsuitable and (< 1) is supposed to be suitable for irrigation
(Kelley 1951). The ratio can be calculated by using following formula:
Kellys ratio (KR) = Na+ ∕ Ca2+ + Mg2+
( )

where all the concentrations are expressed in meq/l.

13
Geochemical mobility of ions in groundwater from the tropical… 2619

It is observed that most of the samples, i.e., 78.47%, are not suitable for irrigation, while
21.53% are confirming their suitability for irrigation. This represents that sodium is the
dominant cation at many places over the calcium and magnesium; therefore, groundwater
has widespread unsuitability for irrigation.

9 Conclusions

Analytical results inferred that groundwater of Terekhol River basin is acidic to alkaline
in nature. The decreasing order of major ions concentration in the groundwater is as fol-
lows: ­Ca2+ > Na+ > Mg2+ > K+ = HCO3− > Cl− > SO−2 − −
4 > NO3 > F . The Na concentration
increases from northeast to southwest of the basin due to the directional flow of ground-
water plus residence time. A diminutive content of K in groundwater is may be due to less
appearance of K-bearing minerals in lithologies; however, high value of K is reported at
few places indicating leaching of K-rich fertilizers in agriculture. Elevated Ca values in
the central and southwestern parts of basin indicating feldspar, pyroxene and amphibole
present in the country rocks mainly contribute C ­ a2+ to the groundwaters. The source of
magnesium constituent is ferromagnesian minerals in studied lithology. In view of anions,
high concentration of ­SO4, Cl and ­NO3 at few locations indicates the anthropogenic inputs,
whereas high fluoride in groundwater is due to rock–water interaction at deeper source.
The piper trilinear diagram demonstrated mostly Ca-HCO3 and mixed Ca–Cl-HCO3 are the
two major types indicating rainfall recharge and evaporation are the processes responsible
for this type. Gibbs diagrams reveal rock dominance as well as the precipitation dominance
is controlling the groundwater chemistry in the study area. As per WHO standards, pH
(66.16%), ­HCO3 (18.47%) and F (3.07%) surpass the desirable limit but within permissible
limit; hence, groundwater is good for drinking. A positive correlation of pH with EC, Mg
and ­HCO3 suggests dissolution and alkalinity process are dominant in the study area. The
weak correlation of fluoride with Ca (r = 0.13) and Mg (r = 0.04) indicates the low solubil-
ity of fluoride in natural groundwater. The high loading of EC is owed to dissolution of
salts, and high loading of HCO3 indicates groundwater is recharged with freshwater and
­CO2 dissolution during precipitation. A positive loading of Mg indicates olivine and pyrox-
ene minerals from weathering of basalt. Na and Cl show high PC loadings due to their high
solubility behavior. The high loadings of F owed to geogenic origin and ­SO4 and N ­ O3 owed
to leaching of agricultural and animal wastes, fertilizers into aquifer which reflects anthro-
pogenic origin. In view of irrigation suitability, USSL diagram shows that all samples fall
in C1S1 (67.70%) and C2S1 (32.30%) fields, indicating low to medium sodium hazard.
SAR depicts that all samples are found to be excellent for irrigation. The %Na results cor-
roborate that all samples are found excellent (93.85%) to good (6.15%) for irrigation. KR
ratio suggests 78.47% samples are unsuitable for irrigation. Multiple linear regressions for
predicting the fluoride content confirm that equation has better results based on R (0.72)
and RMSE (0.035), which clearly show the efficiency of the proposed model. In nutshell,
overall interpretation confirms that groundwater quality is good for drinking and irrigation;
however, those aquifers are problematic which require remedial measures. The outcomes
of the study may help local inhabitants, policy makers and researchers for better restoration
of groundwater resources and their sustainable management in coastal regions.

Acknowledgements This research work was funded by SPPU-ISRO STC cell, Savitribai Phule Pune Uni-
versity. The funding project number is PU/ISRO STC/1541 dated June 02, 2014. The authors wish to thank
Head, Department of Geology, for providing laboratorial facilities. The authors would like to express their

13
2620 S. Gaikwad et al.

gratitude to the anonymous reviewers for their constructive suggestion for strengthening the manuscript
quality.

References
A.P.H.A. (2005). Methods for the examination of water and wastewater. American Public Health
Association.
Adimalla, N., & Li, P. (2018). Occurrence, health risks, and geochemical mechanisms of fluoride and nitrate
in groundwater of the rock-dominant semi-arid region, Telangana State, India. Human and Ecological
Risk Assessment: An International Journal, 24, 1–23. https​://doi.org/10.1080/10807​039.2018.14803​
53.
Arslan, H. (2017). Determination of temporal and spatial variability of groundwater irrigation quality using
geostatistical techniques on the coastal aquifer of Çarşamba Plain, Turkey, from 1990 to 2012. Envi-
ronmental Earth Sciences, 76(1), 38.
Aryafar, A., & Ardejani, F. D. (2013). R-mode factor analysis, a popular multivariate statistical technique
to evaluate water quality in Khaf-Sangan basin, Mashhad, Northeast of Iran. Arabian Journal of Geo-
sciences, 6(3), 893–900.
Ayers, R. S., & Westcot, D. W. (1994). Water quality for agriculture. FAO. Irrigation and Drainage Paper,
29. Rome: FAO, 174 p.
Bhuiyan, M. A. H., Bodrud-Doza, M., Islam, A. T., Rakib, M. A., Rahman, M. S., & Ramanathan, A. L.
(2016). Assessment of groundwater quality of Lakshimpur district of Bangladesh using water quality
indices, geostatistical methods, and multivariate analysis. Environmental Earth Sciences, 75(12), 1–23.
Brindha, K., & Elango, L. (2013). Geochemistry of fluoride rich groundwater in a weathered granitic rock
region, Southern India. Water Quality, Exposure and Health, 5(3), 127–138.
Brindha, K., Rajesh, R., Murugan, R., & Elango, L. (2010). Natural and anthropogenic influence on the
fluoride and nitrate concentration of groundwater in parts of Nalgonda district, Andhra Pradesh, India.
Journal of Applied Geochemists, 12(2), 231–241.
CGWB. (1992). General guidelines for the evaluation of Groundwater Recharge Schemes with special refer-
ence to Basaltic terrain.
CGWB. (2009). Groundwater information, Sindhudurg district, Maharashtra. Technical Report, 1625/
DB/2009.
CGWB. (2014). Groundwater information, Sindhudurg District, Maharashtra. Technical Report, 1835/
DB/2014.
Chidambaram, S., Ramanathan, A. L., Prasanna, M. V., Lognatan, D., Srinivasamoorthy, K., & Anandhan,
P. (2008). Study on the impact of tsunami on shallow groundwater from Portnova to Pumpuhar, using
geoelectrical technique-south east coast of India.
Chitsazan, M., Aghazadeh, N., Mirzaee, Y., & Golestan, Y. (2017). Hydrochemical characteristics and the
impact of anthropogenic activity on groundwater quality in suburban area of Urmia city, Iran. Environ-
ment, Development and Sustainability. https​://doi.org/10.1007/s1066​8-017-0039-1.
Das, S., & Nag, S. K. (2015). Deciphering groundwater quality for irrigation and domestic purposes—A
case study in Suri I and II blocks, Birbhum District, West Bengal, India. Journal of Earth System Sci-
ence, 124(5), 965–992.
Deshpande, G. G. (1998). Geology of Maharashtra, Geological society of India, Bangalore, 223p.
Gaikwad, S. K. (2012). Geochemistry of fluoride bearing ground waters from the Karli River Basin, South-
ern part of Sindhudurg District, Maharashtra. Doctoral dissertation, Ph.D. thesis, University of Pune.
Gaikwad, S. K., & Pawar, N. J. (2008). Spatio-temporal geochemical distinctiveness of groundwaters allied
to lithological diversity in the area between Karli and Terekhol Rivers, Southern part of Coastal
Maharashtra, India. In International Groundwater Conference on “groundwater dynamics and global
change” Organized by University of Rajasthan, Jaipur, India in March, 2008.
Gaikwad, S. K., & Pawar, N. J. (2012). Imprints of lithological diversity on the chemical composition of
groundwater from Sindhudurg District, Maharashtra. Memoirs of the Journal-Geological Society of
India, 60, 109–126.
Geological Survey of India (GSI). (2006). District Resource Map of Sindhudurg District.
Ghalib, H. B. (2017). Groundwater chemistry evaluation for drinking and irrigation utilities in east Wasit
province, Central Iraq. Applied Water Science, 7(7), 3447–3467.
Gibbs, R. J. (1970). Mechanisms controlling world water chemistry. Science, 170(3962), 1088–1090.
Gnanachandrasamy, G., Dushiyanthan, C., Rajakumar, T. J., & Zhou, Y. (2018). Assessment of hydro-
geochemical characteristics of groundwater in the lower Vellar river basin: Using Geographical

13
Geochemical mobility of ions in groundwater from the tropical… 2621

Information System (GIS) and Water Quality Index (WQI). Environment, Development and Sustain-
ability. https​://doi.org/10.1007/s1066​8-018-0219-7.
Gopinath, S., Srinivasamoorthy, K., Saravanan, K., & Prakash, R. (2018). Discriminating groundwater
salinization processes in coastal aquifers of southeastern India: Geophysical, hydrogeochemical and
numerical modeling approach. Environment, Development and Sustainability. https​://doi.org/10.1007/
s1066​8-018-0143-x.
GSDA. (1984). Groundwater Survey Development Agency, Govt. of Maharashtra. Systematic Hydro-
logical Survey Reports of Sindhudurg District (unpublished).
Handa, B. K. (1975). Geochemistry and genesis of fluoride-containing ground waters in India. Ground-
water, 13(3), 275–281.
Hassen, I., Hamzaoui-Azaza, F., & Bouhlila, R. (2016). Application of multivariate statistical analysis
and hydrochemical and isotopic investigations for evaluation of groundwater quality and its suit-
ability for drinking and agriculture purposes: Case of Oum Ali-Thelepte aquifer, central Tunisia.
Environmental Monitoring and Assessment, 188(3), 135.
Hem, J. D. (1985). Study and interpretation of the chemical characteristics of natural water (Vol. 2254).
Department of the Interior, US Geological Survey.
Hem, J. D. (1991). Study and interpretation of the chemical characteristics of natural water. (Vol. 2254,
3rd edn). Jodhpur: Scientific Publishers.
Hounslow, A. (1995). Water quality data: Analysis and interpretation. Boca Raton: CRC Press.
Islam, A. T., Shen, S., Bodrud-Doza, M. D., & Rahman, M. S. (2017). Assessing irrigation water quality
in Faridpur district of Bangladesh using several indices and statistical approaches. Arabian Journal
of Geosciences, 10(19), 418.
Jebastina, N., & Arulraj, G. P. (2016). Contamination analysis of groundwater in Coimbatore district,
India: A statistical approach. Environmental Earth Sciences, 75(22), 1447.
Jiang, L., Yao, Z., Liu, Z., Wang, R., & Wu, S. (2015). Hydrochemistry and its controlling factors of
rivers in the source region of the Yangtze River on the Tibetan Plateau. Journal of Geochemical
Exploration, 155, 76–83.
Kadam, A. K., Jaweed, T. H., Umrikar, B. N., Hussain, K., & Sankhua, R. N. (2017). Morphometric pri-
oritization of semi-arid watershed for plant growth potential using GIS technique. Modeling Earth
Systems and Environment. https​://doi.org/10.1007/s4080​8-017-0386-9.
Kadam, A. K., Kale, S. S., Pande, N. N., Pawar, N. J., & Sankhua, R. N. (2012). Identifying potential
rainwater harvesting sites of a semi-arid, basaltic region of Western India, using SCS-CN method.
Water Resources Management, 26(9), 2537–2554. https​://doi.org/10.1007/s1126​9-012-0031-3.
Kadam, A., Karnewar, A. S., Umrikar, B., & Sankhua, R. N. (2018). Hydrological response-based water-
shed prioritization in semiarid, basaltic region of western India using frequency ratio, fuzzy logic
and AHP method. Environment, Development and Sustainability. https​://doi.org/10.1007/s1066​
8-018-0104-4.
Kale, S. S., Kadam, A. K., Kumar, S., & Pawar, N. J. (2010). Evaluating pollution potential of leachate from
landfill site, from the Pune metropolitan city and its impact on shallow basaltic aquifers. Environmen-
tal Monitoring and Assessment, 162, 327–346. https​://doi.org/10.1007/s1066​1-009-0799-7.
Kale, S., & Pawar, N. J. (2017). Fluoride accumulation in groundwater from semi-arid part of Deccan
Volcanic Province, India: A cause of urolithiasis outbreak. Hydrospatial Analysis, 1, 9–17. https​://
doi.org/10.21523​/gcj3.17010​102.
Kaliraj, S., Chandrasekar, N., Peter, T. S., Selvakumar, S., & Magesh, N. S. (2015). Mapping of coastal
aquifer vulnerable zone in the south west coast of Kanyakumari, South India, using GIS-based
DRASTIC model. Environmental Monitoring and Assessment, 187(1), 4073.
Kammoun, S., Trabelsi, R., Re, V., Zouari, K., & Henchiri, J. (2018). Groundwater quality assessment in
semi-arid regions using integrated approaches: The case of Grombalia aquifer (NE Tunisia). Envi-
ronmental Monitoring and Assessment, 190(2), 87.
Kanagaraj, G., & Elango, L. (2016). Hydrogeochemical processes and impact of tanning industries on
groundwater quality in Ambur, Vellore district, Tamil Nadu, India. Environmental Science and Pol-
lution Research, 23(23), 24364–24383.
Kanagaraj, G., Suganthi, S., Elango, L., & Magesh, N. S. (2018). Assessment of groundwater potential
zones in Vellore district, Tamil Nadu, India using geospatial techniques. Earth Science Informatics.
https​://doi.org/10.1007/s1214​5-018-0363-5.
Kelley, W. P. (1951). Alkali soils; their formation, properties, and reclamation (No. 04; RMD, S595
K4.).
Kirda, C. (1997). Assessment of irrigation water quality. Options Mediterraneennes Serie A: Seminaires
Mediterraneens (CIHEAM).

13
2622 S. Gaikwad et al.

Kumar, P. S., & James, E. J. (2013). Physicochemical parameters and their sources in groundwater in the
Thirupathur region, Tamil Nadu, South India. Applied Water Science, 3(1), 219–228.
Kwon, S. M., Min, B. K., Son, J. S., Kim, K. H., & Kwon, T. Y. (2016). Durability of resin bond strength
to dental noble metal–ceramic alloys conditioned with novel mercaptosilane-based primer systems.
Journal of Adhesion Science and Technology, 30(5), 506–519.
Li, P., Qian, H., Wu, J., Zhang, Y., & Zhang, H. (2013). Major ion chemistry of shallow groundwater in
the Dongsheng Coalfield, Ordos Basin, China. Mine Water and the Environment, 32(3), 195–206.
Machiwal, D., & Jha, M. K. (2015). Identifying sources of groundwater contamination in a hard-rock aqui-
fer system using multivariate statistical analyses and GIS-based geostatistical modeling techniques.
Journal of Hydrology: Regional Studies, 4, 80–110.
Mayo, A. L., & Loucks, M. D. (1995). Solute and isotopic geochemistry and ground water flow in the cen-
tral Wasatch Range, Utah. Journal of Hydrology, 172(1–4), 31–59.
Mertler, C. A., & Vannatta, R. A. (2005). Advanced and multivariate statistical methods. Glendale: Pyrczak
Publishing.
Mukate, S., Panaskar, D., Wagh, V., Muley, A., Jangam, C., & Pawar, R. (2017). Impact of anthropogenic
inputs on water quality in Chincholi industrial area of Solapur, Maharashtra, India. Groundwater for
Sustainable Development. https​://doi.org/10.1016/j.gsd.2017.11.001.
Mukate, S. V., Panaskar, D. B., Wagh, V. M., & Pawar, R. S. (2015). Assessment of groundwater quality for
drinking and irrigation purpose: A case study of Chincholikati MIDC Area, Solapur (MS), India. SRT-
MUs Journal of Science, 4(1), 58–69.
Nikumbh, J. D. (1997). Geochemistry of groundwater from Behedi basin, District Nashik, Maharashtra.
(Doctoral dissertation, Ph. D thesis, University of Pune.
Panaskar, D. B., Wagh, V. M., Muley, A. A., Mukate, S. V., Pawar, R. S., & Aamalawar, M. L. (2016). Eval-
uating groundwater suitability for the domestic, irrigation, and industrial purposes in Nanded Tehsil,
Maharashtra, India, using GIS and statistics. Arabian Journal of Geosciences, 9(13), 615.
Pawar, N. J., & Kale, V. S. (2006). Waterfall tufa deposits from the Deccan Basalt Province, India: Implica-
tions for weathering of basalts in the semi-arid Tropics (with 9 figures and 2 tables). ZEITSCHRIFT
FUR GEOMORPHOLOGIE SUPPLEMENTBAND, 145, 17.
Pawar, N. J., Pawar, J. B., Kumar, S., & Supekar, A. (2008). Geochemical eccentricity of ground water allied
to weathering of basalts from the Deccan Volcanic Province, India: Insinuation on ­CO2 consumption.
Aquatic Geochemistry, 14(1), 41–71.
Pearson, K. (1896). Mathematical contributions to the theory of evolution. III. Regression, heredity, and
panmixia. Philosophical Transactions of the Royal Society of London Series A, containing papers of a
mathematical or physical character, 187, 253–318.
Piper, A. M. (1944). A graphic procedure in the geochemical interpretation of water-analyses. Eos, Transac-
tions American Geophysical Union, 25(6), 914–928.
Prasanna, M. V., Chidambaram, S., Gireesh, T. V., & Ali, T. J. (2011). A study on hydrochemical character-
istics of surface and sub-surface water in and around Perumal Lake, Cuddalore district, Tamil Nadu,
South India. Environmental Earth Sciences, 63(1), 31–47.
Prasanth, S. S., Magesh, N. S., Jitheshlal, K. V., Chandrasekar, N., & Gangadhar, K. (2012). Evaluation of
groundwater quality and its suitability for drinking and agricultural use in the coastal stretch of Alap-
puzha District, Kerala, India. Applied Water Science, 2(3), 165–175.
Raghunath, H. M. (1987). Groundwater (2nd ed.). New Delhi: New Age International Publishers.
Rao, N. S. (2006). Seasonal variation of groundwater quality in a part of Guntur District, Andhra Pradesh,
India. Environmental Geology, 49(3), 413–429.
Rasouli, F., Pouya, A. K., & Cheraghi, S. A. M. (2012). Hydrogeochemistry and water quality assessment
of the Kor-Sivand Basin, Fars Province, Iran. Environmental monitoring and assessment, 184(8),
4861–4877.
Richards, L. A. (1954). Diagnosis and improvement of saline and alkali soils. Agriculture Handbook, 60,
1–6.
Saager, R., & Sinclair, A. J. (1974). Factor analysis of stream sediment geochemical data from the Mount
Nansen area, Yukon Territory, Canada. Mineralium Deposita, 9(3), 243–252.
Sahu, U., Panaskar, D., Wagh, V., & Mukate, S. (2018). An extraction, analysis, and prioritization of Asna
river sub-basins, based on geomorphometric parameters using geospatial tools. Arabian Journal of
Geosciences, 11(17), 517.
Saleh, S. M. K., Al-Alaiy, S. H. G., Abdul-Razzak, B. I., & Nasher, G. S. H. (2017). Evaluation of ground-
water quality and its suitability for drinking and agricultural use of rural areas for Zabid Directorate
Wadi Zabid, Hodiedah, Yemen. Journal of Scientific and Engineering Research, 4(7), 10–24.
Sarkar, P. K., & Soman, G. R. (1986). Geology of the area around Katta, Sindhudurg District, Maharashtra.
Based on aerospace data. Journal of the Indian Society of Remote Sensing, 14(2), 43–51.

13
Geochemical mobility of ions in groundwater from the tropical… 2623

Selvam, S. (2015). A preliminary investigation of lithogenic and anthropogenic influence over fluoride ion
chemistry in the groundwater of the southern coastal city, Tamilnadu, India. Environmental Monitor-
ing and Assessment, 187(3), 106.
Shanmugasundharam, A., Kalpana, G., Mahapatra, S. R., Sudharson, E. R., & Jayaprakash, M. (2017).
Assessment of Groundwater quality in Krishnagiri and Vellore Districts in Tamil Nadu, India. Applied
Water Science, 7(4), 1869–1879.
Singaraja, C., Chidambaram, S., Jacob, N., Ezhilarasan, E., Velmurugan, C., Manikandan, M., et al. (2016).
Taxonomy of groundwater quality using multivariate and spatial analyses in the Tuticorin District,
Tamil Nadu, India. Environment, Development and Sustainability, 18(2), 393–429.
Singh, C. K., Kumar, A., Shashtri, S., Kumar, A., Kumar, P., & Mallick, J. (2017). Multivariate statistical
analysis and geochemical modeling for geochemical assessment of groundwater of Delhi, India. Jour-
nal of Geochemical Exploration, 175, 59–71.
Singh, V. B., Ramanathan, A. L., Pottakkal, J. G., & Kumar, M. (2014). Seasonal variation of the solute
and suspended sediment load in Gangotri glacier meltwater, central Himalaya, India. Journal of Asian
Earth Sciences, 79, 224–234.
Subramani, T., Rajmohan, N., & Elango, L. (2010). Groundwater geochemistry and identification of hydro-
geochemical processes in a hard rock region, Southern India. Environmental Monitoring and Assess-
ment, 162(1), 123–137.
Tiwari, A. K., De Maio, M., Singh, P. K., & Singh, A. K. (2016). Hydrogeochemical characterization and
groundwater quality assessment in a coal mining area, India. Arabian Journal of Geosciences, 9(3), 177.
Todd, D. K. (1980). Groundwater hydrology (2nd ed.). New York: Wiley.
Touhari, F., Meddi, M., Mehaiguene, M., & Razack, M. (2015). Hydrogeochemical assessment of the Upper
Cheliff groundwater (North West Algeria). Environmental Earth Sciences, 73(7), 3043–3061.
Varade, A. M., Yenkie, R. O., Shende, R. R., Golekar, R. B., Wagh, V. M., & Khandare, H. W. (2018).
Assessment of water quality for the groundwater resources of urbanized part of the Nagpur District,
Maharashtra (India). American Journal of Water Resources, 6(3), 89–111.
Vasant, W., Dipak, P., Aniket, M., Ranjitsinh, P., Shrikant, M., Nitin, D., et al. (2016). GIS and statistical
approach to assess the groundwater quality of Nanded Tehsil (MS) India. In Proceedings of first inter-
national conference on information and communication technology for intelligent systems (Vol. 1, pp.
409–417). Springer International Publishing.
Wagh, V., Panaskar, D., Aamalawar, M. L., Lolage, Y. P., Mukate, S., & Narshimma, A. (2018a). Hydro-
chemical characterisation and groundwater suitability for drinking and irrigation uses in Semiarid
Region of Nashik, Maharashtra, India. Hydrospatial Analysis, 2(1), 43–60. https​://doi.org/10.21523​/
gcj3.18020​104.
Wagh, V. M., Panaskar, D. B., & Muley, A. A. (2017a). Estimation of nitrate concentration in groundwater
of Kadava River Basin-Nashik District, Maharashtra, India by using artificial neural network model.
Modeling Earth Systems and Environment, 3(1), 36.
Wagh, V. M., Panaskar, D. B., Muley, A. A., & Mukate, S. V. (2017b). Groundwater suitability evaluation
by CCME WQI model for Kadava River Basin, Nashik, Maharashtra, India. Modeling Earth Systems
and Environment, 3(2), 557–565.
Wagh, V., Panaskar, D., Muley, A., Mukate, S., & Gaikwad, S. (2018b). Neural network modelling for
nitrate concentration in groundwater of Kadava River Basin, Nashik, Maharashtra, India. Groundwater
for Sustainable Development, 1, 2. https​://doi.org/10.1016/j.gsd.2017.12.012.
Wagh, V. M., Panaskar, D. B., Muley, A. A., Mukate, S. V., Lolage, Y. P., & Aamalawar, M. L. (2016a). Pre-
diction of groundwater suitability for irrigation using artificial neural network model: A case study of
Nanded tehsil, Maharashtra, India. Modeling Earth Systems and Environment, 2(4), 196.
Wagh, V. M., Panaskar, D. B., Varade, A. M., Mukate, S. V., Gaikwad, S. K., Pawar, R. S., et al. (2016b).
Major ion chemistry and quality assessment of the groundwater resources of Nanded tehsil, a part of
southeast Deccan Volcanic Province, Maharashtra, India. Environmental Earth Sciences, 75(21), 1418.
World Health Organization (WHO). (2011). Guideline for drinking water quality (Vol. 1, 14 ed.).
Zheng, L. Y., Yu, H. B., & Wang, Q. S. (2016). Application of multivariate statistical techniques in assess-
ment of surface water quality in Second Songhua River basin, China. Journal of Central South Univer-
sity, 23(5), 1040–1051.
Zhu, B., Wang, X., & Rioual, P. (2017). Multivariate indications between environment and ground water
recharge in a sedimentary drainage basin in northwestern China. Journal of Hydrology, 549, 92–113.

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Affiliations

Satyajit Gaikwad1 · Suryakant Gaikwad1 · Dhananjay Meshram1 · Vasant Wagh2 ·

Avinash Kandekar3 · Ajaykumar Kadam4
Suryakant Gaikwad
suryakantgaikwad7@gmail.com
Dhananjay Meshram
dcmeshram@unipune.ac.in
Vasant Wagh
wagh.vasant@gmail.com
Avinash Kandekar
amkandekar@unipune.ac.in
1
Department of Geology, Savitribai Phule Pune University, Pune, Maharashtra, India
2
School of Earth Sciences, Swami Ramanand Teerth Marathwada University, Nanded, Maharashtra,
India
3
Department of Geography, Savitribai Phule Pune University, Pune, Maharashtra, India
4
Department of Environmental Sciences, Savitribai Phule Pune University, Pune, Maharashtra,
India

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