Applied Water Science (2022) 12:142

https://doi.org/10.1007/s13201-022-01583-w

ORIGINAL ARTICLE

Geochemical evaluation of groundwater and suitability

of groundwater quality for irrigation purpose in an agricultural region
of South India
Sakram Gugulothu1 · N. Subbarao2 · Rashmirekha Das3 · Ratnakar Dhakate1

Received: 26 August 2021 / Accepted: 3 February 2022 / Published online: 25 April 2022
© The Author(s) 2022

Abstract
The objective of the present study was to evaluate the geochemical processes controlling the groundwater chemistry and
also to assess the groundwater quality suitability criteria for irrigation purposes. An agricultural region of Telangana, South
India, was selected for the present study. A total of 100 groundwater samples were collected and estimated for pH, electri-
cal conductivity (EC), total dissolved solids (TDS), calcium ­(Ca2+), magnesium ­(Mg2+), sodium ­(Na+), potassium ­(K+),
bicarbonate ( HCO−3 ), chloride (­ Cl−), sulfate (SO2− −
4 ), nitrate ( NO3 ), and fluoride ­(F ). The groundwater was characterized
−
+
by mostly alkaline conditions with a dominance of N ­ a and HCO3 ions, indicating the prevailing conditions of weather-
−

ing and dissolution of silicate minerals. The various geochemical signatures such as ­Na+ vs ­Cl−, ­Ca2+ + ­Mg2+ vs HCO−3 ,
­Ca2+ + ­Mg2+ vs HCO−3 + SO2− 4 , HCO3 vs ­Cl +
− −
4 , ­Ca
SO2− 2+
+ ­Mg2+ vs total cations, and ­Ca2+ + ­Mg2+ vs ­Na+ + ­K+ and
the saturation indices with respect to calcite, halite, and gypsum suggest obviously the dominant conditions of carbonate
weathering associated with the reverse ion exchange and evaporation processes as the geogenic factors. The linear trend
of TDS vs NO−3 + ­Cl−/HCO−3 clearly specifies the influence of non-geogenic sources on the aquifer system. These are the
important contributors to the variation in the groundwater chemistry. However, the impact of the geogenic source is mask-
ing the influence of the anthropogenic source in some areas of the present study region. According to the salinity vs sodium
adsorption ratio, residual sodium carbonate, magnesium ratio, and Kelly ratio, 99.9%, 7.06%, 63.07%, and 51.27% of the
total study region come under the unsuitable categories for irrigation purposes, respectively. Therefore, the findings of this
study recommended some site-specific appropriate management strategies for the safe supply of groundwater for proper crop
growth and consequently for sustainable development of the rural environment.

Keywords Groundwater chemistry · Groundwater quality · Crop growth · Agricultural region

Introduction (Sundraiah et al. 2014; Subba Rao 2017; Faten et al. 2016;
Chetan et al. 2017; Laxman et al. 2021; Subba Rao et al.
Globally, groundwater is a natural resource for domestic 2021a, b). However, once the groundwater quality becomes
(65%), agricultural (20%), and industrial (15%) purposes an inferior type due to the influences of geogenic and non-
(Saeid et al. 2018). Studies on groundwater resources have geogenic sources, it will not be suitable for any purposes in
become vital in semiarid regions for various purposes general (Subba Rao et al. 2021c). The quality of ground-
water is controlled by geochemical processes that depend
upon the topographical features, flow path, recharge, nature
* Sakram Gugulothu of lithology, and rock weathering associated with mineral
[email protected]
dissolution, ion exchange, and evaporation (Li et al. 2013;
1
CSIR-National Geophysical Research Institute, Saravanan et al. 2015; Subba Rao et al. 2017, 2021a, b).
Hyderabad 500 007, Telangana, India Besides this, increasing exploitation of groundwater, rapid
2
Department of Geology, Andhra University, urbanization and industrialization, over-application of chem-
Visakhapatnam 530 003, Andhra Pradesh, India ical fertilizers and pesticides for higher plant growth, animal
3
Department of Geology, Utkal University, waste, and improper drainage systems are important human-
Bhubaneswar 751 004, Odisha, India induced activities, which damage the natural occurrence of

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the chemical quality of groundwater and consequently not management planning for taking the appropriate remedial
only affect human health but also reduce crop production measures to protect the aquifers from contamination caused
(Deepali et al. 2015; Rahmati et al. 2015; Li et al. 2016a, b; by natural (geogenic) and anthropogenic (non-geogenic)
Kouakou et al. 2017; Wagh et al. 2019). origins. Therefore, the geogenic processes and agricultural
Some recent studies have been exampled here: Contami- activities on the aquifer conditions need to be understood
nation was caused by human and agricultural activities that everywhere for taking the appropriate suitable measures.
directly and/or indirectly damage the groundwater quality The residents in the State of Telangana, South India,
due to the influence of dissolution and transport of excess mainly rely on groundwater resources for their drinking
quantities of fertilizers, and also through the changes in the and irrigation purposes due to the insufficient supply of
water–rock reactions in the soils and aquifers in the deltaic surface water sources. The present study region faces the
region of the Cauvery River in Tamil Nadu, India (Vetrimu- deterioration of the groundwater quality in some places due
rugan and Elango 2014). Because of the dissolution of min- to the lack of proper awareness on the planning of disposal
erals, evaporation, and non-geogenic impact, the quality of of household wastes, septic tank leakages, animal wastes,
groundwater has considerably deteriorated in the Jazan arid and uncontrolled usage of chemical composts, application
area of Saudi Arabia (Alfy et al. 2015). Groundwater quality of irrigation water flows, etc. As a result, the groundwater
was mainly controlled by the lithology, dissolution, precipi- quality may not be suitable for drinking purposes as well as
tation of minerals, and ion exchange in irrigated land on the for irrigation purposes. However, nobody has so far been
Southeastern edge of the Tengger Desert, China (Li et al. carried out any research work from the study region so that
2016a). The lithological variation was caused by the changes the present study would be useful as baseline information
in the groundwater quality due to the weathering of the rock for further work in the future. Therefore, the main objec-
minerals and evaporation processes in the East Wasit Prov- tive of the present study was to evaluate (a) the weathering
ince, Central Iraq (Ghalib 2017). The chemical weathering processes associated with the ion exchange and evaporation
of the country rocks associated with the dissolution of min- controlling the groundwater chemistry by using the vari-
erals and carbonates, and ion exchange, and also man-made ous bivariate diagrams and saturation indices, and (b) the
pollution mainly were influenced the groundwater quality suitability of groundwater quality for agricultural purposes
in Northwestern Tunisia (Ayadi et al. 2018). In Western by adopting various irrigation chemical factors like sodium
India, not only the geogenic processes (silicate weather- adsorption ratio, residual sodium carbonate, magnesium
ing, ion exchange, and evaporation) as the main governing ratio, and Kelly ratio. This assists in implementing the
factors of the chemistry of groundwater, but also the non- proper site-specific remedial measures for the sustainable
geogenic sources (domestic wastes, irrigation-return-flows, development of society.
and animal wastes) as the secondary sources were damaged
the chemical groundwater quality (Wagh et al. 2019) The
water–rock interactions with ion exchanges were caused by Study area
the inferior groundwater quality for drinking and irrigation
purposes in the Lower Ketar Watershed, Ethiopia (Tolera Location
et al. 2020). The water–rock interactions associated with
the ion exchange and evaporation as the prime geochemi- The study region lies between latitude 17°23′–17°25′ N and
cal regulating factors of the geochemical characteristics and longitudes 77°45′–78°50′ E in the State of Telangana, South
also the anthropogenic activities as the secondary factors India, covering an area of 632.45 k­ m2 (Fig. 1a), which falls
were caused by the deterioration of the chemical quality in the toposheets of 56 G/15 and 56 G/16 with a scale of
of groundwater used for irrigation and drinking purposes 1:50,000 of the Survey of India. The region experiences a
in a rural part of Telangana, South India (Subba Rao et al. dry climate with an average annual temperature of 14 °C
2021c). (winter) to 41 °C (summer) and an average annual rainfall
From the review literature, it can be said that knowledge of about 940 mm. The stream pattern comes under the sub-
of the geochemical processes controlling groundwater chem- dendritic type.
istry is a very important aspect of dealing with groundwater-
related issues. The identification of geochemical processes Hydrogeological conditions
helps in understanding the changes occurring in groundwa-
ter quality due to the interaction with aquifer material. On The region has a gentle slope. The calcium carbonate con-
the other hand, understanding the changes in the chemical cretions are intermixed with soil. The important geologi-
quality of groundwater caused by human-induced activities cal formations are basalts and granite (Fig. 1b). Laterite
like agriculture is also an essential issue, especially in arid occurs in patches. The former types are fine-grained with
and semiarid regions. This type of study in turn assists in dark-colored rocks, which contain the minerals calcium

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Applied Water Science (2022) 12:142 Page 3 of 13 142

Fig.1  Location of the study area with (a) groundwater sample locations and (b) geology

plagioclase feldspars and clinopyroxene with olivine, quartz, following the standard field procedures suggested by APHA
hornblende, nepheline, orthopyroxene, etc. The latter types (2012).
are medium- to coarse-grained rocks, which are composed of The hydrogen ion concentration (pH) and electrical con-
quartz, plagioclase and potassium feldspars, biotite, apatite, ductivity (EC) were estimated in the field, using their porta-
hornblende, etc. These rocks are hard. However, the basalts ble meters (Hanna H-198130). Total dissolved solids (TDSs)
become water-bearing formations due to the occurrence of were computed, using a formula, SEC × 0.64 (Hem 1991).
vesicular structures, cracks, and joints in them, while the The chemical parameters, such as calcium ­(Ca2+), magne-
granites become aquifer formations due to the presence of sium ­(Mg2+), sodium (­ Na+), potassium (­ K+), bicarbonate
weathered and fractured rock portions. Though the later- ( HCO−3 ), chloride ­(Cl−), sulfate (SO2−
4 ), nitrate ( NO3 ), and
−

ites are porous, they are poorly permeable. Groundwater fluoride ­(F−), were determined, using the titration, calcula-
exists under the unconfined to semi-confined conditions. tion, and flame photometer (Elico CL-378), UV spectro-
The depth of groundwater level varies from about 18–28 m photometer (Photolab-6600 WTW,), and ion-selective elec-
below ground level. trode (Orion), following the standard water quality methods
In some areas, the taste of the groundwater quality (APHA 2012). The analytical precision between the ionic
appears to be slightly brackish due to the influence of the concentrations of cations and anions was within the stand-
anthropogenic sources (domestic waste, septic tank spill- ard limit of ± 5%, supporting the data precision (Subba Rao
ages, irrigation-return-flows, chemical fertilizers, animal 2017).
wastes, etc.) on the groundwater system, which was observed
during the field work. Computation of chloro‑alkaline indices

To assess the role of cation exchange and reverse ion

Materials and methods exchange in the aquifer system, the chloro-alkaline indices
(CAI-1) and CAI-2) were adopted here (Eqs. 1 and 2) as
Sampling and analytical procedure proposed by Schoeller (1977). A negative index of CA (base
ion exchange process) indicates an exchange of C ­ a2+ and
Sampling was carried out in the present study region during ­Mg2+ ions from the groundwater with ­Na+ and ­K+ ions from
the summer month of May 2015. A hundred groundwater the aquifer material (Deeapli et al. 2015), whereas a positive
samples were collected (Fig. 1a) in one-liter polythene bot- index of CA (reverse ion exchange) reflects the adsorption
tles. They were cleaned with 1:1 dilute HCl and washed of ­Na+ and ­K+ ions on the aquifer material with the release
away with distilled water three times before the sampling, of ­Ca2+ and ­Mg2+ from the groundwater.

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142 Page 4 of 13 Applied Water Science (2022) 12:142

Cl− − (Na+ + K+ ) Na+

CAI − 1 = (1) KR = ( 2+ (7)
Ca + Mg2+
)
Cl−

Cl− − (Na+ + K + )
CAI − 2 = (2) Application of GIS analysis
SO2− 2−
4 + HCO3 + CO3 + NO3
− −

In the analysis of GIS, the toposheets were digitized, using

Computation of saturation index ArcGIS 10.7 software to generate the thematic spatial maps
for observing the variation in the chemical quality of ground-
The saturation index (SI) is widely used to envisage the water. Then, the spatial variation maps were extracted, using
chemical activities of particular minerals in the chemistry inverse distance weighted interpolation tools (Subba Rao
of groundwater (Subba Rao et al. 2017). The SI was com- et al. 2021b).
puted to know the role of evaporation through the evalua-
tion of equilibrium between water and respective minerals
(Eq. 3) by comparing the ion activity product (IAP) with the Results and discussion
solubility product (Ksp), using the geochemical software
PHREEQC (Parkhurst et al. 1999). Generalized groundwater chemistry

KIAP The pH measured from the groundwater samples of the pre-

SI = (3)
KSP sent study region was between 6.30 and 8.90, and its aver-
age was 7.14 (Table 1), indicating mostly alkaline nature
If SI exceeds zero, it represents the oversaturation (pre- (Deepali et al. 2015). The EC, which expresses the level
cipitation) concerning a particular mineral (Subba Rao et al. of transmitting capacity of current for the property of the
2017). If SI is below zero, it indicates the unsaturation (dis- water medium, ranged from 88 to 1600 µS/cm with an aver-
solution) in respect of a concerned mineral. If SI is equal to age of 454.76 µS/cm, indicating multiple processes taking
zero, it signifies the saturation (equilibrium) associated with place in the groundwater system (Subba Rao 2017). The
a particular mineral. TDS varied from 56.32 to 1024 mg/L, which is an average of
291.05 mg/L controlled by both geogenic and non-geogenic
Computation of irrigation water quality indices sources (Subba Rao et al. 2017).
Among cations, the ­C a 2+ content was from 8.02 to
The suitability of the groundwater quality for irrigation pur- 152.30 mg/L, being an average of 49.60 mg/L (Table 1).
poses was assessed, using salinity (EC), sodium adsorption Calcium feldspars are the main source of higher concentra-
ratio (SAR), residual sodium carbonates (RSCs), magnesium ­ a2+ (Subba Rao and Maya Chaudary 2019). The
tion of C
ratio (MR), and Kelly’s ratio (KR), as suggested by Kel- 2+
­Mg was between 2.43 and 92.42 mg/L with an average
ley (1963), Eaton (1950), Richards (1954), and Szaboles of 23.53 mg/L. This is mainly attributed to the ferromagne-
and Darab (1964). These irrigation chemical parameters are sian minerals (olivine, pyroxene, biotite, etc.) present in the
widely used in different parts of the world (Faten et al. 2016;
Kouakou et al. 2017; Subba Rao 2018; Mukate et al. 2020; Table 1  Summary of the chemical composition of groundwater
Subba Rao et a. 2021b), which were computed following the Chemical parameters Minimum Maximum Average
equations (Eqs. 4–7) and taking the ions in milliequivalents
per liter (meq/L). pH 6.30 8.90 7.14
EC (μS/cm) 88.00 1600.00 454.76
Na+ TDS (mq/L) 56.32 1024.00 291.05
SAR = √
(4) Ca2+ (mq/L) 8.02 152.30 49.60
(Ca2+ +Mg2+ )
2 Mg2+ (mq/L) 2.43 92.42 23.53
Na+ (mq/L) 3.00 416.00 54.13
K+ (mq/L) 1.00 118.00 6.20
RSC = HCO−3 + CO2− (5)
) ( 2+
− Ca + Mg2+
( )
3 HCO −3 (mq/L) 20.70 584.79 147.29
Cl− mq/L) 17.73 425.40 127.52
Mg2+ 4 (mq/L)
SO2− 30.00 166.00 97.90
MR = ( 2+ ) × 100 (6) NO−3 (mq/L) 0.04 585.20 56.27
Ca + Mg2+
F− (mq/L) 0.22 5.41 1.13
pCO2 − 3.05 − 0.43 − 1.18

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Applied Water Science (2022) 12:142 Page 5 of 13 142

basement rocks, apart from the sources of non-geogenic ori- on the sources and solubilities of ions (Hem 1991; Subba
gin (domestic wastes, septic tank leakages, etc.) (Subba Rao Rao 2017).
2021). The ­Na+ ranged from 3 to 146 mg/L, and its aver- Since the present study region faces problems relating
age was 54.13 mg/L. This could be due to the influence of to the geogenic and anthropogenic activities, it needs an
sodium feldspars, household wastes, irrigation-return-flows, assessment of the sources of dissolved ions in the aquifer
etc., on the groundwater (Deepali et al. 2020). The ­K+ con- system, using the different bivariate diagrams (­ Na+ vs ­Cl−,
tent varied from 1 to 118 mg/L with an average of 6.20. The ­Ca2+ + ­Mg2+ vs HCO−3 , ­Ca2+ + ­Mg2+ vs HCO−3 + SO2− 4 ,
potassium feldspars are the chief sources, and the potassium HCO−3 vs C ­ l − + SO2−
4 , ­ C a 2+
+ ­
M g 2+
vs total cations,
fertilizers are the secondary sources of K­ + in the groundwa- ­Ca2+ + ­Mg2+ vs N ­ a+ + ­K+ and TDS vs NO−3 + ­Cl−/HCO−3 ,
ter (Subba Rao 2002). The concentrations of groundwater ion exchange indices (chloro-alkaline indices of CAI-1 and
were in the decreasing order of N ­ a+ > ­Ca2+ > ­Mg2+ > ­K+. CAI-2), and saturation indices with respect to calcite, halite,
+
The dominance of N ­ a in the groundwater indicates the and gypsum for taking the site-specific suitable measures
weathering and dissolution of the sources of silicate miner- for sustainable development of the rural community. These
als and anthropogenic origins (Subba Rao and Surya Rao geochemical signatures have been widely used (Subba Rao
2010; Subba Rao et al. 2020). et al. 2017; Wagh et al. 2019; Deepali et al. 2020; Manikan-
Among anions, the HCO−3 content ranged from 20.70 to dan et al. 2020), which are discussed below:
584.79 mg/L with an average of 147.29 mg/L (Table 1).
This is a result of the release of the ­CO2 into the soil zone
Geogenic sources
due to the consequence of the decay of organic matter and
weathering of silicate minerals, apart from the influence
Influence of rock weathering on groundwater chemistry
of atmospheric ­CO2 (Subba Rao et al. 2017). The C ­ l− was
from 17.73 to 425.40 mg/L with an average of 127.52 mg/l.
Rock weathering (or cation exchange) and halite dissolution
Man-made activities (domestic waste, septic tank spillages,
play a significant role in dissolving the ions in the aquifer
irrigation-return-flows, etc.) could be the chief contributors
system (Eqs. 8 and 9). If the groundwater system received
of ­Cl− to the groundwater (Laxman et al. 2019). The SO2− 4 the ­Na+ and ­Cl− ions by the dissolution of halite, the ratio
varied from 30 to 166 mg/L, and its average was 97.90 mg/L,
of these ions would be equal to unity (Deepali et al. 2015;
which may be caused by the application of gypsum used for
Subba Rao et al. 2017). Excess N ­ a+ over C­ l− represents
the alternation of soil conditions (Subba Rao et al. 2012a, b).
the rock weathering or cation exchange, while the excess
The NO−3 was between 0.04 and 585.20 mg/L with an aver-
­Cl− over ­Na+ indicates the reverse ion exchange (Subba Rao
age of 56.27 mg/L. The influence of sewage waste, septic
2008; Subba Rao et al. 2017). Nine percent of the ground-
tank leakage, agricultural compost, and animal waste could
water sampling points in the present study region fall on the
be the chief source of NO−3 (Deepali et al. 2015; He et al.
uniline of ­Na+ and ­Cl− ions (Fig. 2a). This reflects the halite
2019). The ­F− was from 0.22 to 5.41 mg/L, and its average
dissolution process. A few sampling points (13%) are found
was 1.13 mg/L. The fluoride minerals (fluorite, biotite, horn-
above the theoretical line of ­Na+ and ­Cl− ions, specifying
blende, etc.) and phosphate fertilizers may be the sources of
the rock weathering or cation exchange process. Most sam-
­F− in the groundwater body (Deepali et al. 2020; Subba Rao
pling points (78%) are observed below the equiline of ­Na+
et al. 2020a). The decreasing order of abundance of anions
and ­Cl− ions, which measures the contribution of ions from
was HCO−3 > ­Cl− > SO2− −
4 > NO3 > ­F . The higher HCO3 in
− −
the reverse ion exchange process as the chief source. Since
the groundwater indicates the prevailing conditions of min-
the present study region experiences a semiarid climate and
eral dissolution in the groundwater system (Subba Rao 2018;
comes under the agricultural area, it leads not only to the
Deepali et al. 2021).
formation of soil salts (NaCl, ­CaSO4, etc.) but also adds ions
associated with the N ­ a+ and C­ l− to the groundwater body
Controlling processes of groundwater chemistry
through the application of irrigation-return-flows (Subba
Rao et al. 2012a, b). Because ­Cl− is a non-geogenic origin
The dissolved ions in the groundwater system are derived
(Subba Rao 2014), the excess C ­ l− ion over the N
­ a+ ion can
from geogenic origins (rock-forming minerals) as a chief
also be considered as a source of non-geogenic origin.
source (Manikandan et al. 2020). The non-geogenic origin
(domestic waste, septic tank spillages, irrigation-return- Na , K , Ca2+ , Mg2+ silicates + H2 CO3 Rock weathering
( + + )

flows, chemical fertilizers, animal wastes, etc.) may also → Na+ + K+ + Ca2+ + Mg2+ + HCO−3 + H4 SiO4 + clay product
contribute as a secondary source (Sakram et al. 2019). How- (8)
ever, sometimes secondary sources overtake the influence of
geogenic origin (Subba Rao et al. 2019). Generally, the rela- NaCl Halite dissolution → Na+ + Cl− (9)
tive dominance of dissolved ions in groundwater depends

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142 Page 6 of 13 Applied Water Science (2022) 12:142

Fig. 2  Ionic relations a ­Na+ vs

­Cl− and b ­(Ca2+ + ­Mg2+) vs
HCO−3

2+
( HCO−3 + SO2−
4 ) over ­(Ca + ­Mg2+) reveals the removal of
The diagram C ­ a2+ + ­Mg2+ vs HCO−3 is frequently used 2+
­Ca and M 2+
­ g ions from the water by the cation exchange
to confirm rock weathering or cation exchange as the domi- process, or excess HCO−3 that is added to the groundwater
nant controlling process of groundwater quality (Sakram and body by weathering of ­Na+ and ­K+ silicates (Wagh et al.
Admilla 2018; Vinnarasi et al. 2021). Above 1:1 equiline of 2019), apart from the soil C­ O2 released from the decay and
­(Ca2+ + ­Mg2+) and HCO−3 indicates the dominance of C ­ a2+ decomposition of organic matter (Eqs. 10 and 11).
2+
and ­Mg ions over the HCO3 caused by rock weathering
−
Further, the computed partial pressure of carbon diox-
or cation exchange, and below it confirms the release of ide (PCO2) in the groundwater samples of the present study
HCO−3 into the groundwater caused by feldspar minerals with region varied from − 3.05 to − 0.43 with an average of
carbonic acid ­(H2CO3; Eq. 8). In the present study region, − 1.18 (Table 1), which is more than the atmospheric PCO2
8% of the plotted points are observed below the uniline of (− 3.50). The higher PCO2 of the groundwater indicates the
­(Ca2+ + ­Mg2+) and HCO−3 (Fig. 2b). This indicates that the prevailing conditions of the open system weathering with a
­Ca2+, ­Mg2+, and HCO−3 ions are derived from the dissolu- relatively higher rate of solubility (Vinnarasi et al. 2021).
tion of carbonate rocks, which is further supported by the Therefore, the groundwater of the present study regions
plotting of the groundwater samples that move toward HCO−3 shows a higher concentration of HCO−3 (Table 1).
from the theoretical line of HCO−3 :(Cl− + SO2− 4 ; Fig. 3a).
The maximum plotting points (92%) of the chemical data CO2 + H2 O → H2 CO3 (10)
of the groundwater samples between ­(Ca2+ + ­Mg2+) and
( HCO−3 + SO2−4 ) also show the deviation from the equiline H2 CO3 → H+ + HCO3− (11)
and run toward HCO−3 + SO2− 4 (Fig. 3b), indicating an excess
of HCO−3 . Generally, the dissolution of C­ a2+ and M­ g2+ sili- Further, it is also noted that most groundwater sampling
cates and HCO3 and SO4 associated with the soils give
− 2− points in the plots of (­ Ca2+ + ­Mg2+) vs (­ Na+ + K +) move
an equal amount of these ions in the groundwater system toward ­Ca2+ + ­Mg2+ (Fig. 4a), so that they appear as the
(Deepali et al. 2021). High ­Ca2+ + ­Mg2+ compared to HCO−3 major contributors, which exceeds the N ­ a+ and K
­ + ions
indicates the reverse ion exchange due to the derivation of in the groundwater (Subba Rao et al. 2006). All chemi-
­Ca2+ and ­Mg2+ ions from the aquifer material. If excess cal points of the groundwater samples in the diagram of

Fig. 3  Ionic relations a

HCO−3 vs ­(Cl− + SO2−4 ) and b
­(Ca2+ + ­Mg2+) vs (HCO−3 + SO2−
4
)

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Applied Water Science (2022) 12:142 Page 7 of 13 142

Fig. 4  Ionic relations a

­(Ca2+ + ­Mg2+) vs ­(Na+ + ­K+)
and b ­(Ca2+ + ­Mg2+) vs total
cations

Table 2  Particulars of chloro-alkaline index (CAI), situation index (Eq. 13). From Fig. 5, it is noted that 83% of the groundwa-
(SI), and irrigation index (II) ter sampling points fall toward the positive indices of CAI-1
Chloro-alkaline index (CAI) Minimum Maximum Average and CAI-2. It enlightens the reverse ion exchange as the
chief controlling process in the groundwater system (Deepali
CA1-1 − 3.64 0.94 0.12 et al. 2015).
CA1-2 − 0.78 3.36 0.34
Saturation index (SI) 2Na+ + CaX2 → Ca2+ + 2NaX (12)
Halite − 8.77 − 5.61 − 7.01
Gypsum − 2.45 − 1.22 − 1.90
Ca2+ + 2Na+ → 2Na+ + X2 (13)
Calcite − 1.73 0.67 − 0.71
Irrigation index (II)
EC 88.00 1,600.00 454.76
SAR 0.13 6.71 2.21 Influence of evaporation process on groundwater
RSC (meq/L) − 4.22 8.01 0.14 chemistry
MR 4.86 81.10 44.79
KR 0.06 8.09 1.21 The soils in the present study region contain calcium carbon-
ate concretions, which suggest the prevailing conditions of
the semiarid climate. As stated above, evaporate dissolution
­(Ca2+ + ­Mg2+) vs total cations ­(Ca2+ + ­Mg2+ + ­Na+ + ­K+) (halite) occurs in the groundwater system. Thus, it is also
also deviate from the equiline and change their trend toward essential to confirm the role of the evaporation process in the
the total cations (Fig. 4b). This is a result of the total con- groundwater body. Saturation indices (SI) were computed
tribution of the cations from the source (Subba Rao 2008). concerning calcite (­CaCO3), halite (NaCl), and gypsum
Therefore, these diagrams clearly explain the carbonate ­(CaSO4), using Eq. 3. The results are shown in Fig. 6. They
weathering as the major controlling process of groundwater predict the reactive minerals with the help of the chemistry
chemistry due to the occurrence of soil ­CO2. of groundwater (Deepali et al. 2015). All groundwater sam-
ples show negative values of SI concerning halite (− 8.77
Influence of ion exchange process on groundwater to − 5.61 with an average of − 7.01) and gypsum (− 2.45 to
chemistry − 1.22 with an average of − 1.90), indicating their unsatu-
ration (dissolution) state. Twenty-six percent and 74% of
As discussed earlier, the excess ­Cl− ion over the ­Na+ ion the groundwater samples show negative and positive values
in the majority (78%) of the groundwater samples (Fig. 2a) of SI concerning calcite (− 1.73–0.67 with an average of
explains the reverse ion exchange process taking place in − 0.71), representing the unsaturation and oversaturation
the aquifer system. To verify this phenomenon further in the (precipitation) states, respectively. This further supports the
groundwater of the present study area, the chloro-alkaline occurrence of calcium carbonate concretions in the present
indices (CAI-1) and CAI-2) were computed (Eqs. 1 and 2) study area.
and the results are shown in Table 2. The values of CAI-1
varied − 3.64 to 0.94 with an average of 0.12, while those Non‑geogenic source
of CAI-2 were from − 0.78 to 3.36 with an average of
0.34. They demonstrated in Fig. 5 representing the cation The present study region is a part of an agricultural
ion exchange (Eq. 12) and reverse ion exchange processes rural area and also shows poor disposal conditions for

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142 Page 8 of 13 Applied Water Science (2022) 12:142

Fig. 5  Schoeller’s ion exchange

reactions (CA1-1 vs CAI-2) 4.00
3.00
Reverse ion exchange
2.00
1.00

CAI-2
0.00
-1.00
-2.00
Cation exchange
-3.00
-4.00
-4.00 -3.00 -2.00 -1.00 0.00 1.00 2.00 3.00 4.00
CAI-1

Fig. 6  Sample-wise distribution

of saturation indices concerning
calcite, gypsum, and halite

household waste and septic tank spillages, animal waste, chemistry of groundwater, the relationship of TDS and
unlimited use of irrigation-return-flows and agricultural ( NO−3 + ­Cl−/HCO−3 ) is widely used (Li et al. 2019; Subba
fertilizers, etc. Generally, they modify the groundwater Rao et al. 2021c). This relation illustrates a linear trend
chemistry due to the adding of additional concentrations (y = 0.0077x + 1.9265 and R2 = 0.1066; Fig. 7) obviously
of ions and thereby inferior groundwater quality occurs. supporting the influence of the non-geogenic sources on
To know the influence of non-geogenic sources on the the groundwater system. As a result, the impact of the

13
Applied Water Science (2022) 12:142 Page 9 of 13 142

C3S2, respectively (Fig. 8). They represent the good (iso-

lated patch), poor (northern, eastern, and isolated patches
in western parts), and very poor (northern, central and
southern parts) groundwater quality for irrigation purposes,
respectively.

Residual sodium carbonate

Residual sodium carbonate (RSC) is also used to evaluate

the groundwater suitability for crops, which is a relationship
between CO2− 3
+ HCO−3 and ­Ca2+ + ­Mg2+ (Eq. 5). The RSC is
classified into three types (Alaya et al. 2014). They are suit-
able (< 1.25 meq/L), marginally suitable (1.25–2.50 meq/L),
and unsuitable (> 2.50 meq/L) types for irrigation purposes.
The RSC varied from − 4.22 to 8.01 meq/L, and its average
Fig. 7  Bivariate plot showing the relationship between TDS and
(NO−3 + ­Cl−/HCO−3 ) was 0.14 meq/L (Table 2). According to the classification of
RSC, the suitable, marginally suitable, and unsuitable types
are observed in the areas of 86.24%, 6.70%, and 7.06%,
anthropogenic source is masking the influence the geo- respectively, for irrigation purposes (Fig. 9a). The unsuit-
genic source. This is the main reason that the groundwater able groundwater quality is observed from the eastern part
quality in some areas in the present study region appears to of the study region.
be slightly brackish, depending upon the hydrogeological
environmental conditions. Magnesium ratio

Generally, ­Mg2+ damages the soil structure, when the water

Groundwater quality for crop growth has higher ­Na+ and salinity, which decreases the crop yields.
The magnesium ratio (MR) was computed, using Eq. 6
Salinity (EC) vs Sodium adsorption ratio (SAR) (Szaboles and Darab, 1964). The MR was between 4.86 and
81.10, and its average was 44.79 (Table 2). If MR is higher
In the present study region, groundwater is the main than 50% in water, it is harmful to irrigation, and if it is less
source of crop growth. However, its poor quality reduces than 50%, it is suitable for irrigation purposes (Faten et al.
crop growth considerably (Aravinthasamy et al. 2020). 2016; Subba Rao 2017). Accordingly, 36.93% and 63.07%
Hence, the assessment of the suitability of the groundwa- of the spatial areas come under the suitable and non-suitable
ter quality is essential for taking management measures to types for irrigation purposes, respectively (Fig. 9b). Ground-
ensure healthy crop growth (Ghalib 2017). Groundwater water quality is observed to be unfit for irrigation purpose
salinity expressed in terms of EC plays a significant role from the areas of the central part spreading from western to
in crop growth. The salinity of groundwater is classified as eastern side of the study region.
low, C1 (EC < 250 μS/cm), medium, C2 (250–750 μS/cm),
high, C3 (750–2250 μS/cm), and very high, C4 (> 2250 Kelly’s ratio
μS/cm). With the increase in the groundwater salinity, crop
production can be reduced (Subba Rao 2017). The sodium Kelly’s ratio (KR) is used to assess the irrigation water
adsorption ratio (SAR) evaluates the influence of the ­Na+ quality (Kelley 1963), which measures the levels of ­Ca2+
content about C ­ a2+ and M­ g2+ (Eq. 4), which is expressed and ­Mg2+ ions (Eq. 7). If KR is below one, it is suitable for
in terms of alkalinity. If SAR increases, it reduces soil irrigation, and if it is above one, it is not suitable for irriga-
permeability, which has adverse effects on crop growth tion purposes (Aravinthasamy et al. 2020). The KR was
(Subba Rao 2018; Subba Rao et al. 2021c). from 0.06 to 8.09 with an average of 1.21 (Table 2). As per
The SAR is classified as low, S1 (< 10), medium, S2 the classification of KR, 48.73% and 51.27% of the study
(10–18), high, S3 (10–28), and very high, S3 (> 28) (Subba region fall into the suitable and unsuitable water quality
Rao 2017). The EC ranged from 88 to 1600 μS/cm with an types for irrigation purposes, respectively (Fig. 9c). The
average of 454.76 μS/cm (Table 1), while the SAR varied unsuitable groundwater quality zone for irrigation purpose
from 0.13 to 6.71 with an average of 2.21 (Table 2). Based is mainly observed from the southern part of the study
on the EC vs SAR, 0.10%, 29.83%, and 70.07% of the total region.
study region fall into the zones of the C2S1, C3S1, and

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142 Page 10 of 13 Applied Water Science (2022) 12:142

Fig. 8  Classification of groundwater quality suitability for irrigation purposes based on EC vs SAR

Recommendations for groundwater quality central, and southern parts, respectively. The quality of
management groundwater in these zones may not support crop yields due
to the reduction in the soil permeability (Subba Rao et al.
According to the EC vs SAR, RSC, MR and KR, 99.9%, 2012a, b, 2021c). Thus, the plant roots are unable to receive
7.06%, 63.07%, and 51.27% of the total study region come water properly and, consequently, nutrients from the soils.
under the poor groundwater quality type for irrigation pur- Therefore, the following site-specific suggestions are rec-
poses. These zones spread mainly in the whole area, eastern, ommended for the sustainable development of groundwater

Fig. 9  Spatial distribution of suitability of groundwater quality for irrigation purposes based on a RSC, b MR, and c KR

13
Applied Water Science (2022) 12:142 Page 11 of 13 142

resources for proper crop growth and consequently for better Acknowledgements The authors are sincerely thankful to the Direc-
living conditions of the rural community. tor, CSIR-National Geophysical Research Institute, Hyderabad, India,
for permitting submission of the paper to the journal. The manuscript
Reference No. is NGRI/Lib/2021/Pub-143. The authors express their
• Inferior groundwater quality should not be used for crop sincere thanks to Editor-in-Chief and anonymous reviewers for their
growth without treatment, valuable and significant comments to improve the manuscript in the
• Application of gypsum as an amendment is necessary to present form.
increase the soil permeability for proper plant growth,
Author’s Contribution Sakram Gugulothu contributed to supervision,
• The quality of groundwater should be improved through methodology, and original draft preparation. N. Subbarao was involved
the implementation of the rainwater recharging strategies in writing and reviewing. Rashmirekha Das contributed to literature
in the entire study region, collection and editing. Ratnakar Dhakate was involved in statistical
• Drainage systems and septic tanks should be maintained analysis and literature collection.
properly to reduce groundwater pollution, especially
Funding The present work did not receive any financial assistance from
where the build-up areas occur, any funding agency.
• Biological treatment plants and recycling of solid waste
are necessary for a clear and clean rural environment, Declarations
particularly where the population is more, and
• Creating public awareness on environmental issues must Conflict of interest The authors declare that they have no known com-
be needed for building a healthy society. peting financial interests or personal relationships that could have ap-
peared to influence the work reported in this paper.

Open Access This article is licensed under a Creative Commons Attri-

Conclusions bution 4.0 International License, which permits use, sharing, adapta-
tion, distribution and reproduction in any medium or format, as long
The following important conclusions were drawn from the as you give appropriate credit to the original author(s) and the source,
present study region of Telangana, India, after observing the provide a link to the Creative Commons licence, and indicate if changes
were made. The images or other third party material in this article are
geochemical processes controlling the chemistry of ground- included in the article's Creative Commons licence, unless indicated
water chemistry, using the various geochemical ratios, and otherwise in a credit line to the material. If material is not included in
groundwater quality suitability, using the irrigation chemical the article's Creative Commons licence and your intended use is not
parameters: permitted by statutory regulation or exceeds the permitted use, you will
need to obtain permission directly from the copyright holder. To view a
copy of this licence, visit http://​creat​iveco​mmons.​org/​licen​ses/​by/4.​0/.
• The groundwater was mostly alkaline with a characteriza-
tion of ­Na+ and HCO−3 ions.
• The geochemical ratios such as ­Na+ vs ­Cl−, ­Ca2+ + ­Mg2+
vs HCO−3 , ­C a 2+ + ­M g 2+ vs HCO−3 + SO2− 4 , HCO3
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2019.​15714​03

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