Journal of Hydrology 612 (2022) 128172

Contents lists available at ScienceDirect

Journal of Hydrology
journal homepage: www.elsevier.com/locate/jhydrol

Research papers

Tracing thermal and non-thermal water circulations in shear zones of

Eastern Ghats Mobile Belt zone, Eastern India- inferences on sustainability
of geothermal resources
Tirumalesh Keesari a, b, *, Sitangshu Chatterjee a, b, Mukund Kumar c, Hemant Mohokar a,
Uday Kumar Sinha a, Annadasankar Roy a, b, Diksha Pant a, b, Suraj D. Patbhaje d
a
Isotope Hydrology Section, Isotope and Radiation Application Division, Bhabha Atomic Research Centre, Trombay, Mumbai, India
b
Homi Bhabha National Institute, Bhabha Atomic Research Centre, Mumbai, India
c
Geological Survey of India, Nagpur, India
d
Geological Survey of India, Jaipur, India

A R T I C L E I N F O A B S T R A C T

Keywords: The development of the geothermal resources in India has not progressed mainly due to inadequate under­
Thermal waters standing of the deeper thermal regime and uncertainty over the sustainability of heat source. In this study,
Mahanadi graben isotopes, hydrochemical techniques and integrated geothermometric models have been applied to a low-medium
Eastern Ghats Mobile Belt
enthalpy geothermal system belonging to shear zones of Mahanadi graben, Eastern Ghats Mobile Belt (Eastern
Geothermal energy
Environmental isotopes
India) to gain better insights. Isotope results indicate that thermal waters are meteoric in nature and absence of
Radiocarbon dating δ18O-shift suggests that the subsurface temperatures are below 200 ◦ C. Distinct isotopic and hydrochemical
signatures of thermal waters clearly suggest their origin from different geothermal reservoirs. Thermal waters at
Atri/Tarabalo sites are derived from the southern part of the graben while at Athmalik, from northern part. Away
from graben in southern direction (Taptapani site), the thermal waters are derived from rain occurring at
elevated regions. Seasonal variations in chemical and isotope data are minimum in thermal waters. The esti­
mated reservoir temperatures range between 92 and 124 ◦ C with reservoir depths 1.6 – 2.4 km. Tritium data
suggests that thermal waters are old and have 12–63% mixing with non-thermal water. The modelled radio­
carbon age of thermal waters (13.3 – 20.7 Ka) suggests paleo-recharge of the reservoirs during Last Glacial
Maximum (LGM), characterized by arid climate and low rainfall. A conceptual isotope model illustrating the
genesis and circulation patterns of thermal and non-thermal waters is presented. The study highlights the po­
tential of isotope-based studies in expanding the geothermal energy utilization in India.

1. Introduction
The Proterozoic Eastern Ghats Mobile Belt (EGMB) bordering the
Archaean Dharwar, Bastar and Singhbhum cratonic blocks is an
important Precambrian geological entity of Peninsular India known as a
blueprint for models of reconstruction of Columbia, Rodinia and
Gondwana (Dasgupta et al., 2013; Valdiya, 2016) (Fig. 1a). EGMB is
considered to be a collage of several juxtaposed terrains separated by
major shear zones and is characterized by stretching lineation and in­
ternal homogeneity in terms of litho-package and tectonic history
(Chetty, 2001; Valdiya, 2016). An ultra-high temperature meta­
morphism at mid to lower crustal depths has been reported by many
researchers and the thermal models of the present-day EGMB crust
estimated a Moho temperature of ~550 ◦ C (Dasgupta, 1993; Bhowmik
et al., 1995). The concentrations of radioactive elements and the heat
production are reported to be highest amongst the granulite belts of
India (Kumar et al., 2007) and therefore EGMB is classified under Zone-
II based on the heat flow values (Fig. 1b). Several surface manifestations,
mainly low to medium enthalpy thermal waters with temperatures
ranging from 42 to 59 ◦ C feature in EGMB (GSI, 1987; GSI, 1991; Thussu,
2002). Considering the heat flow values, many researchers have sug­
gested for exploration of thermal waters for electricity production using
binary cycle power plants or through enhanced geothermal systems
(Chandrasekharam and Chandrasekhar, 2010).

* Corresponding author at: Isotope Hydrology Section, Isotope and Radiation Application Division, Bhabha Atomic Research Centre, Trombay, Mumbai, India.
E-mail addresses: tiruh2o@gmail.com, tirumal@barc.gov.in (T. Keesari).

https://doi.org/10.1016/j.jhydrol.2022.128172
Received 11 April 2022; Received in revised form 30 June 2022; Accepted 2 July 2022
Available online 11 July 2022
0022-1694/© 2022 Elsevier B.V. All rights reserved.
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

Studies were conducted on the thermal waters of India covering all
the ten geothermal provinces, which mainly reported the thermo-
tectonic aspects, quality of thermal water, reservoir temperatures and
geochemical processes (GSI, 1987; GSI, 1991; Minissale et al., 2000;
Thussu, 2002; Craig et al., 2013; Zimik et al., 2017). Environmental
isotopes of water (2H, 18O & 3H) and its dissolved species (13C, 14C, 15N
and 34S etc.) were also applied in some cases to gain better insights into
genesis, mixing processes, geochemical evolution and residence time
distribution of thermal fluids (Sammel and Craig, 1981; Navada and
Rao, 1991; Chatterjee et al., 2016, 2017; Keesari et al., 2019). As per the

Fig. 1. a) Major Palaeoproterozoic sutures in Peninsular India classified as the Eastern India, Central India and Western India Suture zones. The Southern Granulite
Terrain was mostly assembled during late Neoproterozoic–Cambrian during the final assembly of the Gondwana supercontinent (modified from Santhosh, 2012), b)
Heat flow map of EGMB, India (cropped from Roy and Mareschal, 2011), c) Geology map with lineaments and geothermal sites (redrawn from Thussu, 2002), a-a′
transect used for generating topographic elevation map from Cartosat 1 (https://bhuvan-app3.nrsc.gov.in, access date and time: 22/11/2020, 8:28 pm) shown in
conceptual diagram (Fig. 12), d) Eastern Ghat Mobile Belt of Proterozoic age surrounded by Singhbhum, Bastar and Dharwar cratons. Mahanadi and Godavari
grabens divide the EGMB into 3 segments and the studied thermal sites fall in central segment (modified from Ramakrishnan, 1987).

2
T. Keesari et al.
current database, the thermal waters age ranges from 40 years in Hi­
malayan province to 18.6 Ka in Godavari Valley (Chatterjee et al., 2018,
Chatterjee et al., 2019) and the estimated temperature ranges from
<50 ◦ C (Himachal region, NW Himalaya) to 250 ◦ C (Puga Valley,
Ladakh) (Craig et al., 2013; Tiwari et al., 2016).
Thermal waters of EGMB did not attract much attention from re­
searchers and authorities due to their low enthalpy and uncertainty over
their sustainability. Studies on these thermal waters were mainly
focused on the water quality and hydrochemical aspects (Thussu, 2002;
Zimik et al., 2017 and references therein). But a few studies were also
conducted to understand the source and recharge of the thermal waters
using isotope techniques (Navada et al., 1995). The chemical geo­
thermometry estimated a wide range of reservoir temperatures from 92
to 277 ◦ C (Navada et al., 1995; Mahala, 2019) while radiocarbon ages
were found to vary from 5 − 18 Ka (Keesari et al., 2019). A few studies
attempted isotope characterization of the non-thermal waters in this
region (Farooq, 2018) but a detailed geochemical analysis of the thermal
groundwaters and their intermixing with the non-thermal waters is still
missing. Poor understanding of the origin and subsurface temperature of
thermal water, its recharge history and sustainability act as major
impediment to the development of strategies for economic exploitation
of these thermal waters.
We constrained the resident time and temperature of the thermal
waters (age and heat content of subsurface thermal reservoirs), there by
trying to understand the upwelling of the juvenile/geothermal waters
that is a novel observation in cratonic, crystalline aquifer with non-
specific magmatic sources. The use of radioisotopes, chemical geo­
thermometers, mixing models and integrated multi-component geo­
thermometry provided unconventional tools to understand the hydro
(geo)dynamic processes of thermal waters that can help to establish the
future Enhanced Geothermal Systems (EGS) of this region.
By using a combination of stable and radioisotope tracers, hydro­
chemistry, geochemical modeling and geothermometry, we developed a
conceptual model for the geothermal reservoir and the associated fluid
circulations and pathways in the Mahanadi graben, EGMB. The objec­
tives of this study are to; i) estimate the subsurface reservoir tempera­
ture, ii) understand the hydrochemical evolution of thermal and non-
thermal waters and their interactions, iii) estimate mean transit times
of thermal water as well as trace the flow paths and iv) develop a model
for the thermal and non-thermal water circulations in EGMB, Indian
Shield.
2. Regional and structural components
The EGMB falls in a tectonically stable, non-orogenic field of Indian
shield. This was formed along the eastern coast of peninsular India due
to Neoproterozoic collisions between the Indian cratons and east
Antarctica (Dasgupta et al., 2013; Valdiya, 2016). These collisional
events and the subsequent successive deformations created a number of
faults and shear zones, paving way for complex groundwater circulation
patterns and geothermal activity (Ramakrishnan, 1987; Valdiya, 2016).
The Mahanadi and Godavari rift systems divide the EGMB into three
segments, viz., northern, central and southern (Fig. 1d). The EGB is
broadly divided into the three groups, viz., Khondalite Group, Char­
nockite Group and Migmatite Group. Moving from east to west, the
sequence of these groups is Eastern Khondalites, Central Migmatites,
Western Khondalites & Charnockites and Westernmost Transition Zone
(Ramakrishnan, 1987). The geological succession of the study area is
shown in Table (S1). Petrological studies infer that the EGB Group of
rocks comprises garnet-sillomanite schist and gneisses (Khondalite
rocks), hypersthene bearing granulite and gneisses (Charnockite rocks),
biotite bearing granite gneisses, pink granites and porphyritic granite.
The EGB Group of rocks is directly overlain by the rocks of the Gond­
wana Supergroup, which in turn are overlain by alluvium. The Khon­
dalite rocks display well developed foliation trending NW-SE to NNW-
SSE and dipping at high angles 45◦ -75◦ towards NE and north
3
Journal of Hydrology 612 (2022) 128172
respectively. Many faults and joints exist in Khondalite and Granitic
Group of rocks, among which the lineaments trending NE-SW (i.e.,
Taptapani to Tarabalo) and NW-SE (i.e. Athmalik to Atri) play a critical
role in thermal water circulation in EGMB (Fig. 1c). The generalized
litho-units and digital elevation model of the study area are shown in
Fig. 2a and b.
The Atri site falls in a lateritic terrain within the EGB Group of rocks
and has Charnockite and Granite rock exposures in the northwestern and
Khondalite and Charnockite in the southern, southeastern and south­
western parts. Gondwana Supergroup rocks are exposed in the north­
eastern part. In general, the foliation shows moderately higher dips i.e.
50◦ − 70◦ towards north. Four sets of joints are observed trending N-S, E-
W, NW-SE and NE – SW, and the thermal sprout is present at the
intersection of NE-SW and NW-SE trending joints (Fig. 2c). Tarabalo site
is located within alluvium of the granitic terrain surrounded by isolated
hill masses of Charnockite and Khondalite in the northeastern and
southeastern parts respectively while the exposures of Charnockite and
granite are present in the southern, western and northwestern parts
respectively. The foliation within the granite and Charnockite trends E-
W dipping 40◦ − 60◦ towards north while the foliation in the Khondalite
trends NW-SE to ENE-WSW dipping 50◦ − 65◦ towards NE to NW. The
foliations within the granite are not prominent suggesting latter
emplacement. The joints are found to be E-W and N-S trending in the
southern and WNW-ESE and NE-SW trending in the western and
northwestern parts respectively. The multiple thermal sprouts are found
at the intersection of NW-SE and NE-SW lineaments (Fig. 2d). The
Athmalik site is located on NNE-SSW trending fracture and is very close
to the intersection of NE-SW and NW-SE trending major fracture
(Fig. 2e). Two sets of foliations are observed dipping NW and NE with
high dip. The thermal sprout at Taptapani site fall in the contact zone of
Khondalite and Charnockite rocks (Fig. 2f). Two sets of deep to shallow
vertical fractures trending NE-SW and NW-SE are noticed. Massive grey
granite and micaceous rock exposures with foliation having 57◦ dip
towards SE direction are also observed in this site.
The study area has tropical climate characterized by high tempera­
ture, high humidity and medium-to-high rainfall. The annual rainfall
varies from 1008 to 1988 mm with an average of 1481 mm. The water
levels range from 2 to 10 m below ground level during pre-monsoon
(April 2016) and 2 to 5 m during post-monsoon (November 2016).
The depths of the sampled wells range from 80 to 180 m and the
groundwater flow is controlled by the topographic slope (Kundu et al.,
2002). The minimum aquifer thickness was found in the high topo­
graphic area and it gradually increases towards the hot springs and at­
tains a maximum thickness of about 66 m near the Tarabalo hot spring
(Farooq et al., 2018).
3. Materials and methods
3.1. Sampling
Water samples were collected from both thermal (sprouts) and non-
thermal sources (dug wells, tube wells and bore wells) at four sites
during pre-monsoon (39), i.e. May 2016 and post-monsoon (46), i.e.,
September 2016. A total of 19 thermal waters and 27 non-thermal water
samples were collected. Thermal water discharges during post-monsoon
period were measured using float and stopwatch method. The sample
locations for individual sites are shown in Fig. 2c–f. The field parameters
like pH, electrical conductivity (EC), temperature, and dissolved oxygen
(DO) were measured on site using multi-parameter kit (Hanna Make).
The temperature range of this equipment is 0.0 to 70.0 ◦ C with a
sensitivity of ± 0.15 ◦ C. Gran method was used to determine alkalinity.
Before sample collection, wells were flushed/pumped until a stable
temperature is obtained. Multiple sets of samples were collected at each
site, which include a 100 mL of untreated water for anions, 100 mL of
0.45 µm filtered water acidified with concentrated HNO3 for cation and
trace elements, 50 mL of unfiltered and untreated water for
T. Keesari et al.
Fig. 2. a) The generalized lithozones and lineaments falling in the study area (drawn from Ramakrishnan et al., 1987, Mahala, 2019), b) Digital elevation model of
the study area with thermal water sites identified, Sampling locations of thermal and non-thermal waters from c) Atri, d) Tarabalo, e) Athmalik and f) Taptapani sites.
Lineaments along with the elevation of the site and its surroundings are also shown. Numbers indicate sample ID’s listed in Table S2.
environmental stable isotopes and 500 mL of unfiltered and untreated
water for environmental tritium. The details of collected thermal and
non-thermal water samples are provided in Table S2.
3.2. Chemical measurements
The anions (Cl , F ,
− −
NO–3
& SO2−
) and cations (Na , K , Mg &
4
+ +
Ca2+) were quantified using Ion Chromatograph (Dionex DX-500)
coupled to a conductivity detector (ED 40). A total of 38 samples were
collected for chemical analysis (21 post-monsoon and 17 pre-monsoon).
The analytical columns used for anions and cations separation were
AS11 and CS12A respectively. Elution was performed by 20 mN H2SO4
and 5–15 mN NaOH for cations and anions respectively. Suppressed
conductivity detection was employed to quantify the ion concentrations
and the typical detection limits for major ions were 0.01–0.5 mg/L. The
trace elements (Rb, Li, B, Cs and Si) were measured using ICP-OES and
the detection limits were in the range of 1–5 µg/L. Sigma-Aldrich 1000
ppm standard solutions were used to prepare the working standards for
Journal of Hydrology 612 (2022) 128172
calibration purpose. The chemical accuracy was determined by
computing error in charge balance (Eq. (1)), which was found to be
within acceptable limits (±5%). The chemical data of pre- and post-
monsoon samples is presented in (Tables S3 and S4).
meq(cations) − meq(anions)
CBE(%) = × 100 (1)
meq(cations) + meq(anions)
2+
3.3. Stable isotope measurements
A continuous flow Isotope Ratio Mass Spectrometer (IRMS, Isoprime
100) located at Bhabha Atomic Research Centre (Mumbai, India) was
used for isotope (2H and 18O) measurements. One milli-liter of water
sample was equilibrated with H2 and CO2 gases respectively for δ2H and
δ18O measurements. The operating conditions like, temperature, cata­
lyst and equilibrium time for δ2H and δ18O analysis are adopted from
Keesari et al. (2016). After equilibration, the gas was introduced into the
mass analyser for isotope ratio measurements. For δ13C measurement,
4
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

dissolved inorganic carbon (DIC) was precipitated in the form of BaCO3
in one-liter bottle by adding NaOH (to increase the pH above 10) and
carbonate free saturated BaCl2 solution. This precipitate was dried and
transferred into a vial on site. δ13C analysis was performed on the CO2
gas generated by combusting BaCO3 precipitate in an elemental analyser
(EA) coupled with the mass spectrometer (IRMS, Isoprime 100).
The results are reported in δ-notation and expressed in units of parts
per thousand (denoted as ‰). The δ values are calculated using the Eq.
(2) (Coplen, 1996):
( )
Rx
δ(‰) = − 1 × 1000 (2)
Rs
2 1
where R denotes the ratio of heavy to light isotope (e.g. H/ H or
18
O/16O or 13C/12C) and Rx and Rs are the ratios in the sample and
standard respectively. The measured values are normalized on VSMOW/
SLAP scale. The precision of measurement for δ2H is ± 0.5 ‰ (2σ) and
for δ18O is ± 0.1 ‰ (2σ). A total of 75 water samples were collected for
isotope measurements (pre-monsoon 29 and post-monsoon 46). The δ2H
and δ18O isotope data is given in Table S5. δ13C values are reported
against Vienna Pee Dee Belemnite (VPDB) and the precision of mea­
surement is ± 0.30 ‰ (2σ). Laboratory CaCO3 salt calibrated against the
VPDB standard was used for daily calibration. The measurement preci­
sion is estimated by repeated analysis of laboratory standards while the
accuracy is estimated from the deviation of isotopic ratio of standard
from the assigned value.
3.4. Radioisotope measurements
For tritium (3H) measurement, 250 mL of water sample was distilled
and electrolyzed in a cool bath (1 – 4 ◦ C) for tritium enrichment. The
enriched sample was mixed with scintillator mixture (8:12 mL) and
counted for beta activity using an ultra-low background liquid scintil­
lation counter (LSC, Quantulus model 1220) (Nair et al., 1990). The 3H
value is expressed in tritium unit (TU), where one TU has 3H/1H ratio
equals to 10− 18 and corresponds to an activity of 0.118 Bq/kg of water.
The IAEA zero tritium blank and NIST 4926e standard were used for
calibrating raw data. The limit of detection of enriched sample for 500
min counting time is 0.4 TU (2σ) (Morgenstern and Taylor, 2009). The
counting efficiency and the calibration factor of the counter are about
25% and 70 TU/cpm respectively. A total 24 samples (11 pre-monsoon
and 13 post monsoon) were collected for this study and the data is given
in Table S5. For quality assurance, spiked samples and distilled water
samples are added in each batch of samples so that consistency of
measurements is monitored. The measurements are periodically cross­
checked through IAEA inter-comparison exercise.
For radiocarbon (14C) measurement, the DIC was precipitated from
60 L of water and the procedure for BaCO3 precipitation is same as given
for 13C isotope. In the laboratory, phosphoric acid was added to the
BaCO3 precipitate to evolve CO2 in a vacuum line, which was then
passed through the cold trap (mixture of acetone and liquid nitrogen of
temperature – − 70 ◦ C) to remove the water moisture from the gas. The
cylinders filled with CO2 gas were stored for 15–30 days to allow radon
decay. Finally, the CO2 was absorbed in the mixture of carbosorb (11.5
mL) and permafluor (11.5 mL, scintillator) and counted in LSC (Quan­
tulus model 1220) for 20 cycles of 50 min (total 1000 min). The raw 14C
activity data was calibrated against SRM 4990C (Oxalic acid) and the
14
C data is reported as pMC (percent Modern Carbon). Nine samples
were collected for radiocarbon measurements (Table 1).
3.5. Estimation of reservoir temperature
Since 1960s, chemical geothermometers have been widely used
worldwide to predict the subsurface temperature of the geothermal
reservoir. Commonly employed chemical geothermometers, also known
as “classical” geothermometers include silica (Fournier, 1977), Na-K
(Fournier, 1979, Arnorsson, 1983, Giggenbach et al., 1988), Na-K-Ca
(Fournier and Truesdell, 1973) and K-Mg geothermometer (Giggen­
bach, 1988). The implicit assumption in applying chemical geo­
thermometer is that there exists a chemical equilibrium between the
interacting thermal water and aquifer mineral. For example, if the
quartz geothermometer is used to estimate the reservoir temperature, it
is assumed that thermal water has attained equilibrium with Quartz
mineral present in the host rock. Similarly, Na-K geothermometer
(Fournier, 1979, Arnorsson, 1983) is based on the equilibrium between
albite and K-feldspar minerals. The equations used for estimating
reservoir temperature using chemical geothermometric methods are
provided in Table S6. In silica enthalpy mixing model, enthalpy derived
from steam tables is used as an axis rather than temperature. This is
because the combined heat content (enthalpy) of the two waters is
conserved on mixing whereas the combined temperature is not (Four­
nier and Truesdell, 1970). In this mixing model, the silica concentrations
of the examined samples were plotted against their corresponding onsite
enthalpies. The enthalpy values were determined using the steam tables
of Keenan et al. (1969). For the application of this model two end
member fluids were considered: viz., thermal (highest temperature
water) and non-thermal (nearby cold water). The subsurface enthalpy of
the geothermal reservoir can be estimated by extrapolating a line joining
the data points of local groundwater with that of hot springs which in­
tersects the quartz solubility curve. The intersection point represents the
silica content of the parent geothermal water before mixing. Next, a
vertical line is drawn from the intersection point of the quartz solubility
curve to the enthalpy axis and the intersection point in the enthalpy axis
denotes the enthalpy of the parent geothermal water before mixing. In
integrated multicomponent solute geothermometry (IMG) method, the
representative reservoir temperature is estimated based on the satura­
tion state analysis of suitable mineral assemblages (Spycher et al.,
2014). The saturation indices (SI) of potential reservoir minerals over a
range of temperatures are calculated and plotted as a function of tem­
perature. Reservoir temperature is estimated from the clustering of log
(Q/K) curves near to the zero. A stand-alone computer program (GeoT)
is used to solve the mass balance/mass action equations using Newton-
Raphson iterative method (refer Spycher et al., 2014 for details). The

Table 1
Carbon isotopes data and modeled radiocarbon ages of thermal and non-thermal waters.
Sample ID δ13C (‰) 14
C (pMC) Error (1σ pMC) Apparent age T1 Negative Error Positive Error T2 Remarks
(years) (years) (years)

1 − 21 20.1 1.1 13,189 14,482 − 443 467 13,096 Very old

2 − 20 50.1 1.5 5594 7647 − 244 251 5066 old
3 − 19.3 87.1 1.8 1026 2820 − 169 173 179 modern
6 − 17.24 76.2 1.6 2128 3040 − 172 175 265 modern
8 − 16.22 55.7 1.5 4723 4363 − 220 226 2305 old
11 − 18.75 19.5 1.1 13,415 13,795 − 455 481 12,309 very old
15 − 14.71 98.6 2.1 3 − 326 − 174 178 − 3309 modern
19 − 19.88 10.1 1.1 18,919 19,712 − 863 963 18,337 very old
25 − 20.16 10.2 1.1 18,771 19,807 − 848 945 18,315 Very old

Note: T1 and T2 represent age estimates computed from IAEA model and equation given by Wang et al. (2019) respectively.

5
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

thermodynamic database SOLTHERM.H06 is used to compute the ion

average
activity product (Q), the thermodynamic equilibrium constant (K) and SI

107.3

161.3

162.9
32.1

11.7

87.3

80.3
23.3

34.7

76.4
values. GeoT also computes different statistical parameters i.e. median

793
8.0
0.4

3.7

4.7

3.5
(RMED), standard deviation (SDEV), mean (MEAN) and root mean
square error (RMSE) of SI values as well as the temperatures at which

maximum
these statistical parameters attain minimum value (TRMED, TMEAN, TSDEV

1256
34.2

19.0

94.0

50.0

66.7

14.7
Non-thermal n = 8
and TRMSE). For a perfectly clustered system, TRMED, TMEAN, TSDEV and

189

290
198

227
123
8.8
0.4

8.0

8.0

4.3
TRMSE should be identical and this temperature reflects the computed
reservoir temperature. The main limitations of this approach are; need

minimum
for exhaustive mineralogical data, dependency on steam loss and non-

<0.1
29.9

32.0

83.0
89.0
12.0

98.7
29.7
thermal mixing and sensitivity towards the choice of the thermody­

198
6.7
0.3

1.0
5.0
2.0

2.0
2.3
2.6
namic database (Pang and Reed, 1998).

average
4. Results

179.2

196.2
1147
48.8

13.2

93.2
97.3

62.8

73.7

21.7
219
126
8.0
0.3

9.5

3.0

3.7
The thermal discharge is highest at Atri site (233 lpm) followed by

maximum
Taptapani (82 lpm) and Athmalik sites (36 lpm). The thermal manifes­
tations at Tarabalo site are at multiple points and are under marshy

1312
58.4

12.0
16.0

99.0

78.0

78.3

22.1
218

110
244

232
128
8.3
0.5

4.0

4.1
condition, hence the discharge could not be quantified accurately. The

Thermal n = 13
previous reports estimated thermal discharges in the range of 33–420

Minimum
lpm and found overall discharge rates constant throughout the year

Athmalik
(Thussu, 2002; Mahala, 2019).

1084
38.8

32.0

85.0
80.0
12.0

69.0

21.2
206
124
7.6
0.2

1.0
5.0
2.0

2.0
2.3
4.1. Hydrochemical characteristics

average

970.3

<0.1
29.5

59.0

47.0
34.0
51.0

38.0

36.6
The temperature of the thermal water ranges from 38.8 to 58.4 ◦ C in

419
8.2
0.3

1.0

6.0
1.4
1.3
4.5
pre-monsoon and 35.8 to 58.9 ◦ C in post-monsoon seasons. The non-
thermal waters show temperature variations from 29.0 to 34.2 ◦ C in

maximum
pre-monsoon and 26.6 to 38.5 ◦ C in post-monsoon (Fig. S1). Irrespective

1592
29.7
of location, the thermal waters are colorless and have gas bubbling with Non-thermal n = 6

8.6
0.3
sulfur odor while the non-thermal waters are colorless and odorless.
Navada et al. (1995) reported similar thermal water temperatures dur­
minimum

4 , F , – mg/L; Rb, Li, B, Cs - µg/L.

ing 1995, suggesting that the temperature of thermal water did not
29.0

change for the past 25 years.

645
7.6
0.3

+
During pre-monsoon, the non-thermal waters show a wider variation
in electrical conductivity (198–1592 µS/cm) than thermal waters
average

52.3

61.3
85.0

23.7
12.6

42.4
65.0
8.5
0.4

4.7
2.7
2.3

1737.5

1.4
793.7

143.7

144.7
(788–1312 µS/cm). A similar trend is observed in the case of post-
monsoon samples. The summary of the hydrochemical data is pro­
vided in Table 2 and 3.
maximum

Dominance of ions in thermal waters during post-monsoon period is

in the order of;

3434
56.9

65.0
99.0

24.0
13.2

44.4
68.8
797

145

147
8.6
0.5

5.0
3.0
3.0

1.5
Na+ (150–220 mg/L) > Ca2+ (4–18 mg/L) > Mg2+ (0.5–11 mg/L).
Summary table for thermal and non-thermal samples during pre-monsoon season.

−
Thermal n = 5

Anions follow the order,

Note: Temp- oC; EC- µS/cm; DO, Na+, K+, Ca2+, Mg2+, SiO2, HCO–3, Cl− , SO2−
Cl− (140–245 mg/L) > HCO–3 (54–99 mg/L) > SO2−
minimum

4 (36–101 mg/L).
Tarabalo

Only thermal water at Taptapani site show a conspicuous reduction

43.6

57.0
70.0

23.0
12.2
41.0
40.3
61.2
788

143

143
8.5
0.3

4.0
2.0
2.0

1.3
in Cl− (10 mg/L) and SO2− 4 (5 mg/L) concentrations compared to other
thermal waters.
average

The non-thermal waters show the cation order similar to thermal

8.0
0.3

2.7

6.3
4.6
8.2
663.8

255.7
30.7

67.7

38.0
17.3
53.7

58.3

14.2
56.1

waters,
–

Na+ (18–180 mg/L) > Ca2+ (6–70 mg/L) > Mg2+ (1–35 mg/L).
But the anions show a different order compared to the thermal
maximum

waters,
352.0

HCO–3 (102–446 mg/L) > Cl− (8–138 mg/L) > SO2−

32.0

61.0
30.0
60.0

13.0
12.3
21.5
31.4
90.0
Non-thermal n = 6

4 (0–24 mg/L).
997

149

120
8.9
0.4

4.0

The major ion trends in thermal and non-thermal waters are shown
in Schoeller diagrams (Fig. S2a and b). No significant difference in the
minimum

major ion concentration ranges is observed among non-thermal waters

<0.1
29.3

10.0

50.0

24.0

34.5

of different sites. The Piper’s classification shows that the thermal and
333

198
7.3
0.3

2.0
6.0
3.0

0.0
0.4
1.3
4.0

non-thermal waters have different facies suggesting different sources or

processes governing geochemistry (Fig. 3a). The hydrochemical facies of
Thermal n = 1

the samples indicate that thermal waters barring Taptapani site, show
dominance of Na+ and Cl− ions (cluster-i) in both seasons. However,
253.0

four clusters are observed for non-thermal waters, cluster-ii (dominated

1192
57.6

59.0
40.0

26.0

63.0
67.3
53.2
Atri

180
8.6
0.5

8.0
8.0
3.0

9.2

4.1

by Ca2+ and HCO–3) indicates recharging nature of water while cluster-iii

(dominated by Na+ and HCO–3) indicates influence of water-rock inter­
Table 2

HCO–3
Temp

Mg2+

action mainly silicate weathering and ion exchange reactions as dis­

Ca2+

SiO2

SO2−
Na+

+
4

Cs+
DO

Li+
pH

K+
EC

Rb
Cl−

F−

cussed in section 5.2. A few non-thermal samples also fall in cluster-i

6
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

indicating the possibility of mixing with thermal sources, which is

minimum maximum average

supported by warmer temperatures in those samples (34.9–38.5 ◦ C).

272.3

150.3
38.7

54.3
Samples falling in cluster-iv with relatively higher EC values (~750 µS/

6.7
3.3

2.3
1.9
29

20

14
6

6
cm) suggest dissolution of salts from the formation. The enrichment of
Cl− (average: 169 mg/L) and Na+ (average: 170 mg/L) in thermal waters
Thermal n = Non-thermal n = 6
over non-thermal waters (average Cl− : 29.26 mg/L; average Na+: 65.6

38.5
382

236
7.3

4.4
70
15
25

67

21
5

4
mg/L) may be attributed to greater leaching of minerals present in rocks
due to elevated temperatures (Tables S3 and S4). The common sources
for Na+ and Cl− could be minerals like biotite, hornblende and feldspar
present in the study area (Mahala, 2019; Maitra et al., 2020). Among
trace elements, fluoride (2.25–13.2 mg/L) concentration is found to be
Taptapani

higher while boron (53.2–128 µg/L), lithium (40.3–232 µg/L) and

rubidium (41–3434 µg/L) are lower in concentrations. Like, major ions,
42.7
369

225
7.4
2.1

4.9
72

18

62

10
the trace elements concentrations are also higher in thermal waters
1

5
compared to non-thermal waters (Table S4), which underlines the in­
minimum maximum average minimum maximum average minimum maximum average minimum maximum average minimum maximum average

694.1

274.7
31.3

81.7

30.3

17.3
fluence of greater water – rock reactions favoured by high temperature.
7.3
2.5

2.6

3.3

7.4
97

11
4.2. Stable isotopes (2H, 18
O and 13
C)
Non-thermal n = 8

1311
34.9

130

132
362
8.5
4.1

9.2
70

12
23

The δ18O and δ2H values of the thermal waters vary from − 6.30 to
5

− 2.80 ‰ and − 36.8 to − 14.02 ‰ respectively during post-monsoon and

− 4.42 to − 2.96 ‰ and − 26.05 to − 15.34 ‰ respectively during pre-
29.5
174

188
6.9
1.1

0.7

4.3
55

78

10
14

monsoon (Table S5). The thermal water from Taptapani site shows
6
1

most depleted isotopic signature (δ18O: − 6.3 ‰) as compared to other

218.3
1090

95.3

sites (Table S5). Like thermal water, the non-thermal waters also show
200

121
0.6

8.3

1.5
47

17

92
8

relatively depleted isotope values at Taptapani site (average δ18O and

δ2H, − 6.4 ‰ and − 40.9 ‰). In general, a wide scatter in isotope data is
observed in non-thermal waters, δ18O: − 5.28 to 0.98 ‰, δ2H: − 31.94 to
1130
58.9
Thermal n = 13

220

126

224
101
8.6
4.2

5.1
18

99

− 3.58 ‰ in pre-monsoon and δ18O: − 6.82 to 0.87 ‰, δ2H: − 45.4 to

9

− 0.97 ‰ during post-monsoon season.

Athmalik

The isotope plots of the thermal and non-thermal waters are shown
35.1
975

190

117

214
7.6

4.7
16

86

85

in Fig. 4a, b. The Global Meteoric Water Line (GMWL: δ2H = 8 × δ18O +
0

10) and Local Meteoric Water Line (LMWL) of the study area (δ2H =
1031.8

7.92 × δ18O + 5.74, after Kumar et al., 2010) are also shown in the plots.
29.4

446
7.5
0.8

0.7

1.7
61

57
35
62

32
11

The possibility of presence of any magmatic component is ruled out

considering the wide contrast between the thermal water isotope values
Non-thermal n = 6

and magmatic sources isotope signatures, which are enriched in δ18O

1915
30.3

7.9

(+6 to +9 ‰) and depleted in δ2H (− 40 to − 80 ‰, Giggenbach, 1992).

2

Low EC (369–1130 µS/cm), low Cl− contents (10–245 mg/L) and

4 , F – mg/L.

absence of enriched stable isotope (δ18O & δ2H) values preclude the
28.9
571
7.2

possibility of marine contribution to the studied thermal waters. The

0
Summary table for thermal and non-thermal samples during post-monsoon season.

geothermal waters fall along the GMWL and LMWL clearly demon­
−
714.2

162.5

strating their meteoric origin (Fig. 4a) and the slope close to 8 indicates
50.2

81.3
87.5

36.8
142
8.8
2.4

3.8
5.8
0.8

Note: Temp- oC; EC- µS/cm; DO, Na+, K+, Ca2+, Mg2+, SiO2, HCO–3, Cl− , SO2−
16

the recharge without significant evaporation (Clark and Fritz, 1997;

Kumar et al., 2010). No δ18O-shift in the δ2H vs. δ18O plot is observed in
thermal waters (Fig. 4a), which further indicates that the reservoir
57.1

16.2
721

170

144
8.9
4.3
Thermal n = 5

86
97

38

temperature is not sufficient enough (i.e. >150 ◦ C) to shift δ18O value

5
7
1

through extensive water – rock interaction. In geothermal systems with

Tarabalo

high water to rock ratio the fresh rock surface available for isotopic
44.3

15.6
706

150

140
8.6

0.5

exchange would be very small resulting low to negligible 18O-shift

77
70

36
0

2
4

(Nicholson, 1993).
682.2

261.3

There are multiple sources for DIC in subsurface waters like atmo­
31.1

14.3
68.7

61.7
11.3
7.2
2.8

1.7

5.5
78

43

spheric CO2, oxidation of dissolved organic matter, carbonate or silicate

mineral weathering, which can be identified through examining the
Thermal n = Non-thermal n = 6

δ13C-DIC (Clark and Fritz, 1997; Das et al., 2005). The average δ13C of
1050
32.2

180

403
138
8.2
6.6

69
26
80

24
15

the atmospheric CO2 is − 8.1 ‰ (Cerling et al., 1991). C3 vegetation is

3

characterized by more depleted δ13C composition (-25 ‰) than for C4

plants (-13 ‰). The magmatic CO2 shows δ13C values from − 7.5 to − 5.5
30.4
317

161
6.6
0.8

0.9
0.4

‰ VPDB (Exley et al., 1986). The marine carbonates have enriched δ13C
20

63

19
1
6
2

values (0 ‰) while the organic sources are characterized by depleted

δ13C values − 30‰ (Evans et al., 2008). Geogenic CO2 present in deeply
circulating geothermal systems typically has high pCO2 and moderately
1019
57.7

11.8
Atri

180

245
8.5

enriched δ13C value (-6 ‰, Marty and Jambon, 1987). In the present
11
11
98
54

42
1

study, the δ13C values range from − 21 to − 16.2 ‰ for thermal waters
Table 3

HCO–3
Temp

Mg2+

and − 20 to − 14.7 ‰ for non-thermal waters (Table 1). These ranges

Ca2+

SiO2

SO2−
Na+

4
DO
pH

K+
EC

Cl−

F−

overlap with the δ13C – DIC derived from silicate weathering reactions

7
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

Fig. 3. a) Piper’s plot of major ions of thermal and non-thermal waters, b) facies variations in thermal springs of different sites illustrating the minor differences due
to host rock composition, c) geochemical evolution of non-thermal waters and d) Ca2+/sum cations versus temperature plot indicating the shallow non-thermal
water mixing.

(Das et al., 2005). The contributions from marine carbonate, mantle tritium are also reported from other geothermal systems in India (Nav­
degassing and organic matter oxidation seems to be negligible or absent. ada et al., 1995; Chatterjee et al., 2018). In the present study, the tritium
These aspects are further discussed in section 5.4. content of non-thermal waters from all sites ranges from 0.9 to 3.4 TU
indicating modern recharge (Table S5). The 14C values range from 10 to
56 pMC while non-thermal waters show values from 50 to 99 pMC
4.3. Radioisotopes (3H and 14
C)
(Table 1). A close examination of the data suggests that 14C values of the
thermal waters with highest temperature are 20 pMC or lower. Similar
Tritium content in thermal waters provides estimation of residence
low 14C values have been reported from Godavari Valley geothermal
time and shallow groundwater mixing proportions (Sammel and Craig,
systems (Chatterjee et al., 2019). The radiocarbon dating of thermal
1981; Chatterjee et al., 2018) Samples with tritium >1.0 TU indicate
waters is further discussed in section 5.4.
recent recharge or mixing with modern water whereas low tritium (<1.0
TU) indicates recharge prior to 1951 (Clark and Fritz, 1997). Tritium
5. Discussion
data of thermal waters during both seasons (pre-monsoon: 0.4 – 0.9 TU
and post-monsoon 0.4–1.5 TU) is typically 1.5 TU or less (Table S5). This
5.1. Subsurface temperature estimation
suggests that modern recharge to thermal waters is negligible and the
residence time of thermal water could be >50 years. Low tritium (<1
5.1.1. Chemical geothermometry:
TU) thermal waters with high temperatures up to 97 ◦ C are also
A wide scatter is observed in the estimated reservoir temperatures at
observed in other geothermal fields of India (Sarolkar, 1996; Chatterjee
different sites of the study area (Table 4). Quartz geothermometer (no
et al., 2016, 2017). The thermal water at Taptapani site has relatively
steam loss) estimated subsurface temperatures from 112 to 136 ◦ C and a
higher tritium, 1.5 TU, suggesting modern recharge (<50 years) or
similar range of temperatures (111–132 ◦ C) is observed from adiabatic
mixing with modern waters during ascent. Thermal waters with modern

8
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

Fig. 4. Plots of δ2H vs. δ18O of a) thermal waters (GMWL- Global Meteoric Water Line, LWML – Local Meteoric Water Line (Kumar et al., 2010), Rainwater data taken
from Keesari et al. (2016) and b) non-thermal waters, EL – evaporation line, the mean isotope values (with 1σ deviation) of thermal waters of respective site
are mentioned.

Table 4
Estimates of chemical geothermometry, silica enthalpy mixing and integrated multicomponent solute models and reservoir depth.
Sample ID T Q1 Q2 C Na-K (1) Na-K (2) Na-K (3) Na-K (4) Na-K (5) K-Mg Na-K-Ca Na-K-Ca Avg std SiM IGT RD
Mg corr

1 (Atri) 58 136 132 109 156 175 141 144 125 76 148 * 134 3 145 118 2.3
11 (Tarabalo) 57 123 121 95 127 147 104 116 92 65 131 * 122 1 127 112 2.1
12 (Tarabalo) 56 112 111 83 141 160 122 129 108 70 139 * 112 1 ** ** **
19 (Athmalik) 59 133 129 106 164 182 151 152 133 87 151 105 131 3 163 124 2.4
25 (Athmalik) 56 133 129 106 174 192 164 162 145 92 159 109 131 3 ** ** **
28 (Athmalik) 57 132 128 104 165 183 152 153 134 87 118 101 130 3 ** ** **
40 (Taptapani) 43 112 111 83 91 112 62 81 54 * * * 112 1 119 92 1.6

Note: T – thermal water temperature (◦ C), Q1-Quartz conductive, Q2-Quart adiabatic, C- Chalcedony, * estimates lower than thermal water temperature, **- not
determined. The silica and cation geothermometer equations are given in Table S6. Avg- mean of silica geothermometry estimates, std – standard deviation, SiM- Silica
enthalpy mixing model, IGT- Integrated geothermometry model, RD –Reservoir depth in km.

quartz geothermometer (maximum steam loss), indicating no appre­
ciable steam separation from the thermal water system. Chalcedony
geothermometer estimated temperatures (83–109 ◦ C) lower than Quartz
geothermometer values. The Na-K-Mg ternary diagram aids in inferring
whether thermal water is immature or in partial equilibrium or attained
full equilibrium with the rocks at a given temperature (Giggenbach,
1988). The sample data falls near Mg-corner in the ‘Immature waters’
region, suggesting that the estimates from Na-K geothermometers may
be erroneous (Fig. 5a). This is further witnessed in the wide range of
subsurface temperatures (54–192 ◦ C) estimated from the Na-K geo­
thermometers. The Na-K-Ca and magnesium corrected Na-K-Ca geo­
thermometers estimate reservoir temperatures from 118− 159 ◦ C and
101–109 ◦ C respectively (Table 4). The plot of 10 K/(10 K + Na) vs. 10
Mg/(10 Mg + Ca) is presented in Fig. 5b. The sample data falls above the
line inferring that thermal waters are not completely equilibrated with
alkali feldspars. The subsurface temperature estimated from K-Mg geo­
thermometer ranges from 65 to 92 ◦ C and is lower than the Quartz
geothermometer estimates. This lowering of the estimated temperatures
suggests contribution of near surface rock-water interaction or non-
thermal water mixing. From the above discussion, temperature esti­
mates of Quartz geothermometry are found to be reliable and repre­
sentative. The average reservoir temperatures for Atri, Tarabalo,
Athmalik and Taptapani sites are found to be 134 ± 3 ◦ C, 117 ± 1 ◦ C,
131 ± 3 ◦ C and 112 ± 1 ◦ C respectively (Table 4).
5.1.2. Mixing model
Positive correlations between the conservative elements and pres­
ence of environmental tritium in thermal water confirm the mixing
between thermal and non-thermal waters (Table S5). The non-thermal
mixing fraction to thermal water is estimated to be 0.12 to 0.63
(Table S5). The end member pairs for Atri, Tarabalo and Athmalik and
Taptapani sites are ID-1 & 3, ID-11 & 13, ID-19 & 31 and ID-40 & 42
respectively. The average silica values (pre- and post-monsoon data) are
used in the plot. Points A, B, C and D represent the enthalpy and the
silica content of the parent geothermal water before mixing for Tapta­
pani, Tarabalo, Atri and Athmalik sites respectively (Fig. 6). The sub­
surface temperatures computed using this method (119 to 163 ◦ C) are
found to be slightly higher than the estimates obtained from chemical
geothermometers (Table 4).
5.1.3. Integrated multicomponent solute geothermometry
Both the classical geothermometry and silica enthalpy mixing
models though provided a similar range of reservoir temperatures, the
estimates for individual reservoirs are not consistent. This is a common
issue for the low to medium enthalpy geothermal systems owing to non-
attainment (or partial attainment) of equilibria. This limitation is
addressed by applying IMG method. In this study; quartz, magnesite,
albit-lo, enstatite, hercynite, grossular, sanidine, pyrite, osumilite are
taken as ten main clustering minerals based on the geological informa­
tion of the study area (Dasgupta, 1993; Mahala, 2019; Maitra et al.,
2020). GeoT is applied over the four thermal water samples (Samples ID-
1, 11, 19 and 40) and deep fluid temperature is computed from the ten
best clustering minerals. For ID-1 (Atri thermal water), the chemical
composition of water suggests equilibrium with minerals such as quartz,
calcite, magnesite, grossular, hercynite, sanidine, osumilite etc. (Fig. 7a)
and estimated equilibrium temperature (TRMED) is found to be 118 ◦ C
(Fig. 7b). In case of ID-11 (Tarabalo thermal water), the clustering is
observed with minerals such as quartz, albit-lo, calcite, magnesite, dolo-

9
T. Keesari et al.
Fig. 5. a) Na–K–Mg Giggenbach plot determining the water rock equilibrium
conditions and b) Plot of 10 K/(10 K + Na) vs. 10 Mg/(10 Mg + Ca) (after
Giggenbach, 1988).
Fig. 6. Silica-enthalpy diagram for estimating the reservoir temperatures.
dis, osumilite, sanidine, enstatite etc. (Fig. 7c) and the estimated equi­
librium temperature is (TRMED) 112 ◦ C (Fig. 7d). In Athmalik area (ID-
19), quartz, albit-lo, magnesite, grossular, osumilite, sanidine etc. are
found to be the main clustering minerals (Fig. 7e) and the estimated
reservoir temperature (TRMED) turns out to be 124 ◦ C (Fig. 7f). In Tap­
tapani site (ID-40), quartz, magnesite, osumilite, sanidine, calcite,
dolomite, etc. are found to be the main clustering minerals (Fig. 7g) and
the estimated reservoir temperature (TRMED) is found to be 92 ◦ C
(Fig. 7h). It is observed that the estimates of reservoirs temperature
10
Journal of Hydrology 612 (2022) 128172
range from 92 to 124 ◦ C and fall on the lower side of the values obtained
from silica enthalpy mixing model and chemical geothermometry
(Table 4) but the spread in the estimates is much smaller than the pre­
viously reported values, 92 to 277 ◦ C (Navada et al., 1995). These es­
timates indicate a lower enthalpy thermal system in Mahanadi graben
compared to SONATA mobile systems, conforming to the heat flow
values of Indian shield (Kumar et al., 2007; Roy and Mareschal, 2011).
5.2. Geochemical processes
Along the flow groundwater accumulates salts leading to higher EC;
therefore, the geochemical reactions are examined in tandem with EC
values in Piper’s trilinear plot (Fig. 3b and c). In the case of thermal
waters, a clear distinction is noticed in the chemical facies. Athmalik
thermal water shows Na-Cl-SO4 facies while Atri and Tarabalo sites
show Na-Cl-HCO3 facies. Similar nature of subsurface geology at these
sites could be the reason for the observed similarity in water facies.
Thermal waters represented by Na-Cl type with high salinity (~5000 µS/
cm) are common in the West coast geothermal systems in India due to
mixing with marine waters (Chandrasekhar et al., 2018), however in this
study, though the hydrochemical facies is Na-Cl type, the salinity range
is lower (EC ~ 1000 µS/cm) in thermal waters. A similar pattern of low
EC and Na-Cl facies of thermal waters is observed in the Hazaribagh and
Dumka (Jharkhand) and Bakreswar and Tantloi (West Bengal)
geothermal regions (Singh et al., 2020).
The second dominant anion, after Cl− , in the thermal waters of Atri/
Tarabalo and Athmalik sites is HCO–3 and SO2− 4 respectively. The HCO3
–
concentration of thermal waters is similar in these three sites (54–99
mg/L), however the SO2− 4 concentration is lower (<40 mg/L) in Atri/
Tarabalo sites but relatively higher (80–100 mg/L) in Athmalik site
(Tables S3 and S4). This clearly suggests that the thermal waters are
circulating through different rock types in these sites. At Athmalik site,
the thermal waters issue along the northern fringe while at Atri and
Tarabalo sites the thermal waters issue along the southern fringe of the
Mahanadi graben (Fig. 2a). Northern part of the EGMB is dominated by
Iron Ore Supergroup consisting of pyritic minerals (Mahala, 2019).
Oxidation of pyrite releases high SO2− 4 and H , which reduces the pH of
+
2−
the water. High SO4 concentration and reduced alkaline nature of
thermal water at Athmalik site (pH: 8.0 ± 0.3) compared to other sites
(pH: 8.7 ± 0.2) further substantiate this observation.
In contrast, thermal water at Taptapani site is Na-Ca-HCO3 type
water. Similar type of thermal water was reported in Taptapani and
Salbardi areas of SONATA belt and Rajapur area of West coast
geothermal systems (Minissale et al., 2000). Relatively higher concen­
tration of Ca2+ and HCO–3 in Taptapani site can be attributed to
weathering of mixed plagioclase minerals. Lower temperature (42.7 ◦ C),
lower EC (369 µS/cm) and neutral pH (7.38) compared to rest of the
thermal waters as well as its location away from the Mahanadi graben,
as shown in Fig. 1c, d and 2a, indicate that the geothermal reservoir is
different for this site. This observation is further supported by its distinct
isotopic as well as geothermometry values, discussed in subsequent
sections. Thermal waters do not show any temporal variations in
chemical composition whereas non-thermal waters do (Fig. 3a–c).
The source rocks contributing to the dissolved species in thermal
waters are evaluated by ionic ratios. Low HCO–3/SiO2 ratio (<5) and
intermediate (Na++K+-Cl− )/(Na++K++Ca2+-Cl− ) ratio (0.2 to 0.8)
shown in Table S7, infer silicate weathering (Hounslow, 1995). The
plots of Na-normalized molar ratios (Mg2+/Na+ vs. Ca2+/Na+ and
HCO–3/Na+ vs. Ca2+/Na+) also suggest the contribution of evaporite and
silicate minerals towards dissolved ions in thermal waters (Fig. 8a and
b). None of the samples fall in the carbonate mineral zone indicating
less/no influence of carbonate minerals on the hydrochemistry of ther­
mal and non-thermal waters. Presence of high SiO2 and high F− further
supports the contribution of minerals from granitic and hornblende
gneissic rocks. These observations conform to the nature of rocks present
in EGMB (Mahala, 2019; Maitra et al., 2020). The sample data fall in the
T. Keesari et al. Journal of Hydrology 612 (2022) 128172

Fig. 7. Computed saturation indices (SI) as well as statistical analysis of SI as a function of temperature using multicomponent geothermometry (GeoT) for a, b) Atri
(ID-1), c, d) Tarabalo (ID-11), e, f) Athmalik (ID-19) and g, h) Taptapani (ID-40). The convergence point is taken as representative temperature of the ther­
mal reservoir.

chloride region of the Cl-SO4-HCO3 ternary diagram in the case of Atri,
Tarabalo and Athmalik sites indicating that the thermal waters are not
steam heated local groundwater and are mature in nature (Fig. 8c).
Thermal water from the Taptapani region falls in the bicarbonate region
representing mixed water or immature waters.
The non-thermal waters show low EC and the hydrochemical facies
are either Ca-Mg-HCO3 type (cluster i) or Na-HCO3 type (cluster iii)
evolving to Na-Ca-HCO3 or Ca-Na-HCO3 type (cluster ii) as shown
Fig. 3c. These facies variations agree with the increasing EC values from
200 to 650 µS/cm. Some samples with higher EC (~750 µS/cm) are
characterised by Na-Cl-HCO3 type, similar to that of diluted thermal
water, suggesting mixing between thermal and non-thermal waters. It is
observed that the less percent of Ca2+ the thermal water contains the
higher temperature it has (Fig. 3d). The facies variations can result from
various geochemical reactions such as weathering of minerals, ion ex­
change or evaporite dissolution. From Fig. 9a and b, it can be concluded
that the silicate weathering exerts a major control on the chemistry of
non-thermal waters, which is supported by presence of moderately high

11
T. Keesari et al.
Fig. 8. Plots of Na-normalized molar ratios of a) Mg2+ vs. Ca2+ and b) HCO–3 vs. Ca2+ demonstrating the relative contribution of evaporite, silicate and carbonate
minerals, c) Anion variation diagram (Cl-SO4-HCO3 ternary diagram) classifying thermal waters into different water fields and d) plot of Na+-Cl− vs. Mg2++Ca2+-
SO2−
4 –HCO3 illustrating ion exchange process in non-thermal waters.
–
silica concentration (37–132 mg/L). The ion plot of Na+-Cl− vs.
Mg2++Ca2+-SO2− 4 –HCO3 evaluates the ion exchange process occurring
−
in thermal and non-thermal waters (Fig. 8d). The non-thermal waters
fall along the line with slope − 1 indicating Na+ in water is being
replaced by Ca2+ from clay. But, thermal water data fall as a cluster in
the plot indicating less significance of ion exchange process.
In order to estimate the extent of water – mineral equilibrium,
saturation indices (SI) were estimated using the formula (Eq. (3));
IAP
SI = − log (3)
Ksp
Where IAP – ion activity product, Ksp – solubility product. The SI = 0,
>0 and <0 indicates saturation, supersaturation and unsaturation
respectively. WATEQ4F program was used to compute SI of common
minerals. The ranges of saturation indices of thermal and non-thermal
waters with respect to common minerals are represented in Table S8.
Saturated to supersaturated condition is exhibited for silicate minerals
while carbonate minerals demonstrate unsaturated to saturated condi­
tion. Sulphate and fluoride minerals demonstrate unsaturation in both
thermal and non-thermal waters. The degree of saturation seems to be
higher for thermal waters than non-thermal waters, which agrees with
the enrichment of major ions as well as trace elements. However, the SI
variations are similar for both thermal and non-thermal waters, which
can be attributed to their interaction with common rock types. This
could also imply that the thermal water circulations are not deep enough
to encounter different kind of rock types in EGMB.
The characteristic ionic ratios of thermal waters are used to infer the
nature of reservoir and the associated flow paths. The Na+/Ca2+ ratio
(wt. ratio, 1.0 – 40) is different for different thermal waters indicating
12
Journal of Hydrology 612 (2022) 128172
different reservoirs or different flow paths (Wright et al., 1991), while
the near uniform ratios observed in the case of SiO2/Cl− (wt. ratio
0.4–0.6) and (Na++K+)/(Cl− +F− ) (wt. ratio 0.72 – 1.1) reflect signifi­
cant interaction with country rocks (Table S7). These observations agree
with the inferences obtained from SI variations (Table S8). The ionic
ratios are quite different in the case of Taptapani thermal water sug­
gesting completely a different source reservoir and/or flow path for
thermal water. Presence of high B and Cl− concentrations in thermal
waters suggests deep circulation paths and extended interaction with the
rocks (Arnorsson, 2000). The Cl− /B ratio is used to trace the ground­
water flow paths and assess the mixing proportions of different water
masses in geothermal systems (Aggarwal et al., 2000). Atri, Tarabalo
and Athmalik sites exhibit different Cl− /B ratios, 4750, 2237 and 1810
respectively. But the thermal waters located at a particular site showed
similar Cl− /B ratios (Table S7). These non-uniform Cl− /B ratios at
different sites demonstrate that these conservative constituents are
originated from different reservoirs (Fournier and Truesdell, 1970).
The interrelationships among Li, Rb and Cs also help in evaluating
the secondary processes. Due to the large differences in the respective
concentrations of these elements, a scaling factor is applied to spread the
data evenly in the Li-Rb-Cs ternary diagram. It is observed that the
thermal water data of Atri, Tarabalo and Athmalik sites fall away from
the crustal rock’s composition indicating the presence of different sec­
ondary processes (Fig. 9a). Thermal waters in Athmalik site show lowest
Li+/Cs+ ratio (wt. ratio 9.7 – 15.4) whereas Tarabalo thermal water
shows highest Li+/Cs+ ratio (wt. ratio ~30), indicating incorporation of
Cs+ in clay minerals at Tarabalo site (Table S7). In the Cl-B-Li ternary
diagram, the sample data falls near the chloride corner, which suggests
that these thermal waters are part of a very old hydrothermal system
T. Keesari et al.
Fig. 9. Ternary diagrams of a) Li-Rb-Cs and b) Cl-B-Li for themal waters in
different sites.
(Fig. 9b). The relatively low B content in the thermal springs (<0.13 mg/
L) reflects the high degree of maturity in the geothermal system
(Table S4). During the early heating up stages, volatile components such
as B are likely to be expelled from the system. Thus, fluids from the
‘older’ hydrothermal systems normally show lower B concentration.
5.3. Isotope systematics
The stable isotopic composition of the thermal waters indicates
different clusters, as shown by shaded regions in Fig. 4a. The isotope
data of these thermal waters measured during 1995 by Navada et al.
(1995) also fall in the respective groups indicating that the reservoir
isotope characteristics have not changed during the last 25 years. The
seasonal variation in isotope data is very small indicating less influence
of current hydrological cycle on the reservoir source. The isotopic values
of thermal waters are similar for Atri and Tarabalo sites with mean δ2H
and δ18O values − 24.01 ± 2.2 ‰ and − 4.1 ± 0.3 ‰ respectively. At
Athmalik site, the mean values of δ2H and δ18O are − 17.1 ± 1.05 ‰ and
− 3.2 ± 0.17 ‰ respectively. Isotope data of thermal waters from Atri
and Tarabalo sites fall in a single cluster indicating possibility of a
common reservoir, however, thermal waters of Athmalik and Taptapani
have different and distinct stable isotopic signatures inferring the pos­
sibility of different source reservoirs (Fig. 4a). Considering the similarity
in basement rocks of EGMB, the discrepancy among the temperature
values, ionic ratios and isotopic compositions rules out the possibility of
a common reservoir feeding these thermal waters. In other words, this
confirms the presence of different reservoirs or/and flow paths for
thermal sprouts at these sites. In order to verify if the means of the
isotope data of these groups, viz., Atri & Tarabalo (n1 = 12) and Ath­
malik (n2 = 10) are statistically significant, ANOVA single factor test
was conducted. It is found that the Fstat (60.6) > Fcritical (4.35) (p <
13
Journal of Hydrology 612 (2022) 128172
0.001), indicating the means belong to different population (α = 0.05), i.
e. the thermal waters are fed by different reservoirs. Presence of multiple
subsurface thermal reservoirs are reported by Chatterjee et al. (2017) in
peninsular India, viz., the Manuguru geothermal area (Telangana).
Compared with the local rainwater (δ2H: –32 ‰ and δ18O: − 5.5 ‰,
Keesari et al., 2016) the isotope values are enriched for Athmalik, Tar­
abalo and Atri thermal waters, possibly indicating the recharge during
arid climate (discussed in section 5.4). Depleted stable isotope values
(δ2H: − 36.8 ± 0.8 ‰ and δ18O: − 6.3 ± 0.2 ‰) and moderate temper­
ature of the thermal water at Taptapani site indicate a greater mixing of
thermal water with non-thermal water, which can also be substantiated
geochemically. The chemical facies of the Taptapani thermal water is
found to be Na-Ca-HCO3 type whereas the other thermal waters are Na-
Cl type. The preponderance of bicarbonate type of thermal water in
Taptapani area indicates a greater extent of mixing with non-thermal
waters, which is also corroborated from high tritium value of the Tap­
tapani thermal water (1.5 TU) compared to other thermal waters (<1
TU). The approximate degree of mixing is estimated from tritium con­
centrations assuming the deep-seated thermal water has zero tritium
content (Sammel and Craig, 1981). The percentage of non-thermal
water contribution was found to be highest for Taptapani site (63%)
followed by Atri/Tarabalo (~20%) and Athmalik site (~10%). These
estimated mixing proportions justify the lower temperature and
depleted isotopic composition of the thermal water at Taptapani site and
higher temperature and enriched isotopic composition of the thermal
waters in other sites. The EC correlations with δ2H and δ18O also indi­
cate different groups for thermal waters collected from different sites
(Fig. S3), which rules out the possibility of a common reservoir as the
source for the thermal waters in all the four studied sites. This inference
further strengthens the observations obtained from the hydrochemical
classification (Fig. 3a and b) and isotope trends (Fig. 4a).
The deuterium excess (Dx = δ2 H − 8 × δ18 O) provides a reliable
measure of the physical conditions (surface temperature, humidity) of
the source region responsible for vapor transport to the site of precipi­
tation (Dansgaard, 1964). The Dx of oceanic origin is normally + 10 ‰
in temperate climate (Clark and Fritz, 1997). The mean Dx values of
thermal water during pre- and post-monsoon periods are found to be
similar in this case, i.e., 8.6 ± 1.3 ‰ and 9.0 ± 2.3 ‰ respectively, while
thermal water at Taptapani site has slightly higher Dx value (+13.6 ‰).
The Dx values of the thermal waters suggest their oceanic origin with
some modifications during the infiltration. The modifications include
contribution of recirculated moisture, evaporative enrichment or mixing
with different moisture sources. The non-thermal waters also fall along
the GMWL and LWML indicating precipitation recharge to shallow
aquifer system (Fig. 4b). A few samples mainly from Tarabalo site fall
below LMWL on a line with slope 3.49 indicating evaporation effect.
Higher evaporation is observed in samples during pre-monsoon
compared to post-monsoon (Fig. 4b), which could be due to evapora­
tive enrichment. This seasonal variation in isotope data of non-thermal
waters suggests contribution of local precipitation to the shallow aquifer
system. Unlike thermal waters, there is no site-wise clustering in non-
thermal waters excepting for Taptapani site (Fig. 4b). This observation
suggests that the thermal and non-thermal water circulations in EGMB
follow different flow paths. Furthermore, the non-thermal waters show a
wider scatter in the EC correlations with δ2H and δ18O (Fig. S3) and do
not show a particular grouping, like in the case of thermal waters. This
clearly suggests the influence of soil-water interaction in the top
weathered formation and contribution of precipitation to non-thermal
waters. Depleted isotope composition of non-thermal waters of Tapta­
pani site (mean δ18O: − 6.4 ‰) suggests their origin from rainfall
occurring at higher elevation. The DEM of this area indicates that the
altitude of Taptapani site is ~450 m amsl (above mean sea level) while
other three sites have altitude in the range of 50–75 m amsl (Fig. 2b).
Therefore, it can be concluded that shallow aquifer system of Taptapani
site is recharged by precipitation occurring at higher elevations.
T. Keesari et al.
5.4. Age dating of thermal waters
Very low environmental tritium content observed in thermal waters
of Atri, Tarabalo and Athmalik sites clearly suggests that ages are very
old (>50 years) while at Taptapani, the thermal water is modern water.
Most of the non-thermal waters have tritium content >1.5 TU indicating
modern recharge. A few non-thermal waters show low tritium (~1 TU),
which can be attributed to thermal water mixing. Radiocarbon dating
was carried out to estimate the age of thermal waters. The major chal­
lenge in estimating accurate radiocarbon age of waters is assigning the
initial radiocarbon value for DIC. Several models are in use, which can
account for the different isotope and geochemical processes modifying
the initial signatures of 14C of DIC (Clark and Fritz, 1997; Blaser et al.,
2010 and references therein). The source of CO2 is important in
geothermal waters since different processes provide different initial
radiocarbon values for the DIC. The thermo-metamorphic decarbon­
ation of carbonates and upper mantle degassing contribute to CO2,
which has a 14C value of 0 pMC (Evans et al., 2008). Both these sources
contribute to radiocarbon dilution and overestimation of thermal water
ages. However, the large difference between the δ13C –DIC values of the
studied thermal waters (− 20 to − 16 ‰ VPDB) and the expected values
of decarbonation and degassing processes (− 2 to +2 ‰ and − 8 to − 3 ‰
respectively) indicate that radiocarbon dilution is not significant. This is
further supported by presence of low CO2 concentration (<0.2 %) in gas
emissions from these sites (Mahala, 2019). The oxidation of organic
material in the presence of dissolved sulphate within the aquifer also
complicates 14C dating due to addition of 14C free carbonate to the DIC
reservoir (Aravena et al., 1995). There is no data available on the H2S
Fig. 10. Plots of a) δ13C-DIC vs. HCO–3, line (1) represents DIC derived from atmospheric CO2, line (2) – closed system dissolution of calcite and line (3) – non-
equilibrium dissolution of carbonates, line (4) – DIC under equilibration with soil CO2, b) log pCO2 vs. HCO–3 displaying the open/close condition of thermal and
non-thermal waters with respect to CO2, dashed line represents log pCO2 of recharging water, c) δ13C vs. 14C, d) pH vs. 14C illustrating the influence of deep carbon
sources. The arrows shown in (b), (c) and (d) are eye-guide lines.
14
Journal of Hydrology 612 (2022) 128172
concentration of these thermal waters. However, DIC derived in the
sulphate reduction process normally has δ13C in the range of − 5 to − 10
‰ (Hoefs, 1997), which again different from the range of δ13C –DIC
values observed in this case, therefore the influence of sulphate reduc­
tion on the dating of thermal waters can be ignored.
The silicate mineral weathering reactions supply DIC to waters
through dissolution of soil and atmospheric CO2. Recharging waters
dissolve root zone CO2 to form carbonic acid (log pCO2 − 2.6) facilitating
silicate mineral weathering. In the case of closed condition, the
consumed CO2 is not replenished by the soil gas and that results in
lowering of log pCO2 values, as observed in this case (− 2.3 to − 3.9,
Table S8). The log pCO2 also plays a crucial role in controlling the
saturation state of carbonate minerals (Charlet et al., 1990) and indicate
the microbial oxidation of organic matter (Benedetti et al., 1996). The
open/closed condition of thermal water with respect to CO2 is further
examined from δ13C-DIC vs. HCO–3 plot (Fig. 10a). Atmospheric CO2 has
a typical δ13C value − 8 ‰ (Cerling et al., 1991) therefore the corre­
sponding δ13C-DIC would be +1.6 ‰ shown by line 1 in Fig. 10a. The
closed system dissolution of carbonate rocks without any fractionation is
shown by line 2 (δ13C: 0 ‰). The non-equilibrium dissolution of car­
bonates (1:1 mixture of soil CO2 with δ13C: − 25 ‰ and carbonates with
δ13C: 0 ‰) is shown by line 3. The equilibration of DIC with soil CO2
(δ13C: − 25 ‰) yields − 17.5 ‰ value as shown by line 4. From the graph,
it can be observed that the sample data fall along the line 4 indicating
equilibrium of DIC with soil CO2. Both thermal and non-thermal waters
show a similar source of DIC. The radiocarbon content of the DIC also
modifies similar to δ13C-DIC. Under open system condition, the DIC
exchanges continuously with the 14C active soil gas; therefore, the initial
T. Keesari et al.
activity of DIC (14CDIC) remains at 100 pMC. But, under closed equi­
librium condition, the 14C-DIC decays with time without being replen­
ished. An increasing trend in log pCO2 is noticed in thermal waters from
− 3.9 to − 2.3, which reaches to the value similar to non-thermal water
(Fig. 1b) indicating that the DIC is derived dominantly from soil CO2 and
the decrease in log pCO2 clearly suggests a closed CO2 condition. Cor­
relation between δ13C and 14C is found to be positive implying the
contribution of carbon sources with dead radiocarbon and depleted δ13C
(Fig. 10c). The dissolution of carbonates with time (mineralized organic
matter) is further ascertained by the negative relationship between 14C
and pH (Fig. 10d).
Radiocarbon correction using Pearson model was not applied in this
study as the model demands recharge conditions of the aquifer to obtain
accurate ages. Fontes and Garnier’s (F & G) model though does not
require input parameters and removes the recharge conditions uncer­
tainty, it is applicable to only carbonate systems and therefore was not
considered. In closed system, like that typically exhibited by deep
groundwater, the IAEA model is apt (Clark and Fritz, 1997), as it takes in
to account the temperature dependent isotope fractionation among
carbonate species (CO2-HCO–3–CO2− 3 ), which is highly effective for
thermal waters. The relatively high pH (mean: 8.3) and lower log pCO2
(<-2.6) observed in thermal waters would not support an open CO2
evolutionary pathway, since the continuous supply of CO2 would render
acidic pH.
The general formula for corrected 14C groundwater age is given as
(equation (4));
a14 Cmeasured
Age = − 8267 × ln (4)
q × a14 Cinitial
The correction factor q is calculated using the following equation (5):
δ13 CDIC − δ13 Ccarb
q= (5)
δ Csoil − εgb − δ13 Ccarb
13
where εgb = − 9483
T + 23.89, which considers isotope exchange among
2–
carbon species (CO2 gas ↔ HCO–aq
3 ↔ CO3 solid).
where, δ13CDIC = measured 13C in groundwater, δ13Csoil = δ13C of the
soil CO2, δ13Ccarb = δ13C of the calcite, Ɛgb = additive fractionation
factor between CO2 gas and HCO–3 and T is the temperature in kelvin.
In order to account for the contribution of deep inorganic carbon
sources and subsequent radiocarbon dilution, we have used the equation
(6) proposed by Wang et al. (2019);
δ13 CDIC − δ13 Cdeadcarb
q= (6)
δ13 Crech − δ13 Cdeadcarb
δ13Crech represents the recharge area; δ13Cdead carb represents the deep
source inorganic CO2. The δ13C value of deep source inorganic CO2 of
gas reservoirs and geothermal water is usually around − 1.5 ‰ (Wang
et al., 2019), which is selected as the value of δ13Cdead carb to correct the
14
C age of deep source “dead carbon”. The apparent ages were also
provided for comparison, which is estimated by considering 98.6 pMC
(highest 14C measured in the study area) as initial 14C value. The cor­
rected ages of thermal waters are shown in Table 1.
The results obtained from the 14C correction models slightly differ
from the apparent age estimates (uncorrected), indicating the impact of
temperature dependent fractionation on 14C value and impact of mixing
with deep inorganic carbon source (Table 1). The conformity between
the corrected and uncorrected radiocarbon age dating is largely due to
the absence of dissolution of the dead carbon from the aquifer matrix,
which is exemplified from the δ13C - DIC (-18.75 to − 21 ‰) values of the
thermal water. The δ13C values of DIC clearly reflect the silicate
weathering with soil CO2 derived from C3 type of plants that has an
average value of about − 19.1 ‰ (Das et al., 2005). The phenomenon of
silicate weathering is also substantiated from the subsurface geological
formation of the study area. However, the three modeled age estimates
are found to have similar range. The agreement among different
15
Journal of Hydrology 612 (2022) 128172
modelled values provided confidence to the reliability of the ages
determined. The residence time of thermal waters at Atri (T1: 14.0 – 14.9
Ka) and Tarabalo (T1: 13.3–14.2 Ka) is found to be similar while thermal
waters at Athmalik are relatively older (T1: 18.8 – 20.7 Ka). Thermal and
non-thermal mixed sources show ages in the range of 2.8 – 7.6 Ka. Non-
thermal water is shown by negative radiocarbon age indicating modern
recharge. The estimated ages of the thermal waters suggest that these
waters are recharged during Last Glacial Maximum (LGM), a relatively
arid climatic regime. This interpretation is supported by the enriched
δ18O values of the thermal waters (δ18O: − 3.2 and − 4.1 ‰ for Athmalik
and Atri/Tarabalo respectively) compared to the present-day meteoric
waters (average rainwater δ18O: − 5.5 ‰, Keesari et al., 2016). We
interpret the enriched δ18O value of thermal waters to represent
recharge during the decreased summer monsoon rainfall, which is
characterized by enriched mean annual δ18O of the rainfall. High
evaporative flux reflects a significant reduction in the soil moisture
which facilitates greater fractionation and leads enriched δ18O compo­
sition in recharging waters, as was observed in this case. The inter-
tropical aridity in EGMB (Delang-Puri sector, Odisha) during 12 – 17
Ka has been reported by Kulkarni et al (1998), wherein the authors also
noted that the isotopic composition of groundwater is enriched
compared to modern precipitation hinting at the possible recharge
during arid climate.
The global sea level data indicate that the sea level during the period
20 Ka was 130 m below the current level (Lambeck et al., 2014). This
could have displaced the shoreline to further east from the current
location. A similar phenomenon was reported in Bengal basin
(Bangladesh) where the shoreline during the LGM (20 Ka) was displaced
100–150 km to the south (Ravenscroft et al., 2018). Considering the age
of the thermal waters and the sea level during that time, the sea water
component as the source of thermal water can be squarely ruled out. The
monsoonal circulation was greatly reduced during LGM and the resul­
tant precipitation was also isotopically enriched (δ18O: ~ − 3.5 ‰),
which matches well with the isotopic composition of thermal waters.
The deep groundwater from Chittagong coastal aquifer (Bangladesh)
showed a radiocarbon age of 17 Ka age and an enriched stable isotope
composition (Ravenscroft et al., 2018). The paleo-recharge history of
thermal waters is clearly displayed in the positive correlations among
Temperature, δ18O and water age (Fig. 11). The trends observed in this
figure clearly suggest that the observed enrichment in thermal waters is
due to their recharge during arid climate. The deep groundwaters from
Middle Ganga Plains are found to be 3.5 to 4.7 Ka old while in Deltaic
Plains the typical ages range from 1 to 10 Ka (Lapworth et al., 2018) and
3–9 Ka (Hoque and Burgess, 2012). A comparison of the deep ground­
water ages from Ganga Basin with the thermal waters of EGMB suggests
Fig. 11. Temperature – δ18O – water age correlations throwing light on the
recharge history of thermal waters.
T. Keesari et al.
longer circulation path of the thermal waters compared to the deep non-
thermal groundwater systems. However, the thermal waters from the
adjacent Godavari river basin show a similar age, between 9 and 18.6 Ka
(Chatterjee et al., 2019) which essentially infers that the evolution his­
tory of both the geothermal systems is same.
5.5. Thermal water genesis, circulations and reservoir depth
There are many speculations on the source of heat in shear zones of
EGMB since very little data is available. Field studies supplemented by
satellite data also indicate that the thermal springs lie along lineaments
(Fig. 1c, 2b), which infer close relationship between tectonics and
thermal activity. There is no evidence of any recent magmatic activity
around these thermal springs and hence the likely source of heat is the
rocks of EGMB. The radioactive elements concentrations and the heat
production (71.3–142.8 mW/m2) in the EGMB is reported to be highest
amongst the granulite belts of India (Kumar et al., 2007). Very high
levels of radioactive elements (U, 600 mg/kg; Th 1500 mg/kg and K,
5%) are reported in metamorphic rocks (Baranwal et al., 2006). Another
study conducted on gas emissions of these thermal springs indicated a
considerable amount of helium gas (0.27 to 1.7% by volume) and the N2-
Ar-He ternary diagram suggested a long residence time of the gas phase
in the crust affected by U and Th decay (Mahala, 2019). From the cor­
relations among the temperature and water age, it is observed that
temperature of thermal waters increases with residence time of water.
From this observation and tectonic and thermal information provided
above, it can be concluded that the thermal waters in EGMB are pro­
duced due to the long contact and deep circulation of the rainwater
inside the Precambrian metamorphites (high heat producing)
comprising elevated levels of radioactive elements.
The water flows in geothermal systems are complex due to the
occurrence of complex subsurface stratigraphy and heterogeneity in
geology, temperature gradients and fractures or other conduits in the
permeable zones. The E-W trending graben bounding faults provide
permeable pathways for a thermal water circulation system along the
northern sector of EGMB. Based on the hydrochemical, isotopic and
residence time values as well as variation of temperatures in thermal
waters, two modes of thermal flow paths can be suggested in EGMB. The
first mode is N-S flow system that originates from Iron Ore Super Group
(IOSG) plateau and proceed to graben floor through fractures and fis­
sures to ultimately issue on the surface along the contact zones of IOSG
plateau and northern edge of Mahanadi graben. The second mode is S-N
directional flow system that originates from Eastern Ghats Super Group
(EGSG) plateau and reach graben floor, which subsequently appear as
thermal sprouts along the contact zones of IOSG plateau and southern
edge of Mahanadi graben.
The rainwater which upon penetrating downwards along the faults
and fractures is heated by geothermal gradient and then rises to the
surface through the permeable zones. The non-thermal water also cir­
culates in the same way, but do not flow through the permeable fault
zones and hence restricted to shallow depths. The circulation depth of
thermal waters is estimated using the equation (7);
Tz − To
Z= + Zo (7)
G
where Z is the circulation depth (m), To is the local annual average
temperature (26.6 ◦ C from https://en.climate-data.org); G is thermal
gradient of the region (0.04 ± 0.01 ◦ C/m after Padhi and Pitale, 1995),
and Zo is the thickness of the constant temperature zone (taken as 0 m).
Tz is the temperature (◦ C) of the geothermal reservoir calculated by a
reasonable geothermometer (IMG in this case, Table 4). The estimated
circulation depths for Atri, Tarabalo, Athmalik and Taptapani sites are
2.3 ± 0.6 km, 2.1 ± 0.5 km, 2.4 ± 0.6 km and 1.6 ± 0.4 km respectively
(Table 4). Reservoir depths of similar order (1–3 km) have been reported
in several geothermal systems of India (Chatterjee et al., 2016, 2017;
16
Journal of Hydrology 612 (2022) 128172
Singh et al., 2020). A conceptual hydrogeological-hydrochemical-
isotope model for thermal water genesis and circulations in Mahandi
graben, EGMB is presented in Fig. 12. From the above calculations, it can
be inferred that the geothermal reservoir in EGMB lies in the depth range
of 2.1 ± 0.35 km.
5.6. Future scope
Limberger et al. (2018) reported that the geothermal electrical pro­
duction is mostly confined to the areas containing high geothermal
gradients and sufficient reservoirs, which are very limited. Hence
development of technology focusing exploitation of low-enthalpy
geothermal systems would pave way for reduction in fossil burning
and leading to cleaner environment. Till now about 4000 thermal
springs have been identified in Indian subcontinent and except few high
temperature thermal springs (i.e. Puga and Chumathang in Indus valley-
Ladakh, Panamik in Nubra valley- Ladakh, Parbati and Beas valley in
Himachal Pradesh, Tapoban and Badrinath in Uttarakhand) all other
thermal springs fall in the medium to low enthalpy category (Singh
et al., 2016). Indian shield has an estimated potential of 10,000 MW
(www.indiaenergyportal.org) the majority of which are low to moderate
enthalpy systems. Extensive investigations have been carried out with
regard to geological, geochemical and geophysical aspects of
geothermal systems but the drilling investigations have been very
limited. Though it was realized a long time ago that India has good
potential to harness geothermal energy (Krishnaswamy and Rav­
ishanker, 1982), the development of the geothermal resources has not
progressed mainly due to inadequate understanding of the deeper
thermal regime, leading to uncertainty over the proposed reservoir
models as well as the sustainability of heat source.
There are only a couple of geothermal energy-based power plants
constructed/planned at a few places, such as, a 25 MW geothermal
power project in the West Coast hot spring belt (Sharma and Trikha
2013), a 35 MWe geothermal power plant in Gujarat (Chandrasekharam
and Chandrasekhar, 2015; Singh et al., 2016), a 5 KW pilot power plant
at Manikaran (Razdan et al., 2008), an approved 25 MWe geothermal
power project in Andhra Pradesh (Chandrasekharam and Chan­
drasekhar, 2015). But with regard to power production, the geothermal
resources are entirely undeveloped in the country at present.
Reservoir temperature, its depth and volume are the primary factors
considered while planning geothermal energy exploitation. India fares
well with regard to the information on the geothermal reservoir tem­
perature and its depth, but the information on genesis, recharge history
and movement of thermal fluids is very limited. There are reports on the
reduction of thermal water discharges and drying up of reservoirs after
the commencement of thermal water exploitation (Chandrajith et al.,
2013; Pingheng et al., 2017), which clearly demonstrate the importance
of understanding the genesis and estimating the flow patterns of the
thermal fluids in any geothermal system. Therefore, in order to expand
the footprint of geothermal energy use in India, it is very important to
determine the genesis, recharge history and thermal water circulations
of geothermal systems. In this regard, isotope techniques are very
valuable tools that can address uncertainty over the sustainability of
geothermal reservoirs as demonstrated in this study.
6. Conclusions
The genesis and circulation of thermal and non-thermal waters in
shear zones of Mahanadi graben of Eastern Ghats Mobile Belt region are
investigated using multi-tracers including chemical and isotope tracers.
The thermal waters issue along the faults of Mahanadi graben and are
classified as low to medium enthalpy systems (55 – 59 ◦ C). Thermal
waters close to graben are alkaline (pH = 8.75 – 9.13), less saline (EC
<1500 µS/cm) and Na-Cl type while away from the graben thermal
water has low temperature (42 ◦ C), neutral pH and is Na-Ca-HCO3 type.
The characteristic ionic ratios and major ion trends indicate that bulk of
T. Keesari et al.
Fig. 12. Conceptual map depicting the genesis and circulation patterns of thermal waters in shear zones of Mahanadi graben, EGMB. Transect a-a’ (shown in Fig. 1c)
runs parallel to the coast from Singhbhum craton to EGB province.
the chemical ions is derived from the silicate weathering in both the
thermal and non-thermal waters.
Isotope characteristics of the thermal waters indicate meteoric
source and presence of three different thermal reservoirs. Stable isotope
and environmental tritium data indicate that the non-thermal waters are
recharged by modern precipitation. Influence of evaporative enrichment
in non-thermal waters is observed during pre-monsoon period. The
thermal circulations seem to originate from northern side of the graben
in the case of Athmalik site and southern side in the case of Atri/Tar­
abalo sites. The estimated reservoir temperatures range between 92 and
124 ◦ C and the circulation depths are found to be 1.6 – 2.4 km. The
radiocarbon age of 13.3 to 20.7 Ka for thermal waters suggests dominant
recharge during LGM, which is characterized by arid climate and low
rainfall. The stable isotope and hydrochemical inferences clearly
establish the improbability of marine sources while the age and tem­
perature correlations indicate thermal gradient as the source of heat.
The emergence of thermal waters is controlled through fracture systems,
and the hydrogeochemical and isotopic compositions reflect minimum
mixing with non-thermal waters during their rise to surface. However,
thermal water located away from graben indicates significant mixing
with non-thermal water and hence lower outlet temperature and
depleted isotopic content.
CRediT authorship contribution statement
Tirumalesh Keesari: Conceptualization, Methodology, Investiga­
tion, Data curation, Writing – original draft. Sitangshu Chatterjee:
Conceptualization, Software, Visualization, Investigation, Validation.
Mukund Kumar: Methodology, Investigation. Hemant Mohokar: .
Uday Kumar Sinha: Supervision, Resources. Annadasankar Roy:
Formal analysis, Investigation. Diksha Pant: Formal analysis, Investi­
gation. Suraj D. Patbhaje: Methodology, Investigation.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
17
Journal of Hydrology 612 (2022) 128172
Data availability
The data is provided in the supplimenatary file available online
Acknowledgements
Authors thank Dr. H.J. Pant, Head, Isotope and Radiation Applica­
tion Division (BARC) for the constant encouragement and support dur­
ing the course of this work. Mr. Ajay Jaryal and Mr. S.N. Kamble (Isotope
Hydrology Section, IRAD, BARC) and personnel from GSI are duly
acknowledged for their help during field sampling. Authors would like
to thank Dr. Diana Sharma (NPDF, Isotope Hydrology Section, BARC) for
critically editing the manuscript and helping in map preparation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jhydrol.2022.128172.
References
Aggarwal, J.K., Palmer, M.R., Bullen, T.D., Ragnarsdottir, K.V., Arnorsson, S., 2000. The
boron isotope systematics of Icelandic geothermal waters: 1. meteoric water charged
systems. Geochim. Cosmochim. Acta. 64, 580–585.
Aravena, R., Wassenaar, L.I., Plummer, L.N., 1995. Estimating 14C Groundwater Ages in
a Methanogenic Aquifer. Water Resour. Res. 31 (9), 2307–2317. https://doi.org/
10.1029/95WR01271.
Arnorsson, S., 1983. Chemical equilibria in Icelandic geothermal systems-implications
for chemical geothermometry investigations. Geothermics 12, 119–128.
Arnorsson, S., D́ Amore, F., Gerardo, J., 2000. Isotopic and chemical techniques in
geothermal exploration (ed. S. Arnórsson). Vienna, International Atomic Energy
Agency, 351p.
Baranwal, V.C., Sharma, S.P., Sengupta, D., Sandilya, M.K., Bhaumik, B.K., Guinc, R.,
Saha, S.K., 2006. A new high background radiation area in the Geothermal region of
Eastern Ghats Mobile Belt (EGMB) of Orissa. India. Rad. Measure. 41, 602–610.
Benedetti, M.F., van Riemsdijk, W.H., Koopal, L.K., 1996. Humic substances considered
as a heterogeneous Donnan gel phase. Environ Sci Technol 30 (6), 1805–1813.
Bhowmik, S.K., Dasgupta, S., Hoernes, S., Bhattacharya, P.K., 1995. Extremely high
temperature calcareous granulites from the Eastern Ghats, India: evidence for
isobaric cooling, fluid buffering and terminal channelized fluid flow. Europ. J. Min.
7, 689–703.
Blaser, P.C., Coetsiers, M., Aeschbach-Hertig, W., Kipfer, R., Van Camp, M., Loosli, H.H.,
Walraevens, K., 2010. A new groundwater radiocarbon correction approach
T. Keesari et al.
accounting for palaeoclimate conditions during recharge and hydrochemical
evolution: The Ledo-Paniselian Aquifer. Belgium. Appl. Geochem. 25, 437–455.
Cerling, T.E., Solomon, D.K., Quade, J., Bowman, J.R., 1991. On the isotopic composition
of carbon in soil carbon dioxide. Geochem. Cosmochim. Acta. 55, 3403–3405.
Chandrajith, R., Barth, J.A.C., Subasinghe, N.D., Merten, D., Dissanayake, C.B., 2013.
Geochemical and isotope characterization of geothermal spring waters in Sri Lanka:
Evidence for steeper than expected geothermal gradients. J. Hydrol. 476, 360–369.
Chandrasekhar, T., Minissale, A., Vaselli, O., Chandrasekharam, D., D., Singh, H.K.,,
2018. Understanding the evolution of thermal fluids along the western continental
margin of India using geochemical and boron isotope signatures. Geothermics.
https://doi.org/10.1016/j.geothermics.2018.03.007.
Chandrasekharam, D., Chandrasekhar, V. 2010. Energy independence through CDM
using geothermal resources: Indian scenario. Proceedings of the World Geothermal
Congress 2010, Bali, Indonesia, 5 pp.
Chandrasekharam, D., Chandrasekhar, V. 2015. Geothermal energy resources, India:
country update. World Geothermal Congress. 2015.
Charlet, L., Wersin, P., Srumm, W., 1990. Surface charge of MnCO3 and FeCO3. Geochim
Cosmochim Acta 54 (8), 2329–2336.
Chatterjee, S., Sinha, U.K., Biswal, B.P., Jaryal, A., Jain, P.K., Patbhaje, S., Dash, A.,
2019. An Integrated Isotope-Geochemical Approach to Characterize a Medium
Enthalpy Geothermal System in India. Aqua. Geochem. 25, 63–89. https://doi.org/
10.1007/s10498-019-09352-z.
Chatterjee, S., Ansari, M.A., Deodhar, A.S., Sinha, U.K., Dash, A., 2017. A multi-isotope
approach (O, H, C, S, B and Sr) to understand the source of water and solutes in some
the thermal springs from West Coast geothermal area. India. Arab. J. Geosci. 10, 242.
https://doi.org/10.1007/s12517-017-3022-0.
Chatterjee, S., Sharma, S., Ansari, M.A., Deodhar, A.S., Low, U., Sinha, U.K., Dash, A.,
2016. Characterization of subsurface processes and estimation of reservoir
temperature in Tural and Rajwadi geothermal fields, Maharashtra. India. Geotherm.
59, 77–89. https://doi.org/10.1016/j.geothermics.2015.10.011.
Chatterjee, S., Sinha, U.K., Ansari, M.A., Mohokar, H.V., Dash, A., 2018. Application of
lumped parameter model to estimate mean transit time (MTT) of the thermal water
using environmental tracer (3H): Insight from Uttarakhand geothermal area (India).
Appl. Geochem. 94, 1–10. https://doi.org/10.1016/j.apgeochem.2018.04.013.
Chetty, T.R.K., 2001. Eastern Ghats Mobile Belt, India: a collage of juxtaposed terranes
(?). Gond. Res. 4, 319–328.
Clark, I.D., Fritz, P., 1997. Environmental Isotopes in Hydrogeology. Lewis Publishers,
New York.
Coplen, T.B., 1996. New guidelines for reporting stable hydrogen, carbon and oxygen
isotope-ratio data. Geochim Cosmochim. Acta 60, 3359–3360.
Craig, J., Absar, A., Bhat, G., Cadel, G., Hafiz, M., Hakhoo, N., Kashkari, R., Moore, J.,
Ricchiuto, T.E., Thurow, J., Thussu, B., 2013. Hot springs and the geothermal energy
potential of Jammu & Kashmir State, N.W. Himalaya. India. Earth-Science Rev. 126,
156–177.
Dansgaard, W., 1964. Stable isotopes in precipitation. Tellus 16, 436–468.
Das, A., Krishnaswami, S., Bhattacharya, S., 2005. Carbon isotope ratio of dissolved
inorganic carbon (DIC) in rivers draining the Deccan Traps, India: sources of DIC and
their magnitudes. Earth Plan. Sci. Lett. 236, 419–429. https://doi.org/10.1016/j.
epsl.2005.05.009.
Dasgupta, S., 1993. Contrasting mineral parageneses in high temperature calc-silicate
granulites: examples from the Eastern Ghats. India. J. Metamor. Geo. 11, 193–202.
Dasgupta, S., Bose, S., Das, K., 2013. Tectonic evolution of the Eastern Ghats Belt.
Precam. Res. 227, 247–258.
Evans, M.J., Derry, L.A., France-Lanord, C., 2008. Degassing of metamorphic carbon
dioxide from the Nepal Himalaya. Geochem. Geophys. Geosyst. 9 (4) https://doi.
org/10.1029/2007GC001796.
Exley, R.A., Mattey, D.P., Clague, D.A., Pillinger, C.T., 1986. Carbon isotope systematics
of a mantle “hotspot”: a comparison of Loihi Seamount and MORB glasses. Earth
Planet. Sci. Lett. 78, 189–199.
Fournier, R.O., 1977. Chemical geothermometers and mixing models for geothermal
systems. Geothermics 5, 40–41.
Fournier, R.O., 1979. A revised equation for Na/K geothermometer. Geotherm.
Resources Council Trans. 3, 221–224.
Fournier, R.O., Truesdell, A.H., 1970. Chemical indicators of sub-surface temperatures
applied to hot spring waters of Yellowstone national park, USA. Proc. UN Symp. On
development and utilization of geothermal resources. Pissa, 2 (1). Geothermics Spl
Issue. 2, 529–535.
Fournier, R.O., Truesdell, A.H., 1973. An empirical Na-K-Ca geothermometer from
natural waters. Geochim. Cosmochim. Acta 37, 1255–1275.
Giggenbach, W.F., 1988. Geothermal solute equillibria. Derivation of Na-K-Mg-K
geoindicators. Geochim. Cosmochim. Acta 52, 2749–2765.
Giggenbach, W.F., 1992. Isotope shift in waters from geothermal and volcanic systems
along convergent plate boundaries and their origin. Earth and Planetary Sci. Lett.
113, 495–510.
Gsi.,, 1987. Records of the geological survey of India. Geological Survey of India,
Calcutta.
Gsi.,, 1991. Geothermal atlas of India. Geological Survey of India, Calcutta.
Hoefs, J., 1997. Stable Isotope Geochemistry, Fourth Edition. New York, Springer-Verlag.
Hoque, M.A., Burgess, W.G., 2012. 14C dating of deep groundwater in the Bengal Aquifer
System, Bangladesh: Implications for aquifer anisotropy, recharge sources and
sustainability. Journal of Hydrology 444–445 (2012), 209–220.
Hounslow, A.W., 1995. Water quality data- Analysis and Interpretation. Lewis
Publishers, CRC Press, Florida, USA.
Keenan, J.H., Keyes, F.G., Hill, P.G., Moore, J.G., 1969. Steam Tables – Thermodynamic
Properties of Water Including Vapour, Liquid and Solid Phases (international edition
– metric units). Wiley, New York, p. 162.
18
Journal of Hydrology 612 (2022) 128172
Keesari, T., Sinha, U.K., Deodhar, A., Krishna, S.H., Ansari, A., Mohokar, H.V., Dash, A.,
2016. Occurrence of fluoride in groundwater from an industrial area in Odisha State,
India – A geochemical perspective. Environ Earth Sci. 75, 1090. https://doi.org/
10.1007/s12665-016-5874-0.
Keesari, T., Chatterjee, S., Pant, D., Singh, M., Sakhare, V., Sinha, U.K., Mohokar, H.,
Jaryal, A., Roy, A., Maitra, A., 2019. Dating of hot springs at Atri, Tarabalo and
Athmalik sites in Odisha, India using radiocarbon technique. J. Radioanal. Nucl.
Chem. https://doi.org/10.1007/s10967-019-06867-1.
Krishnaswamy, V.S., Ravishanker,, 1982. Scope of development, exploration and
preliminary assessment of geothermal resources potential of India. Records GSI, VIII
2, 17–40.
Kulkarni, K. M., Navada, S. V., Nair, A.R., Rao, S. M., Shivanna, K., Sinha, U. K., Sharma,
S. 1998. Drinking water salinity problem in coastal Orissa, India: Identification of
past transgressions of sea water by isotope investigation. IAEA: N. 1998. Web. 293-
306.
Kumar, B., Rai, S.P., Kumar, U.S., Verma, S.K., Pankaj, G., Vijaya Kumar, S.V., Rahul
Jaiswal, B.K., Purendra, S.R., Kumar, N.G., 2010. Isotopic characteristics of Indian
precipitation. Water Resour. Res. 46, W12548. https://doi.org/10.1029/
2009WR008532.
Kumar, P.S., Menon, R., Reddy, G., 2007. The role of radiogenic heat production in the
thermal evolution of a Proterozoic granulite-facies orogenic belt: Eastern Ghats.
Indian Shield. Earth Planet. Science. Lett. 254 (1), 39–54.
Kundu, N., Panigrahi, M., Sharma, S., Tripathy, S., 2002. Delineation of fluoride
contaminated groundwater around a hot spring in Nayagarh, Orissa, India using
geochemical and resistivity studies. Environ. Geol. 43, 228–235.
Lambeck, K., Rouby, H., Purcell, A., Sun, Y., Sambridge, M. 2014. Sea level and global ice
volumes from the Last Glacial Maximum to the Holocene. PNAS October. 28. 2014.
111 (43). 15296-15303.
Lapworth, D.J., Zahid, A., Taylor, R.G., Burgess, W.G., Shamsudduha, M., Ahmed, K.M.,
Mukherjee, A., Gooddy, D.C., Chatterjee, D., MacDonald, A.M., 2018. Security of
Deep Groundwater in the Coastal Bengal Basin Revealed by Tracers. Geophysical
Research Letters 45 (16), 8241–8252. https://doi.org/10.1029/2018GL078640.
Limberger, J., Boxem, T., Pluymaekers, M., Bruhn, D., Manzella, A., Calcagno, P.,
Beekman, F., Cloetingh, S., van Wees, J.-D., 2018. Geothermal energy in deep
aquifers: A global assessment of the resource base for direct heat utilization.
Renewable and Sustainable Energy Reviews 82 (1), 961–975.
Mahala, S.C. 2019. Geology, Chemistry and Genesis of Thermal Springs of Odisha, India,
Springer Briefs in Earth Sciences, https://doi.org/10.1007/978-3-319-90002-5.
Maitra, A., Chatterjee, A., Keesari, T., Gupta, S., 2020. Forming topography in granulite
terrains: the (un) importance of chemical weathering. J. Earth Syst. Sci. 129, 17.
https://doi.org/10.1007/s12040-019-1293-4.
Marty, B., Jambon, A., 1987. C/He in volatile fluxes from the solid Earth: Implications for
carbon geodynamics. Earth Planet. Sci. Lett. 83, 16–26.
Minissale, A., Vaselli, O., Chandrasekharam, D., Magro, G., Tassi, F., Casiglia, A., 2000.
Origin and evolution of ‘intra cratonic’ thermal fluids from central-western
peninsular India. Earth Planet. Sci. Lett. 181 (3), 377–394.
Morgenstern, U., Taylor, C.B., 2009. Ultra low-level tritium measurement using
electrolytic enrichment and LSC. Isotopes Environ Health Stud. 45 (2), 96–117.
https://doi.org/10.1080/10256010902931194.
Nair, A.R., Joseph, T.B., Rao, S.M., 1990. Measurement of low-level tritium in water by
electrolytic enrichment and liquid scintillation counting. Bulletin of Radiation.
Navada, S.V., Rao, S.M., 1991. Isotope studies of some geothermal waters in India.
Isotopenpraxis. 27, 153–163.
Navada, S.V., Nair, A.R., Sharma, S., Kulkarni, U.P. 1995. Geochemical and isotope
studies of the geothermal areas of Central and Northern India. In: IAEA (Ed.), Isotope
and Geochemical Techniques Applied to Geothermal Investigation. IAEA, Vienna.
63–82.
Nicholson, K., 1993. Geothermal Fluids Chemistry and Exploration Techniques. Springer-
Verlag 1–215.
Padhi, R.N., Pitale, U.L., 1995. Potential geothermal fields in the context of national
scenario on non-conventional energy resources development programme in India.
Proc. WGC 1995, 525–530.
Pang, Z.H., Reed, M.H., 1998. Theoretical chemical thermometry on geothermal waters:
problems and methods. Geochim Cosmochim Acta 62, 1083–1091.
Pingheng, Y., Qun, C., Shiyou, X., Jianli, W., Longran, C., Qin, Y., Zhaojun, Z., Feng, C.,
2017. Hydrogeochemistry and geothermometry of deep thermal water in the
carbonate formation in the main urban area of Chongqing. China. J. Hydrol. 549,
50–61.
Ramakrishnan, M., 1987. Stratigraphy, sedimentary environment and evolution of the
late Proterozoic Indravati basin, Central India. Mem. Geol. Soc. India. 6, 139–160.
Ravenscroft, P., McArthur, J.M., Rahman, M.S., 2018. Identifying multiple deep aquifers
in the Bengal Basin: Implications for resource management. Hydrol. Proc. 32,
3615–3632. https://doi.org/10.1002/hyp.13267.
Razdan, P.N., Agarwal, R.K., Singh, R., 2008. Geothermal Energy Resources and its
Potential in India. e-J. Earth Scien. Ind I I, 30–42. http://www.earthscienceindia.in
fo/.
Roy, S., Mareschal, J.C., 2011. Constraints on the deep thermal structure of the Dharwar
craton, India, from heat flow, shear wave velocities, and mantle xenoliths.
J. Geophys. Res. 116 (B02409) https://doi.org/10.1029/2010JB007796.
Sammel, E.A., Craig, R.W., 1981. The geothermal hydrology of Warner valley, Oregon: a
reconnaissance study. US Geological Survey Professional Paper. 1044 (1), 47.
Santhosh, M., 2012. Geological Society. London, Special Publications. 365, 263–288.
https://doi.org/10.1144/SP365.14.
Sarolkar P.B. 1996. Characteristics of Thermal water from shallow reservoir at Tattapani
geothermal field, Dist. Surguja, Madhya Pradesh, India, Geothermal Energy in India,
Eds. U.L. Pitale and R.N. Padhi, GSI. Spl. Pub. No. 45. 1996. 75-82.
T. Keesari et al.
Sharma, O.P., Trikha, P., 2013. Geothermal energy and its potential in India. Renewable
Energy. AkshayaUrja. 7 (1), 14–18.
Singh, H.K., Chandrasekharam, D., Trupti, G., Mohite, P., Singh, B., Varun, C., Sinha, S.
K., 2016. Potential Geothermal Energy Resources of India: A Review. Curr.
Sustainable Renewable Energy Rep. https://doi.org/10.1007/s40518-016-0054-0.
Singh, H.K., Satish, K.S., Mohammad, A.A., Dornadula, C., 2020. Tracing the evolution of
thermal springs in the Hazaribagh area of Eastern Peninsular India through
hydrogeochemical and isotopic analyses. Geotherm. 85, 101817 https://doi.org/
10.1016/j.geothermics.2020.101817.
Spycher, N., Peiffer, L., Sonnenthal, E.L., Saldi, G., Reed, M.H., Kennedy, B.M., 2014.
Integrated multicomponent solute geothermometry. Geothermics. 51, 113–123.
Thussu, J.L., 2002. Geothermal energy resources of India. Geol. Surv. India. Spec. Publ.
69, 210.
Tiwari, S.K., Santosh, K.R., Sukesh, K.B., Anil, K.G., Manju, N., 2016. Stable isotopes
(δ13C-DIC, δD, δ18O) and geochemical characteristics of geothermal springs of
19
Journal of Hydrology 612 (2022) 128172
Ladakh and Himachal (India): Evidence for CO2discharge in northwest Himalaya.
Geothermics. 64, 314–330.
Valdiya, K.S., 2016. The making of India. Geodynamic evolution, (2nd ed.),. Springer,
p. 923 pp..
Wang, H., Mao, X.M., Wang, T., Feng, L., Liang, L., Zhu, D., Yang, K., 2019.
Hydrogeochemical characteristics of hot springs exposed from fault zones in western
Guangdong and their 14C age correction. J. of Groundwater Sci. and Eng. 7 (1),
1–14. https://doi.org/10.19637/j.cnki.2305-7068.2019.01.001).
Wright, J.D., Miller, K.G., Fairbanks, R.G., 1991. Evolution of modern deepwater
circulation: evidence from the late Miocene Southern Ocean. Paleoceanography. 6,
275–290. https://doi.org/10.1029/90PA02498.
Zimik, H.V., Farooq, S.H., Prustry, P., 2017. Geochemical evaluation of thermal springs
in Odisha. India. Environ. Earth Sci. 76, 593. https://doi.org/10.1007/s12665-017-
6925-x.