STOTEN-151888; No of Pages 15

Science of the Total Environment xxx (xxxx) xxx

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Science of the Total Environment

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Salinity and temperature profiling for the submarine groundwater discharge

simulations: Quantification through heat and solute transport model
Chandrashekhar Bhagat a, Anant Misra b, Pranab Kumar Mohapatra a, D.S. Suresh Babu c, Manish Kumar d,
⁎
a
Discipline of Civil Engineering, Indian Institute of Technology, Gandhinagar 382355, India
b
Discipline of Earth Sciences, Indian Institute of Technology, Gandhinagar 382355, India
c
National Centre for Earth Science Studies, Akkulam, Thiruvananthapuram 695031, India
d
Sustainability Cluster, School of Engineering, University of Petroleum & Energy Studies, Dehradun, Uttarakhand 248007, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Temperature emerged as a better indica-

tor than salinity for the delineation of
mixing zones.
• SGD flux varied between 1.04 and
181 m3.year−1 which is lower than SGD
along the Bay of Bengal.
• Trace metal flux varied from below detec-
tion to 77.41 kg. year−1 along the Gujarat
cost of India.
• Order of metal flux (kg. year−1) was
Zn2+ ≫ Fe2+ > Cr2+ implying agricul-
tural imprints.
• Higher Fe and Zn loading corresponds to
higher environmental pollution vulnera-
bility.

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

Article history: Developed coastal regions are the hotspots for contaminated groundwater discharge, affecting sensitive marine ecosys-
Received 12 August 2021 tems. The present study aims to identify submarine groundwater discharge (SGD) locations and quantify the contam-
Received in revised form 14 November 2021 inant load reaching to the western coast of India (Gujarat coast) using stable isotopes, seepage meter, heat and solute
Accepted 18 November 2021
transport model. The coastal aquifers are highly enriched in trace metals due to various active natural processes and
Available online xxxx
anthropogenic activities across the coast. Terrestrial and recirculated SGD was a significant contributor to flow and
Editor: José Virgílio Cruz metal load, which ranged from 1.04 to 181.1 m3.year−1 and 0–77.41 kg.year-1, respectively. The highest estimated
SGD in the Gujarat coast was relatively less than the SGD reported in the Bay of Bengal and comparable to the
Keywords: South Chennai coast. The order of metal flux found in the study was Zn > Fe > Cr > Pb > Ni > Cu > Mn, whereas
SGD the highest flux of Zn (77.41 kg. year−1) was reported at Fansa beach, which was 7x Fe-flux and 45 x Cr-flux, respec-
Quantification tively. Higher micronutrients (Fe and Zn) load in the southern coast leads to increased vulnerability of eutrophication,
Seepage meter algal blooms and biotic ligand formation in aquatic species. This enrichment of micronutrients in the coastal ecosystem
Numerical modelling was evident by the growth of seaweeds on the seabed at SGD identified locations.
Metal load
Gujarat coast

⁎ Corresponding author at: Energy Acres, UPES, Dehradun, Uttarakhand 248007, India.
E-mail addresses: manish.kumar@ddn.upes.ac.in manish.env@gmail.com (M. Kumar).

http://dx.doi.org/10.1016/j.scitotenv.2021.151888
0048-9697/© 2021 Elsevier B.V. All rights reserved.

Please cite this article as: C. Bhagat, A. Misra, P.K. Mohapatra, et al., Salinity and temperature profiling for the submarine groundwater discharge
simul..., Science of the Total Environment, http://dx.doi.org/10.1016/j.scitotenv.2021.151888
C. Bhagat et al.
1. Introduction
Interaction between two hydrological masses, i.e. seawater and ground-
water, manifests as seawater intrusion (SWI) or submarine groundwater
discharge (SGD) (Taniguchi et al., 2002; Babu et al., 2021) in the coastal re-
gions. SGD can be defined as the seepage of fresh groundwater and
recirculated seawater through a sand bed or coastal aquifers reaching into
the sea(Moore, 2006; Taniguchi et al., 2002). The rate of SGD is influenced
by numerous factors such as the coastal water table, aquifer characteristics,
local climate, anthropogenic factors and density variations due to salinity
and temperature anomalies (Babu et al., 2021; Valiela et al., 1992). In addi-
tion to these, seasonal intrusion/extrusion of seawater, changes in aquifer
thermodynamics due to geothermal heat (Valiela et al., 2002; 1992) and
tidal influence (Taniguchi et al., 2002) can also be the potential factors af-
fecting the process. SGD has been recognised as a potential pathway that in-
troduces solutes/contaminants from the land to the sea (George et al., 2021;
Liu et al., 2001; Rodellas et al., 2014; Slomp and Van Cappellen, 2004;
Taniguchi et al., 2019; Urquidi-Gaume et al., 2016). The contaminants
like nutrients (Oehler et al., 2019), trace metals (Rodellas et al., 2014)
and several others which were originated from anthropogenic activities
(Chidambaram et al., 2015; Oehler et al., 2021; Bhagat et al., 2021;
Kumar et al., 2010; Selvam et al., 2021) were transported to the coastal wa-
ters through subsurface flow in the form of SGD along with a hydrological
flux from coastal aquifers. This flux of materials in the dissolved form has a
profound impact on the coastal ecosystems (Oehler et al., 2019; Slomp and
Van Cappellen, 2004; Urquidi-Gaume et al., 2016) and the biogeochemical
cycles of several elements (Johannesson and Burdige, 2007; Kwon et al.,
2014; Rodellas et al., 2014). The subsurface flow of SGD was an invisible
pathway and hence, not considered as a significant pathway for the earth's
hydrological cycle. (Peterson et al., 2009; Ravindran and Ramanujam,
2014). Considering the massive discharge of water and solutes to the
oceans (Moore, 2006), SGD can consider as a crucial component of the hy-
drological and biogeochemical cycle in the coastal regime (Johannesson
and Burdige, 2007). In recent years, direct/indirect seepage of groundwater
to the marine environment has attracted many researchers, wherein most of
the studies (Erler et al., 2014; Oehler et al., 2021; Wang et al., 2021) have
focused on SGD and solute fluxes, and their associated impacts on the ma-
rine ecosystem.
Identification and quantification of SGD is a tedious task as it is
governed by several factors such as the coastal water table, aquifer charac-
teristics, local climate, anthropogenic factors and density variations due to
salinity and temperature anomalies (Babu et al., 2021; Valiela et al., 1992),
seasonal intrusion/extrusion of seawater, changes in aquifer thermodynam-
ics due to geothermal heat (Valiela et al., 2002; 1992) and tidal influence
(Taniguchi et al., 2002). Therefore, quantification of SGD using conven-
tional techniques can provide only an approximate estimation (Taniguchi
et al., 2019). Also, it is impossible to use sophisticated techniques to inves-
tigate the SGD and associated fluxes reaching into the sea for the vast coast-
line like the Gujarat coast. Thus, a combination of several techniques is
generally employed to quantify the SGD. They include but are not limited
to seepage meters (Debnath et al., 2015), stable isotopes (δ18O and
87
Sr/86Sr), mass fractionation (Peterson et al., 2008; Rahaman and Singh,
2012), nutrient mass balance (Oehler et al., 2019), radon mass balance
model (Peterson et al., 2008; Selvam et al., 2021; Yadav et al., 2019). In
very recent studies, the use of geochemical and isotopic tracers such as
δ18O, 226Ra, 224Ra, 228Ra, 87Sr/86Sr for estimation of SGD has gained sub-
stantial attraction (Babu et al., 2021; George et al., 2021; Povinec et al.,
2012; Selvam et al., 2021; Taniguchi et al., 2019; Wang et al., 2021). How-
ever, these techniques require sophisticated and expensive laboratory
equipment along with the trained personnel. Therefore, these methods
are not used extensively for SGD quantification. Furthermore, these tech-
niques are more effective to understand the mixing sources in a closed sys-
tem (Petermann et al., 2018; Tamborski et al., 2020; Wang et al., 2021) but
may prove to be inaccurate for an open system such as oceans. Moreover,
the heterogeneity of coastal aquifers poses a challenge in pinpointing the
precise location of SGD occurrence.
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The state of Gujarat has the longest (approximately 1600 km) coastline
in India, which makes the identification and quantification of SGD a crucial
task. Only four west draining perennial rivers of India flow through the
state (Bhagat et al., 2021b). Hence, the biogeochemical and hydrological
flux through the coastline of Gujarat is critical for the sustainable manage-
ment of the coastal zone. The presence of deccan traps along the southern
coast of Gujarat, and the prevalence of limestone and quaternary sediments
in the northern area, represents a lithologically diverse aquifer system.
Moreover, the salt flats of the Kutch region, provide a unique interface be-
tween coastal aquifers and the sea. The heavy industrialization along the
southern coast, oil exploration and maritime traffic through the state's
coastline are significant anthropogenic activities that serve as vital sources
of contaminants in coastal groundwater. All the aforementioned factors
may cause massive disturbances to the sensitive marine ecosystem along
the coastal region of Gujarat. Therefore, the present study aims to delineate
the SGD prevalent locations and estimate the hydrological and contami-
nants fluxes reaching the Arabian Sea in the coastal regions of Gujarat. In
our previous article, Bhagat et al., 2021a, we have used the primary basis
for identifying SGD vulnerable zones was the positive hydraulic gradient to-
wards the seashore from the coastal aquifers. Additionally, sea surface tem-
perature anomalies and the EC gradient approach were used to identify the
areas that showed significant anomalies, which was the indication of SGD
in the coastal region. In the present study, these delineated zones of SGD
from Bhagat et al., 2021a was used as a fundamental basis to identify the
specific locations of SGD along the Gujarat coast. We have employed multi-
ple techniques to delineate SGD locations such as salinity gradient along
beaches, stable isotopes of oxygen (δ18O) and strontium (87Sr/86Sr). The sa-
linity gradient along the coast was used to identify the extent of SGD zones
on a preliminary basis. Further, stable isotopes of oxygen (δ18O) and stron-
tium (87Sr/86Sr) were used to validate the occurrence of SGD at the derived
locations.
To quantify the SGD and contaminant flux, we have used seepage me-
ters and two numerical models based on the heat (temperature) and solute
(salinity) mixing models in the beach sediments. In the heat mixing model,
temperature is used as a physical tracer (Debnath et al., 2015; Wilson,
2005) to simulate porewater velocity in a vertical direction by employing
the 1-D heat conduction-advection equation (Bredehoeft and Papaopulos,
1965). Additionally, to understand the process of SGD through the lens of
solute transport, a 1-D advection-dispersion model was used for the quanti-
fication of hydrological flux using salinity as a tracer. This model uses the
advection-dispersion equation, which is based on the mass conservation
principle. The multi-faceted approach was used in this study wherein a pre-
liminary analysis of coastal groundwater table and sea surface temperature
was used to identify vulnerable zones for SGD. Following this, the samples
from vulnerable zones were analysed for isotopic imbalances and salinity
gradients to confirm the SGD occurrence. Finally, seepage meters were
installed at the sites of confirmed SGD occurrences to quantify the SGD
and contaminant flux reaching into the sea. In addition to this, at Dehri
beach, thermal and salinity profiling along the depth was carried out in
order to create a flow simulation indicating SGD occurrences at extremely
high resolution by mapping the plumes of discharging groundwater. The
multiple techniques used in this study aim to create a holistic understand-
ing of the SGD process and contaminant transport for the coastal environ-
ment.
2. Materials and methods
2.1. Study area
The state of Gujarat is located on the western coast of India and has the
longest coastline in the country (1621 km) (Prakash et al., 2012; Book and
Delhi, 2020), situated between latitude N 20° 06′ 00" to N 24° 42' 00", lon-
gitude E 68° 10' 00" to E 74° 28' 00". The coastline starts from Lakhpat
(Kutch district), extends up to Umargam (Valsad district) and also stretches
through the union territory (Daman and Diu). The major west-flowing
Indian rivers through southern Gujarat are Narmada, Tapi and Mahi,
C. Bhagat et al.
discharging into the Arabian sea (Krishnaswami and Singh, 2005). Other
rivers like Vishwamitri and Sabarmati discharge waters into the Gulf of
Khambhat (Ramanathan et al., n.d.). Marshy and saline tracts in Rann of
Kutch, alluvial plains from Banaskantha to Valsad, and low-lying coastal
tracts through Kutch and Saurashtra are observed. Also, Gaj beds belonging
to the Miocene occur along the Saurashtra coast (CGWB Groundwater Year-
book 2016–17).
The geology of Gujarat is divided into three main eras: Precambrian,
Mesozoic, and Cenozoic. Hardrock occupies 49% of the state, while Quater-
nary sediments cover the rest. Quaternary deposits were derived from di-
verse environments such as marine, fluvial, lacustrine and aeolian.
Tertiary formations in the area have been used for commercial mining of
limestone, lignite, and bauxite (CGWB, 2013). Physiographically, the
state is broadly divided into groups: Great Rann of Kutch, northern Aravalli
ranges, Narmada and Tapi floodplains of central Gujarat, and the Deccan
plateau, along with a lengthy and varied coastline consisting of salt flats,
marshes and deltas.
The aquifers along the coastline are covered with extrusive rocks from
the Cretaceous period (Deccan Basalts), followed by quaternary sediments
and some patches of late Pleistocene to early Miocene sedimentary rocks.
Paleogene sedimentary rocks and Jurassic metamorphic rocks are observed
in the Kutch region. Major aquifer systems which govern the hydro-
geological setup of area (as shown in Fig. 1, b) can be classified into: Qua-
ternary to upper Tertiary (impure limestones, sandstones, conglomerates,
silts stones, sands, pebbles, and gravel beds), which are characterised by un-
confined shallow aquifers and leaky confined deep aquifers; and Mesozoic
(sandstones, shales, limestones, and grits) (CGWB 2013). Discontinuous
aquifers of a limited thickness (50 to 300 m) characterize these forma-
tions with a hydraulic conductivity ranging between 2 and 10 m.
day−1. The Mesozoic lava flows (basalt with intertrappean clays), Pa-
leozoic, Archean and Precambrian formations (granites, gneisses, mar-
bles, schists, phyllites, and slates) show limited yield up to 2 to 5 L.
s−1 (Prakash et al., 2012).
Fig. 1. Sampling locations in study area and geological setup and salinity gradient at seven potential SGD locations (a-g). These seven locations show the salinity gradient
along the beach (in longitudinal directions) and hence identify as the prominent locations of SGD in the entire Gujarat coast. Samples collected from these locations were
analyses and further these identified locations were verified.
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3. Methodology
The methodology was designed with the aim of delineating SGD zones.
It was further extended to quantify the hydrological flux as SGD and corre-
sponding solute flux discharging into the sea. Samples of seawater,
porewater, and groundwater were collected; and further supplemented
with groundwater level data and remotely sensed MODIS (further Moder-
ate Resolution Imaging Spectroradiometer) thermal infrared images data
(used to observe a sea surface temperature anomaly). The collected data
was analysed graphically and statistically for detailed insights into the
mixing processes along the coast. Based on the literature survey, a method-
ology for quantification of SGD flux (hydrological and material) was devel-
oped for the present study. Detailed methodology is explained in the
following sections.
3.1. Sampling strategy and data collections
Water (seawater, porewater, and groundwater) sampling was carried
out along the coastline of Gujarat to delineate SGD zones and quantify the
SGD flux reaching to the ocean. A two-fold sampling strategy was adopted,
consisting of a primary study region survey, followed by a detailed collec-
tion of groundwater, porewater and seawater samples. The sampling loca-
tions are shown in Fig. 1. Groundwater samples were collected from the
hand pump, bore well and open well, whichever was available near the
coast. Several in-situ porewater measurements were taken for the delinea-
tion of specific locations for the SGD, along with seawater measurements
at the respective beaches. A pore water samples were collected during the
measurement of SGD using a seepage meter for the quantification of
contamitanant flux. In-situ parameters, such as electrical conductivity
(EC; μS.cm−1), total dissolved solids (TDS; mg.L−1), dissolved oxygen
(DO; mg.L−1), salinity (g.L−1), turbidity (NTU), pH, temperature (°C),
and oxidation-reduction potential (ORP; mV), were measured using a hand-
held DSS-Multiparameter probe (Hanna Instruments, HI98194).
C. Bhagat et al.
Groundwater, seawater and porewater samples were collected in HDPE
bottles at an interval of ~5 to10 km, depending on the accessibility at the
site. Porewater sampling was done using a push-point sampler of 1 to
1.25 m in length. A push-point sampler was inserted vertically inside the
seabed to the desired depth to obtain porewater samples. The groundwater
level of the coastal aquifers was obtained with the help of piezometers,
courtesy of the regional Central Groundwater Board (CGWB), Ahmedabad.
This data was used to delineate the locations/zones prone to SGD along the
coastline of Gujarat.
3.1.1. Temperature profile mapping
The susceptibility of surface water to ambient temperature
abnormalism (NOAA, 2021), is used as the basis for temperature profiling
of porewater (physical tracer) to delineate SGD zones. Generally, regional
shallow and deep groundwater aquifers bear the mean/annual seasonal sig-
nature of ambient temperature (LaSage et al., 2008). Owing to this, there is
a seasonal contrast between the thermal response of groundwater and sea
surface water, which can be used as a tracer for identifying mixing zones
(Debnath et al., 2015). Some of the factors influencing the horizontal and
vertical distribution of porewater temperature are heat conduction, advec-
tion, dispersion, and groundwater flux (Stallman, 1965, Lapham, 1989,
Conant, 2004). Taking this into account, the porewater temperature has
been used as a tracer for delineating the locations of SGD and quantifying
the SGD flux (Stallman, 1965, Conant, 2004). Therefore, in the present
study, porewater sampling has been conducted, and the temperature pro-
files have been investigated along five transects (Fig. 3, c) (AA’, BB’, CC’,
DD' and EE’) at Dehri beach, Valsad to understand SGD patterns within
the diffused zones of seepage in the shallow seabed.
This work presumed that SGD would imitate the ambient diurnal/sea-
sonal air temperature, as groundwater is unaffected by diurnal temperature
variations in seawater. The Porewater column in SGD zones has a lower
temperature than the sea surface during the summer season and vice-
versa for winter seasons, as shown in Fig. 2 (a). The recirculated/marine
component of SGD (R-SGD) has a broader temperature variation because
it inherits the sea surface water temperature before recirculating as R-
SGD (Fig. 2, a), in contrast with the narrow range for fresh/terrestrial com-
ponent of SGD (F-SGD). Hence, this factor helps to differentiate between
Fig. 2. Schematic conceptual diagram infers the relationship between groundwater discharge (i.e. fresh/terrestrial component of SGD (F-SGD)) and recirculated component
of SGD (R-SGD) with variations in porewater (a) temperature and (b) salinity variation along the depth of the seabed. Vz represents the vertical porewater velocity which is a
function of depth (z), temperature (T), thermal conductivity and heat capacity of porewater and sediments. The maximum depth of atmospheric influence was observed up to
the 30 cm depth, and the boundary conditions were taken as Dirchler’s boundary condition to solve the models for the vertical porewater velocity (Vz).
4
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the R-SGD and F-SGD components from the total SGD, as shown in Fig. 2
(a). A DSS-multiparameter probe was used to measure the pore water tem-
perature for obtaining the thermal profiling in the field. Porewater collec-
tion at specified locations was carried out using a push-point sampler.
Thermal mapping was done along a grid of 40 m × 40 m at Dehri beach
near Umargram village with five transects (AA’, BB’, CC’, DD' and EE’) per-
pendicular to the high tide line (Fig. 3 (c and f)). Thermal profiling of
porewater was carried out up to the depth of 90 cm with an interval of
15 cm below the seabed level. Total 175 porewater temperature measure-
ments were taken along the five transects during low tide to avoid any influ-
ence of tidal inflow.
3.1.2. Salinity profile mapping
Salinity has been used as a direct indicator of seawater intrusion in the
salinization investigation of the coastal aquifers (Abdalla, 2015). Salinity in
water represents the sum of all noncarbonate dissolved solutes (Zarras and
Stenger-Smith, 2014). In seawater, the most abundant ions are Cl− and
Na+ (approximately 90%), whereas Ca2+, Mg2+, SO2− +
4 and K are present
in minor quantities whereas, in the case of groundwater, the abundance
patterns are completely different (Bhagat et al., 2021b). Hence, the salinity
profiling of porewater can be used as a proxy to delineate the SGD locations
(Olesnavage, 2012). In the present study, salinity has been used to delineate
the mixing zone and estimation of vertical porewater velocity for the quan-
tification of SGD flux through the 1-D advection-dispersion model. In addi-
tion to this, salinity has also been used to differentiate between F-SGD and
R-SGD. Therefore, porewater samples with low salinity and TDS considered
fresh groundwater inputs as F-SGD, and those with salinity values compara-
ble to seawater are considered as inputs of R-SGD (Debnath et al., 2015).
3.2. Sample analysis
Water samples were collected in high-density polypropylene (HDPE)
bottles (Polylab reagent bottles). 250 mL bottles were used for major
ions, and 60 mL bottles were used for stable isotope analysis, ensuring no
leakage. Samples were labelled and packed immediately to avoid any exter-
nal contamination. Samples in 250 mL bottles were acidified with 2% pure
HNO3 (pH < 2) to stabilize the trace metals and to restrict microbial
C. Bhagat et al. Science of the Total Environment xxx (xxxx) xxx

a. b. c. Dehri beach Gujarat

Dense Seaweeds
Sea water
indicating the nutrient
E’ D’
enrichment C’ B’ A’

E
D
C B A
High tide line
Nargol Beach, Valsad Nagao Beach, Diu
E’

d. e. f.
D
’
C’
E B’
D A’
Grid

90 cm
Udavda Beach C
B
A
Pipe
Concentrated Seepage
Sampling Profile
Outlet
Air vent
Valve

Collection
Safety box Bag
(1 L) Dehri Beach, Umargaon

Fig. 3. a. Nargol Beach Valsad, b. Seaweed at Nagao beach at Diu, c. Sampling grid at Dehri beach, d. Installed Seepage meter, e. Concentrated seepage and f. Diffuse seepage
observed at the Dehri beach. Field photos indicate SGD sites and the installation of a seepage meter to calculate the SGD flux. At Nagao beach, Diu, we have observed dense
seaweed, which indicates that nutrient enrichment on the beach may be due to terrestrial groundwater discharge. We have performed 3D profiling porewater sampling
(Fig. b) on Dehri beach to estimate the SGD flux.

activities in water samples during storage. The standard methodology of
APHA (American Public Health Association, 2012) was adopted for sample
collection, handling, and preservation to ensure data quality and consis-
tency. Samples were kept in a foam icebox and transported to the lab and
stored at 4 °C to avoid temperature influence on samples. 60 mL samples
in sealed bottles were sent to Physical Research Laboratory (PRL) (IWIN di-
vision), Ahmedabad, for stable isotopes analysis. Samples were filtered
through vacuumed filter assembly using Millipore filter paper (0.45 μm)
to analyse major ions and trace metals. The trace metals (Cu, Pb, Zn, Fe,
Cd, Ni, Cr, Mn, and Sr) were analysed using ICP-OES and strontium isotopes
(87Sr/86Sr) were analysed using ICP-MS in the Central Instrumentation Fa-
cility of IIT Gandhinagar. All samples were diluted using deionised water
prior to the analysis with a target TDS of less than 200 mg/L. The accuracy
of estimated ions was tested using the percentage charge balance (%CB)
within an error margin of 5%. Stable isotope (δ18O and δD) analysis was
done using the standard calibration method, where 300 μL samples were
equilibrated with CO2 and H2. The equilibrated gases (CO2 and H2) were
analysed in Delta V Plus isotope ratio mass spectrometer in continuous
flow mode using Gas Bench II for 18O/16O and D/H ratios. The reproduc-
ibility of measurement was better than 0.1 0/00 for δ18O and 1 0/00 for
δD. The results obtained from the analysis were corrected using an inte-
grated calibration curve based on VSMOW2, GISP and SLAP2 measurement
(International Atomic Energy Agency, Vienna).
3.3. Identifying the SGD locations
To identify the SGD locations, we have investigated the delineated SGD
zones in our previous article (Bhagat et al., 2021a), in which delineation
was done based on a three-tier approach, i.e. groundwater level, EC gradi-
ent approach and sea surface temperature anomalies. In the present work
for the investigation of specific SGD locations, we have used two ap-
proaches: salinity gradient and stable isotopes of oxygen (18O) and stron-
tium (86Sr/87Sr). For evaluating the salinity gradient, porewater samples
were collected using a push-point sampler along the coast at intervals of
100-500 m. Then salinity variation in the samples was analysed and plotted
graphically in Fig. 1 (a-h). The locations selected for salinity gradient sam-
pling were based on the thumb rule that porewater salinity was less than
seawater salinity (30 to 35). The investigation was carried out by analysing
porewater salinity along the coast face with a resolution of 100-200 m for a
stretch of 1000-1200 m on either side of the selected locations. Further, we
used stable isotopes of oxygen (18O) and strontium (87Sr/86Sr) signatures to
validate these identified locations. The conservative nature of these iso-
topes makes them ideal indicators for identifying mixing in natural waters
from diverse sources (Turner et al., 1987). Moreover, their stability for an
extended period of time in the water systems due to their high half-life
makes them suitable for these investigations (Maurya et al., 2019;
Rahaman and Singh, 2012). Isotopic ratios of oxygen (δ18O) are reported
as deviations from V-SMOW (Vienna standard mean ocean water) in parts
per thousand or per mil (o/oo) (Bhattacharya et al., 1985) and calculated
using Eq. (1). In Eq. (1), R represents the ratio of 18O/16O atoms.
 
Rsample
δ18 OðÞ ¼ −1  103 (1)
RV−SMOW
Water has a unique isotopic signature making it a valuable tool for un-
derstanding the mixing of seawater and groundwater in the coastal envi-
ronment (Manivannan and Elango, 2019). It has also been used to trace
the sources of contaminants (Xu et al., 2016) and to ascertain their flow di-
rection (Bhattacharya et al., 1985). Generally, the value of δ18O is greater
than or equal to zero for seawater in the Arabian sea. For the Gujrat
coast, Singh et al. (2010) and Delaygue et al. (2001), reported δ18O > 0
for the surface to 50 m deep seawater. Therefore, we have used δ18O to
identify SGD locations along the coastal areas of Gujarat. The concentration
of δ18O in collected porewater and groundwater samples has been plotted
in Fig. 4 (a) to delineate SGD locations.
Similarly, we used isotopes of strontium (86/87/88Sr) to validate the
identified locations of SGD (Capo et al., 1998). 87Sr is a stable isotope
with a residence time of 2.4 million years in water (Kell-Duivestein, n.d.)
and shows the highest abundance, whereas 86Sr and 88Sr have lesser and
fixed abundance in water (Krabbenhöft et al., 2010). In contrast, the

5
C. Bhagat et al.
Fig. 4. a) Stable ratio isotopes (18O) for groundwater and seawater and b) Plots of dissolved 87Sr/86Sr Vs 1/Sr to identify SGD locations along the coast. Seawater is enriched
with δ18O (+ve concentration), whereas groundwater has depleted δ18O (−ve concentration). The dotted line indicates the separation of groundwater zone and seawater
zones. The porewater samples in the groundwater zones indicate the signature of SGD, which is marked by a dotted line circle. The dashed line in fig. b is the theoretical
mixing line for two end-member mixing; groundwater and seawater. Most data points plot away from the theoretical mixing line infering the non-conservative behaviour
of 87Sr/86Sr and mixing of groundwater-seawater.
concentration of 87Sr increases as a result of 87Rb β-decay (87Sr is the
daughter product of 87Rb) with a half-life of 4.92 × 1012 years (Kell-
Duivestein, n.d.). 87Rb barely has any radioactive nature (28% in radioac-
tive form) due to its extended half-life period (Butterman and Reese,
2003). Nevertheless, there is significant production of radiogenic 87Sr as
sediments and aquifer matrix is relatively abundant in 87Rb. The isotopic
ratio of 87Sr/86Sr is globally reported as a constant value at 0.709172
(Richter et al., 1992). Also, the mass balance model for strontium was
used to calculate various end-member contributions in the ocean
(Holmden et al., 2012). As shown in Fig. 4 (b), water samples deviate
from the theoretical mixing line indicating mixing of two end-members
(seawater and groundwater) in the coastal area (Rahaman and Singh,
2012).
3.4. Quantification of submarine groundwater discharge
In the present work, we used seepage meters and two numerical models
to estimate the rate of SGD. The detailed methodology of SGD quantifica-
tion is provided in the subsequent sections.
3.4.1. Seepage meters
Seepage meters were installed at identified SGD locations, and measure-
ments were taken during the low tide. The design of the seepage meter
adopted from Rosenberry, 2008; which consists of a canister with a diame-
ter of 32 cm and 30 cm in height. The canister is provided with an air vent at
the top and an outlet pipe attached on the side to collect seepage into a 1 L
collection bag, as shown in Fig. 3 (d). The air vent helps to remove the
trapped air in the canister during the installation of the seepage meter.
Valves are provided to regulate the flow at the outlet pipe and inlet of the
collection bag. After installing the seepage meter, the valves were closed,
and the collection bag was facilitated to measure the volume of water
over a fixed duration of time. The valves were subsequently opened to
allow the seepage into the collection bag for the fixed duration. The volume
of water was then measured, and the porewater flux was calculated by di-
viding the volume by time (L.s−1). Water samples from the collection
bags were collected in a 250 mL bottle for chemical and isotopic analysis.
3.4.2. Numerical modelling
Diurnal and seasonal (autumn to summer) fluctuations in groundwater
flux (SGD) lead to temperature variability in the seabed and porewater. The
temperature contrast between seabed and porewater can be attributed to
the spatial variation in the porewater beneath the ocean floor (Schmidt
et al., 2006). High-resolution thermal profiling can be used to evaluate
the flow patterns at the interface of porewater and seabed sediments. The
2D (vertical and horizontal) temperature distribution in porewater and sea-
bed is due to convective heat transfer by SGD and conduction of heat
6
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through porewater and sediments (Rodellas et al., 2014). Temperature pro-
filing was carried out at different depths and spatial locations to represent
the quasi-steady-state condition. Vertical flow in the seabed sediments
has been assumed for the flow conditions (Debnath et al., 2015). The
governing equation for 1-D convective-conductive heat transfer in quasi-
steady-state represented by Bredehoeft and Papaopulos (1965) and
Schmidt et al. (2006) has been used in the present work.
The equation is given by;
∂2 T cp ∂T
−v ρðzÞ ¼0 (2)
∂x2 k ∂x


k ¼ εg kf þ 1−εg k s (3)
Where, cp (J.kg−1.0C−1) is the heat capacity of porewater which is calcu-
lated using the empirical relation. Notations for the equations mentioned
above are as follows; k (W.m−1.K−1) - sediment thermal conductivity, v
(m.s−1) - vertical porewater velocity, ρ (z) (kg.m−3) - density of fluid,
which is a function of temperature and depth (z), T- Temperature in degree
Celsius (°C), kf (W.m−1.K−1) – thermal conductivity of porewater calcu-
lated using empirical relation suggested by Caldwell, 1974, ks (W.m−1.
K−1) – thermal conductivity of saturated sediments values adopted from
Goto et al. (2017), εg - porosity of sediments calculated using the empirical
relation suggested by Wu and Wang. (2006). No significant change was ob-
served in the density of porewater and hence assumed to be constant over
depth z (cm). The 1-D conductive and convective heat transfer equation
was solved by using the Dirichlet boundary condition, at z = 0, T = T0,
and at z = L, T = TL (Fig. 2, a). It is interesting to note that Eq. (2) was
the non-linear differential equation which was solved by complementary
error function (Abramowitz and Stegun, 1964). However, in the present
study, this equation is solved numerically, using the finite-difference ap-
proach with the help of MATLAB v.2011. Furthermore, Eq. (2) was solved
for unknown vertical velocity (v), and velocity values were optimised in
order to minimise experimental and theoretical temperature value error.
Another numerical model employed in this study is the 1-D Advection-
Dispersion equation used to estimate the porewater velocity and calculate
the SGD reaching the coast based on solute (salinity concentration) trans-
port (Rodellas et al., 2020). This Advection-Dispersion equation uses a sim-
ple mass conservation principle to trace the contaminant transport in
porous media (Walter et al., 2019). We used salinity concentration as a
tracer (Bönisch et al., 1997) to simulate the model for estimating the
porewater velocity. In the present model, we considered vertical displace-
ment of pore fluid through the seabed sediment and assumed that concen-
tration does not change with respect to time (Eq. (5)). Salinity profiling was
done on the same grid as described in the previous section. Temperature-
salinity concentrations were also measured over 175 locations to evaluate
C. Bhagat et al.
the porewater flux and distinguish between F-SGD and R-SGD depending
on the salinity concentration, as shown in Fig. 2. The same Dirichlet bound-
ary conditions (z = 0, T = T0 and at z = L, T = TL) were used to solve this
equation with the help of analytical solution of finite difference approached
(Taylor series expansion), MATLAB was used to solve this model. 1-D
Advection-Dispersion equation model is given below:
∂C ∂C ∂2 c
þv ¼ DL 2 (4)
∂t ∂x ∂x
∂C=∂t ¼0 (5)
∂C ∂2 c
v ¼ DL 2 (6)
∂x ∂x
Where, C - concentration of salinity in ppt (parts per thousand), v -
porewater velocity in m.s−1, DL – diffusion coefficient in m2.s−1 and
value adopted was 6.5 × 10 −9 m2.s−1 from Toth and Lerman (1975) for
the stratified seabed sediments. Finally, Eq. (6) was solved using the bound-
ary conditions with finite-difference approached in MATLAB v.2011.
4. Results and discussion
4.1. Identification of SGD locations
The groundwater level has proven to be a vital tool for identifying SGD
and SWI vulnerable zones along the coastal areas (Manivannan and Elango,
2019). Based on zoning techniques, areas with a high probability of SGD oc-
currences have been identified. The majority of locations vulnerable to SGD
were identified along the southern coast of Gujarat and surrounding the
Gulf of Khambhat. The second parameter used to identify the SGD affected
areas was the sea-surface temperature (SST) anomaly (Bhagat et al.,
2021a). Based on this approach, three probable zones were identified.
Out of three, two were along the Saurashtra region and one along the
Southern coast. The EC gradient along the coastal waters was used for fur-
ther validation of the SGD occurrences at these locations. The gradient be-
tween EC value of groundwater, porewater and seawater was plotted for
each sampling location, and based on that, SGD probable zones were iden-
tified. EC was observed as a prompt indicator of seawater influence and
hence used as a proxy to understand the mixing of seawater and groundwa-
ter in the coastal areas (Babu et al., 2021; Bhagat et al., 2021b; Manivannan
et al., n.d.). Further identification of specific locations based on probable
zones was identified using three approaches: salinity gradient, stable iso-
topes of oxygen (δ18O), and 86/87Sr isotopes. Porewater sampling along
the entire coastline was done with a high resolution (~1-2kms) for under-
standing the salinity gradient (longitudinal section of beach). For suspected
locations, the resolution was further increased to (~100-500 m) depending
on the salinity of porewater. The locations which displayed salinity values
of <25 ppt were identified as probable SGD hotspots. Fig. 1 (a-g) shows
the salinity gradient along the beach's longitudinal direction at various lo-
cations. Among these seven locations, three sites (Dehri, Udvada and
Fansa beach) were found along the southern coast, other three were ob-
served along the Saurashtra coast (Kuda, Adri and Chorwad holiday camp
beach), and one location on Nagao beach in Diu (Union Territory of India).
Further, we have used stable isotopes of oxygen (δ18O) and strontium
(86/87Sr) to validate our results. Fig. 4 (a) shows the variation of δ18O for
porewater and groundwater samples along the coastline, indicating that al-
most all groundwater samples had a negative signature of δ18O. In contrast,
seawater had a positive value since seawater was enriched with 18O
(Muehlenbachs, 2018). Stable isotopes of oxygen (δ18O) were found
enriched in the seawater in the present investigation (Fig. 4, a), which
was obvious because the lighter isotopes of oxygen i.e., δ16O and δ17O evap-
orate initially and hence the concentration of δ18O increases in seawater.
The porewater samples from the identified location using salinity gradient
give a different signature than seawater, as shown in Fig. 4 (a). These differ-
ent signatures (samples highlighted by dash line circle) were identified for
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Science of the Total Environment xxx (xxxx) xxx
some porewater samples depicted in Fig. 4 (a). The signature of δ18O in
porewater confirmed the mixing of fresh groundwater and recirculated sea-
water into the coast at respective locations.
Furthermore, we used the stable isotopes of (86/87/88)Sr to confirm the
identified SGD locations (Fig. 4, b) to carry out a detailed investigation.
Fig. 4, (b) shows that the theoretical mixing line, joining two end-
members, such as seawater and groundwater, indicate the conservative na-
ture of Strontium (Rahaman and Singh, 2012), which have been used to dis-
tinguish the mixing of seawater and groundwater in the beach. The isotopic
ratio of Sr (86Sr/87Sr) has a unique value for the seawater, i.e. 86Sr/87Sr =
0.7076; based on this signature of seawater and fresh groundwater mixing,
SGD locations can be delineated easily. The range of 86Sr/87Sr ratio for
groundwater varied from 0.71053 to 0.7160 greater than seawater,
which was obvious as the aquifer served as the Sr reservoir. For porewater
samples from the identified locations, the 86Sr/87Sr ratio varied from
0.70838 to 0.71840, which was almost greater than seawater, indicating
the mixing of two end-member in the nearshore as shown in Fig. 4 (b).
Overall, the porewater samples collected from identified locations exhib-
ited deviation from the mixing line (Fig. 4, b), indicating a different signa-
ture than seawater and groundwater, hence confirming the SGD locations.
4.2. Porewater characteristics
Freshwater springs proximal to the coast are easily identifiable as poten-
tial sites for SGD. As freshwater residing in coastal aquifers has a distinct
thermal signature than the surface water (seawater, in this case), any
mixing would be signified by a change in the temperature along the mixing
zone. However, any such freshwater spring was not observed along the
coast of the study area. The temperature during winters varied from 16 to
36 °C (December 2020) during the sampling event. Vertical thermal profil-
ing was carried out up to a depth of 90 cm below the seabed for the five
transects (Fig. 5 (a)) at Dehri beach, near Umargam locality. The tempera-
ture varied from 26.2 to 29.7 °C across the transects. The observed annual
mean groundwater temperature near this site at Umargam was 27-29 °C
(CGWB Data). Vertical porewater temperature profiles across the five tran-
sects showed a wide variation for temperature up to a depth of 30 cm.
Minute variation in temperature was observed between the depth of
30 cm to 75 cm. Among all the transects, AA's transect exhibited minimum
variation in the temperature range, i.e., 26.9 to 29.65 °C with an average
temperature of 27.69 °C.
Fig. 6 (a and b) shows the distribution of temperature and salinity across
the grid of 40 m × 40 m on the Dehri beach. The average annual salinity of
seawater along the Gujarat coast was observed to be 35 ppt (parts per thou-
sand) (Vinayachandran and Nanjundiah, 2009), and TDS was varying from
40 to 42 g.L−1 (Bhadja and Kundu, 2012). Porewater salinity ranged from
5.74–32.7 across the transect. From Fig. 5 (b), it can be observed that a nar-
row range of salinity existed below 30 cm depth conforming to F-SGD
(Debnath et al., 2015), as shown in Fig. 2(b). Also, the maximum depth of
surface water interference was approximately 30 cm below seabed level be-
cause the signature of recirculated SGD component was observed up to this
depth (Fig. 2 (b)). Transect EE’ exhibited the narrowest salinity range
among all transects, as shown in Fig. 5 (b). The salinity was used as a tracer
to trace the SGD, as it has conservative nature and could be easily measured
(Vinayachandran and Nanjundiah, 2009).
4.3. Simulated porewater temperatures and estimation of SGD fluxes
The comparison between simulated porewater temperature and ob-
served field temperature profile for the intermediate transect CC' was repre-
sented in Fig. 7 (a). The range for simulated temperature varied from 27.71
to 29.70 °C, with a residual error between the experimental and simulated
temperature as −0.56 to 0.3 °C. No definite pattern was observed in the dis-
tribution of residual error. Maximum residual (R) error was found at 40 m
from the high tide line corresponding to a depth of 30 cm from the seabed.
The estimated porewater velocity at each node point using Eqs. (2) and (6)
for the boundary condition as shown in Fig. 2 (a). The estimated porewater
C. Bhagat et al. Science of the Total Environment xxx (xxxx) xxx

Fig. 5. a) Temperature profile and b) Salinity profile along the five transects (AA’, BB’, CC’, DD’ and EE’). The temperature is almost constant after 30 cm depth up to the
certain depth indicating the influence of air ambient temperature up to 30 cm. The constant temperature indicates the signature of terrestrial SGD/fresh SGD. The range
of salinity was narrow after 30 cm depth up to the certain cm indicating the influence of recirculated seawater up to 30 cm. The wider window of salinity (up to 30 cm)
indicates the signature recirculated SGD.

flux based on the 1-D convective and conductive heat transfer model
ranged from ~0 to 744.665 m3.m−2. year−1. The range for SGD at each
transect was estimated as ~0 to175.04 m3.m−2. Year−1 (transect AA’),
10.40 to 552.49 m3.m−2. Year−1 (transect BB’), 54.05 to 646.94 m3.
m−2. Year−1 (transect CC’), ~0 to 744.663 m3.m−2. Year−1 (transect
DD') and ~ 0 to 347.61 m3.m−2. Year−1 (transect EE’), respectively. SGD
flux estimated along the Gujarat coast was comparable to SGD flux reported
by Selvam et al., 2021, as shown in Table 1, but characteristically lower
when compared to the SGD flux reaching into the Bay of Bengal (Debnath
et al., 2015; Mukherjee et al., 2007). For the Indian subcontinent, maxi-
mum SGD flux reaching into the Bay of Bengal coast was reported by
Debnath et al., 2015; Dowling et al., 2003; and Mukherjee et al., 2007.
The present study found maximum average flux across the CC’ transects
among all the transects. The mean value of SGD flux reaching the Gujarat
coast could be extrapolated as 115.24 m3.m−2. year−1, using 1-D convec-
tive and conductive heat transport model.
4.4. Simulated porewater salinity and estimation of SGD fluxes
Fig. 7 (b) depicts the comparison between experimental and simulated
porewater salinity for the CC’ transect. The experimental salinity ranged
from 8.0 to 29.3, whereas the simulated salinity was 9.41 to 28.87, with a
residual error (difference between observed salinity minus simulated salin-
ity) of 0.166 to 3.36. Maximum residual error (3.36) was found at a depth

8
C. Bhagat et al.
Fig. 6. 3D profiling of (a) Temperature and (b) salinity along the five transects The figure shows the 3D plots of temperature profiling and salinity profiling below the seabed
up to the 90 cm depth to understand the mixing of groundwater and seawater and estimation of vertical porewater velocity. The thermal response of surface seawater
observed in the figure as the temperature is lower at the sea surface and increases along the depth. In contrast, the salinity decreases along the depth, which means both
the tracer indicates the signature of the mixing process.
of 30 cm below the seabed level. The variation in the residual error of salin-
ity was observed to be inconsistent throughout the depth of the profile.
Porewater velocity was calculated at each point on the grid (175 grid
points) using Eqs. (5) and (6) (1-D advection-dispersion model) for the
boundary condition mentioned in Fig. 2 (b). The value of dispersion coeffi-
cient (DL) was adopted from Toth and Lerman, 1975. The estimated
porewater flux based on the 1-D advection-dispersion solute transfer
model ranged from ~0 to 70.0 m3.m−2. year−1. The quantified SGD flux
along each transect was: ~0 to 70.0 m3.m−2. year−1 (AA’ transect), ~0
to 38.30 m3.m−2. year−1 (BB’ transect), ~0 to 17.10 m3.m−2. year−1
(CC’ transect), ~0 to 54.23 m3.m−2. year−1 (DD' transect), and ~ 0 to
7.59 m3.m−2. year−1 (EE’ transect), respectively. The mean SGD flux for
the 40 m × 40 m grid at Dehri beach Umargram was 4.51 m3.m−2.
year−1. It observed that the SGD flux estimated through the solute trans-
port model was very less than that of the heat transport model and seepage
meter. This relative difference between the magnitude of SGD flux indicates
that the 1-D solute transport model underestimates the flux; this may be due
to the assumed value of the dispersion coefficient.
4.5. Estimation of SGD flux by seepage meter
Seepage meters were installed at the SGD identified locations along the
Gujarat coast, and flux was quantified during the low tide. The seepage
meter does not give the aerial discharge; it can only estimate the point
SGD flux at a shallow depth of 1 to 2 m. However, due to the ease in logistics
and assembly with average efficiency, seepage meters were used to esti-
mate SGD occurrences at point locations. SGD was quantified at six loca-
tions out of seven through seepage meters, as the seepage meter could not
be installed at the seventh location (Adri beach) due to the unfavourable
terrain. Five to six seepage meters were installed simultaneously at each
of the selected sites, depending on suitable terrain for the installation.
The range of estimated SGD flux observed at each location was: 6.37 to
56.01 m3.year−1 (Dehri beach Umargram), 1.24–88.33 m3. year−1(Fansa
beach), 5.21 to 159.72 m3. year−1 (Udvada beach; here, we observed direct
flow from the seepage meter), 1.10 to 1.357 m3. year−1(Nagao beach, Diu
UT), 0 to 1.04 m3. year−1 (Kuda beach, Bhavnagar), 16.93 to 19.91 m3.
year−1 (Chorwad Holiday camp), respectively. Table 1 shows that the
SGD flux reported in the present study was relatively low compared to
the regional fluxes. This type of flux values might have been observed
9
Science of the Total Environment xxx (xxxx) xxx
due to the depleted groundwater in the coastal aquifers, less recharge in
the region, and substantial surface losses due to heavy evaporation and
evapotranspiration from the soil and plants, as Gujarat is classified as a
semi-arid region.
4.6. Quantification of contaminant flux reaching into the coast
SGD is a well-known invisible pathway carrying contaminant load
(mass flux) from the land/aquifer to the marine environment (Babu et al.,
2021; Taniguchi et al., 2019). Fresh SGD (FSGD) carries nutrients along
with trace metals and other anthropogenic contaminants from the land to
the sea via SGD. Every year, huge amounts of hazardous contaminants
reach the seashore, posing severe risks to the sensitive marine ecosystem
such as eutrophication, metal contamination, bioaccumulation of metals,
and ecological disruptions (Liu et al., 2001; Vikas and Dwarakish, 2015).
Excess nutrient input through various pathways leads to eutrophication
along the estuarine zone, creating anoxia in the sea and disrupting the en-
tire food chains of the marine ecosystem (Duarte, 2009; Rathore et al.,
2016). Metal contamination leads to bioaccumulation in aquatic species
(fishes and plankton species) and also increases the carcinogenic impact
on human health (dermal risk) (Achary et al., 2016). To estimate the con-
taminant load reaching the seashore, we have analysed the porewater sam-
ples for the various trace metals (Zn, Sr, Cd, Pb, Cr, Ni, Mn, Cd, Co, Cu and
Fe) and dissolved silica (DSi). The range of trace metals concentration in
porewater was comparable to the concentration reported in nearshore
groundwater. Concentration of Zn reported to be highest among all the
trace metals studied, varying from 78.31 to 4897 mg.L−1, followed by Fe
(58.02 to 115.23 mg.L−1), Sr (7.20 to 85.14 mg.L−1), Mn (2.388 to
20.1 mg.L−1), Cr (7.26 to 9.64 mg.L−1), Cu (2.8 to 7.72 mg.L−1), Pb
(3.59 to 6.32 mg.L−1) and Ni (3.28 to 4.977 mg.L−1). Most of the trace
metal's concentrations exceeded the permissible limits standardised by
the various agencies like WHO 2008, USEPA 2012, BIS 2011. In the study
area, the reported trace metal concentrations were many orders higher
than the required/permissible limits. Such high concentrations of trace
metals pose a serious threat to the marine biota as well as human health.
Fig. 8 illustrates the various contaminants that are being transported into
the Gujarat coast through SGD flux. The highest Zn2+ flux as SGD estimated
for Fansa beach was 77.411 kg. year−1 followed by Dehri beach
(37.824 kg. year−1), Chorwad Holiday camp (13.467 kg. year−1) and
C. Bhagat et al. Science of the Total Environment xxx (xxxx) xxx

Fig. 7. Comparison of observed and simulated porewater a) temperature and b) salinity for the profiles along transects CC’. Comparison were made in this fig. (a) so that we
can understand the error in the simulated values. To understand the error simulated and observed salinity were plot (Fig. b) in the 1D Advection-Dispersion simulated model
values. The positive value of porewater velocity indicates the significant discharge, whereas the negative value indicates no SGD flux.

Nagao Beach Diu (5.866 kg. year−1). Estimated Fe2+ flux ranges from
0.061 to 10.5 kg. year−1. Udvada beach showed the highest load of Fe2+
whereas the lowest load was reported for Kuda beach of Bhavnagar district.
The toxic metals such as Pb2+, Cu2+, Co2+, Cd2+, Ni2+, and Cr2+ exhib-
ited comparable mass fluxes reaching into sea coast at various locations.
The highest toxic metals load was observed at Udvada beach of Valsad dis-
trict. The order of calculated flux as SGD for toxic metals was observed as
follows: Chromium (Cr2+) 1724.93 g.year−1, followed by Lead (Pb2+)
1142.94 g.year−1, Copper (Cu2+) 1080.9 g.year−1, Nickel (Ni2+)
901.37 g.year−1,and Cadmium (Cd2+) 161.5 g.year−1. The estimated
contaminant flux was relatively lower than the flux reported in the various
studies as shown in Table 2.
These contaminants can be geogenic or anthropogenic depending on
the sources of contaminants around the coast (Bhagat et al., 2021b; Singh
et al., 2020). Most of the trace metals might have originated from natural
sources like weathering of minerals, mining, erosion of sediments, and vol-
canic eruption (Linhares et al., 2019; Stellato et al., 2020). The Gujarat
coast is well known in the Indian subcontinent for the chemical processing
industries, ship dismantling workshops, fertilizer and salt production indus-
tries. Therefore, these industries generate huge amounts of waste, mostly

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Table 1
SGD flux and techniques used in the various studies conducted around the world and present study.
Area of Study SGD flux (m3.year−1) Techniques used References

Gulf of Mexico 0.998–1.31 × 106 Seepage Meters Taniguchi et al., 2003

Gulf of Mexico 7.88 × 105 Ra isotope mass balance Moore and Krest, 2004
a. Cockburn Sound, Australia 1.93 × 105 Seepage meters and Bulk Ground Conductivity measurements Stieglitz et al., 2008
b. Shelter Island, USA 5.80 × 105
c. Ubatuba Bay, Brazil 9.27 × 106
d. Flic-en-Flac Bay, Mauritius
Tolo Harbour, Hong Kong 3.022 × 109 226
Ra mass balance Lee et al., 2012
Northern South China Sea shelf 0.839–1.35 × 1011 Total Alkalinity and Ra isotopes (mixing model and mass balance Liu et al., 2012
Chokai, Northern Japan 2.26 × 107 Rn mass balance Hosono et al., 2012
Atlantic and Indo Pacific Oceans (60°N to 9–15 × 1013 228
Ra Optimised Inverse Model Kwon et al., 2014
70°N)
Gautami -Godavari Estuary, India 2.48–4.63 × 109/0.48–2.71 × 109 Ra mass balance model/RaSi Three end member mixing model Rengarajan and Sarma, 2015
(Radium isotopes)/
Tauranga Harbour, New Zealand 1.12 × 109 226
Ra mass balance Stewart et al., 2018
French Mediterranean coastline 3.14–53.6 × 106 Ra isotope mass balance Bejannin et al., 2017
Sydney Harbour, Australia 1.53–4.4 × 108 Ra isotope mass balance Correa et al., 2020
Kuwait 1.27–1.99 × 109 Ra isotope mass balance Bhandary and Sabarathinam,
2020
Hanko, Finalnd 2.82–3.60 × 105 Groundwater flow model simulation Luoma et al., 2021
Osaka Bay, Japan 0.08–0.36 m.d−1 Seepage meter Taniguchi et al. (2002)
Donnalucata, Sicily 10–30 m3 m−2 d−1 Seepage meter Taniguchi et al., 2006
Ubatuba Brazil 0.5–2.7 m.d−1 Seepage meter Burnett et al., 2003
Southwest coast, India 1.8–12.2 × 108 222
Rn isotope mass balance George et al., 2021
Mumbai Harbour, India 2.17–23.6 × 109 Radon mass balance model Yadav et al., 2019
South-East coast of India 0.04 to 0.12 and 0.03–0.15 m3 m−2 222
Ra and 226Ra isotope mass balance Selvam et al., 2021
d−1
Bay of Bengal, India 1.16 × 107 m3 .year−1 Simulated (1D convective and conductive heat transfer model) Debnath et al., 2015
Westren Benagal Basin India 5.9 × 107 Simulated (water balance study) Mukherjee et al., 2007
Coleroon Estuary, Tamil Nadu, India 6.9 × 106 Water budget Raja et al., 2021
3.2 × 103 to 308.3 × 103 Darcy law
Pulluvila Southwest India 9.94 × 106 Simulation of model Anish, n.d.
Western (Gujarat) cost of India 1.1 to 181.2 m3 .year−1 Seepage meter Present study
0–744.5 m3.m−2 .year−1 Numerical models
0–70.5 m3.m−2 .year−1 1D convective-conductive heat transport model
1D advection-dispersion model

enriched with trace metals or toxic elements, owing to poor waste manage-
ment and poor treatment infrastructure (Ahuja and Abda, 2015; Sharma
et al., 2009). The high concentration of Cr found in most of the groundwa-
ter and porewater samples depicted the high influence of anthropogenic ac-
tivities across the coastal region of Gujarat.
4.7. Local fluxes, their implication to Gujarat coast and novelty of work
Some researchers reviewed the global SGD reaching the oceans and
found that a considerable amount of fresh groundwater reaches the coastal
interface per year (Burnett et al., 2003; Taniguchi et al., 2019). Luijendijk

Fig. 8. Submarine groundwater discharge and contaminant load reaching into the Gujarat coast at the six locations. The highest SGD flux was reported at the Udvada beach
among all six locations. Zn2+ load was reported highest among all the contaminants, followed by Fe2+, Cr2+, and Cu2+ respectively. The results indicated the groundwater
reaching the coast is less as compared to flux reported in the various studies around the world. Locations of beaches start from the south coast i.e. Dehri beach to Saurashtra
Gujarat coast (chorwad holiday camp beach).

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et al. (2020) has attempted to quantify F-SGD to the oceans around the

Jeong et al., 2012

Wang et al., 2019
Trezzi et al., 2016
1400 × 103 Tovar-Sánchez
world and reported that approximately 0.6% of total freshwater input

Rodellas et al.,

Present study
et al., 2014
reaches the coast. The proportion of SGD seems insignificant compared to

References
the world's oceans but can be critical for the marine ecosystem as it inter-

2014
rupts/imbalance the biogeochemical cycles (Babu et al., 2021; Luijendijk
et al., 2020). The severe threats such as eutrophication, growth of harmful
algal bloom, and accumulation of trace metals that the contaminants can

0.005–7.3
DSi pose to the marine ecosystem, and the growing dependency on groundwa-

NA

NA

NA

NA
ter in the last few decades, make SGD an integral part of the hydrological
cycle (Taniguchi et al., 2019).

240.6–541.41
Tables 1 and 2 summarize SGD flux and contaminant load reaching the

0.003–0.44
oceans, reported across the world. When compared with the present aver-
× 103 age SGD flux, it was observed that the flux reaching the Gujarat coast was

42.2
Mn

NA

NA

NA relatively low. The range of SGD flux quantified in the present investigation
was varied from 1.1 to 181.2 m3. year−1 (using seepage meter) and
512.4–1404.4

0–744.5 m3.m−2.year−1 (simulated), was relatively less than the simulated

0.009–1.8 SGD reported by Debnath et al., 2015 and Mukherjee et al., 2007 in the Bay
× 103

of Bengal (1.16 × 106 m3. year−1) and Western Bengal Basin, India
NA

5.7–120.7 × 103 100.5–1619.4 × 103 5.27–111.5 × 103 0.44–1.2 × 103 24.8–784.5 × 103 NA

NA

NA
Cr

(5.9 × 107 m3. year−1), respectively. Estimated SGD in the present study
was comparable to SGD flux (10.95 to 54.75 m3.m−2. year−1) reported
by Selvam et al., 2021 on the South-East coast of India. However, in a
10.5–147

semi-arid region and developing state like Gujarat, the loss of such a high
2 × 103

0.6 77.4

volume of water through SGD is alarming as most of the villages in the Sau-
NA

NA
Zn

rashtra, central Gujarat and Kutch region face water scarcity. Seawater in-
trusion (SWI) or salinization of coastal aquifers has become a prevalent
phenomenon resulting in the deterioration of groundwater quality and,
0.004–1.2

hence, is not suitable for domestic use. The loss of freshwater due to SWI
0–3.66

along with its associated problems is another issue arising in the state's
NA

NA

NA
Pb

coastal region. The southern region of Gujarat is drained by four westward

draining perennial rivers (Tapi, Narmada, Mahanadi and Purna), which
help to maintain the coastal aquifer's groundwater reservoir. The long
coastline of Gujarat (~1600kms) makes it difficult to quantify the SGD
`0.004–0.9
12.3–61.3

flux considering its heterogeneity in every aspect, such as the geology

42.8

(surface and subsurface), hydrology, and groundwater discharge/recharge

NA

NA
Ni

pattern.
Estimation of SGD is essential for understanding the mixing processes
and estimating the fresh groundwater loss at the seawater groundwater in-
35.87–1793.5

terface. Moreover, it is important to account for SGD to better understand

111.7–3350
3.2 × 103

4.7 × 103

0.06–10.5

terrestrial solutes transport in the marine environment, separately from sol-

× 103

ute inputs as riverine discharge. The fraction of water being discharged

Fe

from aquifers might seem insignificant compared to riverine discharge

but may have a profound impact on the marine ecosystem, as the mass bal-
ance of organic and inorganic species get disturbed due to the influx of
Contaminant fluxes reported in the various part of the world and present work.

0.004–1.1

these solutes. Therefore, the observed pore water salinity and temperature
7.2–54

13.91

were used to estimate vertical porewater velocity using the 1D convective-

Heavy metal flux (kg. year−1)

NA

NA
Cu

conductive heat transfer model and 1D advection-dispersion model. Hence,

the application of salinity and temperature profiling is not only for the de-
0.12–3.1

0.001–0.17 0–0.042
× 103

lineation of groundwater seawater mixing zones but also to identify the

3.06
NA

NA

NA

sources of total SGD. The outcome of this work is the first-hand approxi-
Co

mated range of SGD flux and contaminants load entering the coast of Guja-
26.8–80.4
0.085–3.7

rat from the inland aquifers of western India.

× 103

× 103

This is the first study highlighting mixing zones, estimating SGD and
3.1 × 107 m3 day−1 NA

NA

NA
Cd

contaminant flux reaching the coastal region. In this study, we have quan-
tified the SGD flux and contaminant load reaching the coastal ecosystem
(3.2–7.7) × 108 m3

Palma Beach, Balearic 56 × 103 m3 day−1

0–744.5 m3. m−2

(0.3–4.8) × 1012

of Gujarat from the shallow aquifers with the help of different techniques,
89 m3. m−2.a−1
Heavy metals

i.e. seepage meter and numerical modelling. While using numerical model-
ling, we made some assumptions and used the defined empirical relation to
SGD flux

m3·y−1

day−1

year−1

calculate the coefficient/constant required for solving the aforementioned

models. The porewater temperatures and salinity mass balance have
been used here effectively to delineate and quantify SGD flux along
Majorca Island, Spain

Mediterranean Sea

Gujarat coast, India

the coast. However, these models are heavily dependent on parameters

Bohai Bay, China

Bangdu bay Jeju

that vary based on location and time. We expect the SGD flux from the
North Western

coastal aquifers of Gujarat to be higher than the estimated discharge

Study area

Islands

Korea

in the present study. In the future, more reliable techniques such as

Table 2

radon (222,226Rn/223,224Ra) mass balance can be used to evaluate the

results of this study. Furthermore, the present study suggests more

12
C. Bhagat et al.
exhaustive research in future, focusing on the seasonal variability of
SGD flux and contaminant load along with their impacts on the marine
ecosystem.
5. Conclusions
The current study presents a methodical scientific approach to estimate
SGD flux and contaminant load that reaches the coastal waters of Arabian
Sea. Signatures of porewater, such as salinity, temperature, stable isotopes
of oxygen (δ18O) and strontium (86,87Sr), were found to be very effective for
identifying the SGD locations or for extent mapping of seawater and
groundwater mixing in the sub-terrain estuaries. Also, the applicability of
salinity and temperature as a tracer to quantify the SGD flux in combination
with seepage meter could help refine the accuracy of the method. The esti-
mated SGD flux across the coast ranged between 1.04 and 181.1 m3.year−1
using seepage meter. Simulated flux using heat transport model and solute
transport model varies from 0 to 774.7 m3.m−2.year−1. SGD flux reported
in the Gujarat coast was relatively lower than the fluxes reported in the Bay
of Bengal, Western Bengal basin, South coast of India and Mumbai Harbour
coast of Western India. In contrast, it was comparable to flux reported in the
South-East coast of India. The associated contaminant load (kg.year−1)
transported into the Arabian sea through SGD is as follows: Zn
(0.59–77.41), Fe (0.061–10.5), DSi (dissolved silica; 0.006–7.3), Cr
(0.008–1.75), Sr (0.0075–1.45), Pb (0.004–1.45), Cu(0.0087–1.73), and
Ni (0.004–0.92). The trace metal load discharging into the coast was ob-
served to be decreasing from the South Gujarat coast to the Saurashtra
coast. Therefore, the South Gujarat coast was more vulnerable to harmful
algal bloom, eutrophication and biotic ligand formation in the aquatic spe-
cies, as loads of contaminants discharging were relatively higher. Also, the
carcinogenic metals flux reaching into the marine environment poses a car-
cinogenic risk to fishers through dermal contact. The trace metal concentra-
tions reported in the porewater samples indicate the high impact of
anthropogenic sources of pollution on the groundwater and seawater in
the coastal region of the state. We speculate that the accumulation of con-
taminants would increase in the future as urbanization and industrial activ-
ities increase along the coast. This study helps to establish a unique and
multidimensional perspective about the SGD phenomenon occurring in
the Gujarat coast. Nevertheless, a more detailed investigation, including
radon isotope survey, electrical resistivity survey, and aquifer modelling,
will be essential in developing a systematic understanding of SGD as fresh
groundwater and contaminant flux reach into the coastal waters along the
Gujarat coastline.
Data availability
All other relevant data are available from the corresponding author on
request.
CRediT authorship contribution statement
Chandrashekhar Bhagat: Conceptualization, Writing original draft &
editing, sampling and analysis, data curation and interpretation, illustration
plotting and revision.
Anant Misra: Writing and editing, sampling and analysis, data curation
and interpretation.
Pranab Kumar Mohapatra: Editing and reviewing.
D. S. Suresh Babu: Editing and reviewing, Project administration.
Manish Kumar: Supervision, Conceptualization, Visualization, Data in-
terpretation, Writing - original draft and editing, Revision, Project adminis-
tration.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
13
Science of the Total Environment xxx (xxxx) xxx
Acknowledgement
This research work was financially supported by the National Centre for
Earth Science Studies Trivandrum Kerala (India) and the Ministry of Earth
Sciences Government of India under the National Mission of Submarine
Groundwater Discharge along the Indian coast. The authors acknowledged
the contribution of the Indian Institute of Technology Gandhinagar (India)
and Physical Research Laboratory (PRL) Ahmedabad (India) for analysing
the groundwater samples for various parameters. The authors express their
gratitude to the WET Lab at IIT, Gandhinagar, for helping in conducting
sampling and analysis. The authors are also grateful to the journal editor
and reviewer for their critical comments and valuable suggestion to im-
prove this research article.
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