Desalination 436 (2018) 15–27

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Desalination
journal homepage: www.elsevier.com/locate/desal

Occurrence of hypersaline groundwater along the coastal aquifers of Kuwait T

⁎
H. Bhandary, Chidambaram Sabarathinam , A. Al-Khalid
Water Research Center, Kuwait Institute for Scientific Research, Kuwait

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

Keywords: To understand the process and the source of origin of the hypersaline/brines along the selected locations in
Groundwater Kuwait's, groundwater and sea water samples were collected. The analysis of the samples reveals that a few
Hypersalinity groundwater samples had Electricity Conductivity higher than that of the seawater. The study was carried out by
Ion ratios calculating the ratio of ions to halides such as NO3/Cl, Mg/Cl, Br/Cl, Sr/Cl, Mn/Cl, Li/Cl and V/Cl. The ratios
Desalination discharge
reveal that there were three different types of groundwater: a) groundwater less contaminated with seawater, b)
groundwater equally contaminated by seawater and c) groundwater with ionic concentration greater than the
seawater. It was inferred that most of the groundwater samples collected near the bay were having higher EC
than those that were collected near the open sea. The hypersalinity of the groundwater samples was inferred due
to the influence of the effluents of the desalination plants and H2S enriched waters, though there were other
processes in operation governed by the pH, anthropogenic sources and infiltration of metal from oil ash near the
thermal power plants. The statistical analysis reveals that in certain locations, multiple processes are active to
make it more salt enriched.

1. Introduction feedwaters. The main freshwater producers by the desalination process

The coast that serves as an interface between the seawater and the
continental aquifer system is a very fragile environment. The variation
in the hydrogeochemical nature of surface and the groundwater with
space along this interface is complex [1–13]. The geochemistry of the
surface water along the bay and its variation was studied by different
authors [14–17]. Studies have also been carried out in the coastal
groundwaters, which serve as a freshwater discharge source to the
seawater [7,12,13,18–26]. Such studies play a very significant role in
the management of the water resources in the arid regions, specifically
along the coastal Gulf areas [14,27,28]. Influence of the anthropogenic
sources also plays a significant role in the water chemistry of the region,
though there is a lesser influence of agriculture [20,29]. There are
several desalination plants located in these regions due to the lack of
freshwater sources, to serve the urban and industrial needs. The study
on the impact of these desalination plants on the seawater along the
Gulf region was carried out by several researchers [30–35]. The
common antiscaling agents are mainly polyphosphates, polymers of
maleic acid or sulphuric acid. The antifoaming agents would be alky-
lated polyglycol fatty acid and fatty acid esters. The metals accumulate
near the discharge region of the effluents [36]. The chemical used in the
pretreatment of seawater is NaOCl, free chlorine, which is used for
chlorination, prevention of biological growth, H2SO4/HCl for pH ad-
justment and NHSO3 to neutralize the remains of chlorine in
along the Gulf coast are United Arab Emirates (35% of the worldwide
seawater desalination capacity), Saudi Arabia (34%, of which 14% can
be attributed to the Gulf region and 20% to the Red Sea), Kuwait (14%),
Qatar (8%), Bahrain (5%) and Oman (4%) [37]. The oil ash generating
from the thermal power plants located near the desalinization regions
results in the leaching of these metals in groundwater [38]. Studies on
the groundwater resources of the Kuwait region were also carried out
by Al-Ruwiah [39], Omar et al. [40] and Mukhopadhyay et al. [41,42].
There are isotopic and geochemical studies based on the aquifers
[43–46]. Regional groundwater flow modeling studies have also been
carried out in the region to know the flow variations [41], distribution
of transmissivity [47] water rise in the region [48]. These studies have
reported the hypersaline/brines in the selected locations of the coast.
The current study aims to understand the hypersalinity of the coastal
groundwater, by studying the geochemistry of the groundwater along
the coast and correlating with the surface water samples collected along
the Bay and in open sea. It also focuses on the possible anthropogenic
contamination of groundwater to address the hypersalinity.
2. Study area
The study area extends from 47o 40′ 8.47″ to 48o 44′ 5.584″E and
28o 32′ 11.590″ to 29o 45′ 18.493″N. The study area extends along the
coastline of Kuwait and parallel to the coast along the sea covering an

⁎
Corresponding author.
E-mail address: csabarathinam@kisr.edu.kw (C. Sabarathinam).

https://doi.org/10.1016/j.desal.2018.02.004
Received 24 October 2017; Received in revised form 11 January 2018; Accepted 1 February 2018
Available online 09 February 2018
0011-9164/ © 2018 Elsevier B.V. All rights reserved.
H. Bhandary et al.
Table 1
Observations of sea surface temperature, salinity and turbidity in different locations along the coast.
Boubyan Port Failaka Island
Minimum Maximum Mean Minimum Maximum
Sea surface 12.77 34.55 26.14 10.83 35.67
temp (deg
C)
Salinity (ppt) 39.15 46.16 42.77 34.14 45.06
Turbidity (ppm) 7 43,098 404 8 48,069
area till the Failaka Island. The physiographic parameters measured
from Boubyan port, Failaka, Sabiya coast guard area, Sabiya Military
area and Warba are presented in Table 1.
The northern territorial waters of Kuwait show a current speed up to
1 m/s, with shallow bathymetry (1–6 m), characterized by muddy
beach, higher suspended sediments and 4.5 m high spring tide. On the
contrary, the southern territorial waters show the current speed around
0.5 m/s, deeper bathymetry up to 35 m, sandy beach, lesser suspended
sediments and the tide ranging space from 1.5 to 2 m. This contrast is
mainly due to the presence of bay in the northern part and open sea in
the south. The annual evaporation in the bay is around 2 m/year, with
an approximate loss of 255 Km3 of water annually from the bay [49].
Kuwait has five desalination plants located in Shuaiba, Shuwaikh,
Doha, Sabiya and Az-Zour producing about 143,196.35 million im-
perial gallons of water/year [50], and the highest volume is observed in
Doha, followed by Az-Zour and then Sabiya. The lowest volume of
desalinized water is produced from Shuwaikh.
2.1. Hydrogeology
The unique geomorphology and lithology in the northern parts of
Kuwait were responsible for the formation of fresh groundwater lenses
that float over the main body of the saline groundwater. In the territory
of Kuwait, the extraction of groundwater is from two main aquifers,
namely, the Kuwait Group aquifer and the Dammam Formation aquifer.
(Details are provided as supplementary table).
2.1.1. Kuwait group aquifer
The three formations comprising the Kuwait Group generally slope
towards the northeast and north. The thickness of the Kuwait Group
increases from about 150 m in the southwestern parts of Kuwait to
about 400 m northeast. The Kuwait Group aquifers are completely sa-
turated with water along the coast and completely dry in the south-
western edge of Kuwait and at the Ahmadi ridge. The water level in
Kuwait Group aquifer varies from about 90 m above the mean sea level
in the southwest to zero along the coast.
The total transmissivity of the Kuwait Group aquifer increases from
southwest (10 m2/d and less) to northeast (1500 m2/d and more) with
the increase in saturated thickness in this direction (from 0 to 400 m). A
shaley unit separates the aquifer from the underlying main Kuwait
Group aquifer. The aquifer is unconfined, within the confines, the
transmissivity of the aquifer increases from about 10 m2/d in the areas
adjacent to the Kuwait Bay to 150–200 m2/d in the northeastern corner
of the country.
2.1.2. Dammam formation aquifer
A major unconformity separates the Dammam Formation, which is
deposited in a marine environment, from the Kuwait Group sediments
that are deposited in a continental environment. The Dammam
Formation has been extensively chertified and silicified in the upper
part, which is responsible for the formation of a chert zone of about 2 m
thickness separating the Dammam Formation from the Kuwait Group.
This zone is not continuous, and it acts as an aquitard between the
aquifers. The piezometric level in the Dammam Formation varies from
Desalination 436 (2018) 15–27
Sabiya Coast Guard Sabiya Military Warba
Mean Minimum Maximum Mean Minimum Maximum Mean Minimum Maximum Mean
25.09 10.77 34.15 23.5 11.31 34.01 23.71 13.24 34.17 25.67
42.16 36.53 47.37 43.85 38.7 48.31 43.56 39.11 47.05 43.28
708 14 10,293 199 35 20,887 331 102 58,008 412
about 90 m in the southwest to only a few meters above the mean sea
level near the coast [51].
In spite of the local presence of clay lenses that may act as aquitards
and the variation in the degree of karstification within the Dammam
Formation, which affects the vertical Hydraulic conductivity, the two
aquifers are hydraulically connected. Under natural undisturbed con-
ditions, there is an upward hydraulic gradient from the Dammam
Formation to the Kuwait Group aquifer [52]. As a result of the ex-
ploitation of the aquifers over the past three to four decades, the head
gradient has reversed over much of the south-central part of Kuwait.
The underground flow from Saudi Arabia is the main source for
recharge. Due to a very low rainfall (average about 110 mm/yr), high
evaporation (3000 mm/yr or more) and the absence of local depres-
sions that allow the surface accumulation of runoff and significant in-
filtration (except for limited depressions in the northern parts of the
country), direct infiltration of rain is generally negligible or absent.
Precipitation is a minor recharge source in the depressions of northern
Kuwait, where limited freshwater lenses occur in the upper part of the
Kuwait Group, especially in the Raudhatain, Umm Al-Aish and Abdally
areas. In normal conditions, groundwater flows from southwest to
northeast and discharges into Shatt-Al-Arab and the Arabian Gulf [53].
There are three drainage systems [54], two in the north (Al-Raudhatain
and Um Al-Aish) and one in the west (Dibdibba), and the southern part
is devoid of any drainage system.
3. Methodology
The groundwater samples (18) were collected from the existing
monitoring wells (represented by prefix AGL) along the coast and the
seawater samples (20) were collected near the coast with a minimum
distance of 20 m and away from the coast, representing the Bay (12)
and the open sea (8), respectively (represented by the prefix AGS). The
seawater sample was collected at a maximum distance of 38 Km from
the coast (Fig. 1). Before purging the screened interval of the well, the
static water level of the well was measured. Then, an electric sub-
mersible pump was introduced into the well 1 to 2 m below the water
table. The other end of the submersible pump was connected to a flow
through cell, in which a number of portable field measurement in-
struments (Themo Orion 5 star plus) were installed to measure the pH,
temperature, electrical conductivity (EC), dissolved oxygen (DO) and
oxidation reduction potential (Eh) using Jenway 370. These field me-
ters were calibrated on a daily basis before taking to the field. The
purpose of measuring these parameters on-site was to ensure that
purging would remove a sufficient quantity of water thereby collecting
the representative groundwater sample. Once the field measurements
stabilized, the groundwater sample was collected for measurement of
radon and other chemical quality measurements. The collected
groundwater and seawater samples were analysed for major cations and
anions (Na, K, Ca, Mg, Cl and SO4) using ion chromatograph (ASTM
D6919-09 and SMEWW Method No.4110). Nutrients (NO3, NH3 and
PO4) and silicate (SiO3) were analysed using discrete analyzer (SMEWW
Method No. 4500 G, E, F and C), trace metals (Fe, Mn, V, Li, Sr, B and
Br) using ICP-OES (USEPA 200.7); and H2S using the Iodometric
method (SMEWW 4500-S2−-F) in the Water Research Center (WRC)
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H. Bhandary et al. Desalination 436 (2018) 15–27

Fig. 1. The sampling locations for groundwater and seawater in the proposed study.

laboratory at the Kuwait Institute for Scientific Research (KISR). Radon
was analysed in situ using RAD7 portable analyzer (Liquid Scintillation
Method- SMEWW 7500-Rn B). The WRC laboratory of KISR is ISO
9001:2008 certified, and standard methods have been adopted to
analyze the water quality parameters in the laboratory as explained in
the standard methods for the examination of water and wastewater
[55].
4. Result and discussion
The analytical results of the 22 variables are listed in the table se-
parately for seawater and freshwater (Table 2). The statistical summary
of the results indicate that a few samples of groundwater have higher
values of EC, total dissolved solids (TDS), Na, K, Ca, SO4, Cl and Br than
those of seawater, indicating hypersaline conditions. But the mean re-
flects higher values for seawater; subsequently, the standard deviation
shows higher or equal to the average values of a few parameters. The
mean values for Mg, Cl, Rn and Li in seawater and those for K, NO3, Fe
and Mn in groundwater indicate that they are higher in certain loca-
tions than the average value observed. The range between the
minimum and maximum indicates that majority of the groundwater
parameters observed, except Mg and PO4, have higher ranges than
those of the seawater. This also indicates that there are large variations
in the geochemistry of the groundwater than that of seawater.

Table 2
Maximum, Minimum and Average Values of the Parameters Analysed; all Values are in mg/L Except EC (in μs/cm), Rn (pCi), Ra (dpm) and pH.

Groundwater (N = 18) Seawater (N = 20)

Parameters Mean Minimum Maximum Range Std. Deviation Mean Minimum Maximum Range Std. Deviation

EC 48,016.1 2650.0 117,500.0 114,850.0 35,533.8 63,530.0 62,200.0 65,100.0 2900.0 922.9
pH 7.1 6.3 8.0 1.7 0.3 8.1 7.9 8.3 0.4 0.1
TDS 35,042.3 1649.0 98,692.0 97,043.0 28,121.2 45,159.7 39,838.0 56,844.0 17,006.0 3242.4
HCO3 136.9 85.0 240.0 155.0 42.0 150.8 101.0 240.0 139.0 29.1
Na 9248.2 449.0 24,553.0 24,104.0 8257.5 13,562.3 10,297.0 14,654.0 4357.0 1045.3
K 328.1 11.0 1147.0 1136.0 332.7 448.8 340.0 486.0 146.0 34.5
Ca 1127.1 72.0 2607.0 2535.0 680.1 689.4 573.0 1531.0 958.0 202.6
Mg 1125.0 78.7 2753.0 2674.3 960.2 2315.4 1251.0 14,197.0 12,946.0 2799.5
SO4 3017.8 623.2 6259.0 5635.8 1702.2 3418.0 2411.0 3736.0 1325.0 342.1
Cl 19,328.3 278.0 54,813.0 54,535.0 17,816.2 24,804.3 16,929.0 27,084.0 10,155.0 2594.9
Br 62.5 1.1 148.5 147.4 58.6 81.7 56.2 90.1 33.9 8.4
PO4 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.1 0.0 0.0
NO3 107.1 33.4 709.9 676.5 151.9 0.9 0.6 1.5 0.9 0.2
TOC 1.3 0.4 3.0 2.6 0.6 1.8 0.7 2.7 2.0 0.4
Rn 70.9 7.2 211.0 203.8 53.6 20.8 0.9 85.4 84.5 20.4
Ra226 0.1 0.0 1.0 1.0 0.2 0.0 0.0 0.1 0.1 0.0
Fe 0.0 0.0 0.4 0.4 0.1 0.0 0.0 0.0 0.0 0.0
B 3.6 1.5 8.1 6.6 1.9 3.0 2.9 3.3 0.5 0.1
Li 0.2 0.0 0.6 0.5 0.1 0.1 0.0 0.5 0.4 0.1
Mn 0.0 0.0 0.3 0.3 0.1 0.0 0.0 0.0 0.0 0.0
Sr 11.7 1.3 26.6 25.3 5.9 4.6 4.5 4.9 0.4 0.1
V 0.0 0.0 0.1 0.1 0.0 0.0 0.0 0.0 0.0 0.0

17
H. Bhandary et al. Desalination 436 (2018) 15–27

Fig. 2. The spatial variation of electrical conductivity in groundwater and seawater samples collected. It also shows the location of desalination plants, thermal power plants and domestic
sewage effluent locations.

EC variation in the groundwater along the coastal region shows that decreases with an increase in temperature [58]. Hence, there exist
majority of the samples fall between 17,000 and 26,000 μs/cm, and the variations in the densities of seawater as there is a difference in an
higher values of 89,000–118,000 μs/cm are represented by 3 samples annual variation of temperature around 25 °C, which may also further
(Fig. 2). It is inferred that higher value samples are also distributed favour the dense sea water to intrude into the aquifer resulting in high
along the south of the Kuwait bay and along the southeastern part of salinities.
Kuwait. Samples from the northeastern part of the study area near the All the seawater samples are Na-Cl type, except AGS-14 (Mg-Na-Cl
Boubyan Island (AGL 14 and 17) and one along the southeastern part is type). Majority of the groundwater samples have the composition si-
AGL12. Competitively lesser values (< 17,000 μs/cm) are observed in milar to that of sea water samples, but there is a gradual evolution
the central coastal region of Kuwait (i.e., between the Bay and AGL 12). noted with variation of ions such as Na-Cl; Na-Ca-Cl; Na-Ca-Cl-SO4; and
EC variation of the seawater samples shows that the variation in Na-Mg-SO4-Cl (Fig. 3). This evolution shows a gradual increase in the
salinity is lesser and it ranges from 62,000 to 65,000 μs/cm. The spatial proportion of the alkaline earth in the composition of groundwater. One
variation of the EC in the seawater shows that values > 63,500 μs/cm sample with Ca-Na-Cl-SO4 type is noted (AGL 09) in the southeastern
are distributed along the Kuwait Bay and the northern part of the
Kuwait coast, but these samples collected from the southern and central
part of Kuwait show lesser values. It is known that the flushing of water
from the Kuwait Bay is lesser, and it is shallow with more evaporation
[49]. Hence, the preliminary results reveal that the lesser the outflow,
the more the evaporation, and shallow bathymetry is one of the reasons
for the increased EC of seawater in the Bay.
The comparison of the seawater and groundwater conductivity re-
veals that about 27% of groundwater samples have greater EC than the
seawater and most of them are from the northern part of the Bay. But it
is also observed that the EC is higher in the groundwater of the
southeastern part of Kuwait, whereas EC in the seawater is lesser in
these regions. The earlier study [56] inferred that higher H2S con-
centration in groundwater encounters higher salinity. Hence, the sam-
ples were analysed for H2S and it was identified only in three
groundwater samples of AGL1 (82 mg/L), AGL11 (6 mg/L) and AGL13
(16 mg/L), and in few seawater samples, with lesser concentration. It
was interesting to note that the higher concentration of H2S was noted
in the same location (AGL1) by Mukhopadhyay et al. [56]. The con-
ductivity values of the seawater near open sea samples are lesser due to
the circulation in the open sea [57]. The seawater samples along the
Bay have comparatively higher EC values than those of the open sea.
Temperature is a factor of salinity at lower temperatures; higher salinity
has more density and comparatively for the same salinity, the density Fig. 3. Cluster of samples in the Standard Piper plot. (AGL represents samples ground-
water and AGS represents sea water).

18
H. Bhandary et al.
160
140
ZONE 3
120
100
Bromide values in mg/L
80
60
40
20
0
0 10000
Fig. 4. The relationship of Br and Cl in seawater and groundwater samples.
part of the study area. It is observed that there is no groundwater
sample representation with the predominance of HCO3. Most of the
groundwater samples and all the seawater samples are characteristic of
Na-Ca-Cl type and shows that they are distributed above the halite
equilibrium line indicating the saline nature. The certain groundwater
samples show higher proportion of Ca than the seawater samples. It is
also noted that Cl values of few groundwater samples are greater than
those of seawater indicating the hypersaline/brine nature.
4.1. Br versus Cl
Since Cl and Br represent conservative behavior, due to their hy-
drophilic nature they act as natural tracers [59–61]. It is significant that
both ions are neither observed onto the mineral surface nor in ion ex-
change reactions. When halite starts to precipitate it begins to be a part
of evaporate mineral at a higher temperature [62–64].
The chemical behavior of Cl and Br shows deviation in the trends
and helps understand the signatures of different process. They are re-
ported as small amounts in volatile compounds [65,66]. The organic
activity near the sea surface and on the continent also favors Br [67,68].
The bivariate plot of both the ions (Fig. 4) indicates three distinct zones
of groundwater spread. Ground water samples falling in Zone 2 have
composition similar to that of seawater, groundwater samples in Zone 3
have values greater than the seawater and those falling in Zone 1 is
lesser than the seawater. The zones/clusters are grouped with seawater
composition as a regional measure. The diagram in general shows linear
relationship between both the ions. There are two distinct regions in
Zone 3, represented by 2 groups and the first group is represented by
samples, AGL 1 and AGL 13 along the southern part of the Bay near the
Kuwait City. This portion has been extensively studied for the H2S in
groundwater associated with the hydrocarbon of the oil field [56], and
it was inferred that H2S correlated with higher TDS in these regions and
in the present observation also AGL 1 has 82 mg/L of H2S. The other
group of samples in this zone are AGL 18, AGL 17, AGL 14 and AGL 12,
where sample AGL 14 and AGL 17 are noted along the northern part of
Kuwait near the Boubyan Island. AGL 18 is located in the eastern part of
the Bay and AGL 12 is located in the southern part of Kuwait's boundary
along the coast. Except AGL 14, the other samples are distributed in the
different region of the coast and near the desalination plants. Zone 2 is
represented by AGL 7 and AGL 3, and these are also along the bay.
Desalination 436 (2018) 15–27
13
Hydrocarbon 12
17
influenced 14
1
samples
18
3
SW
7 ZONE 2
GW
10
ZONE 1
20000 30000 40000 50000 60000
Chloride values in mg/L
The rest of the samples have lesser values than those of seawater
representing Zone 1, but in general, a linear trend exists heading to an
inference of the conservative nature of the halogens. It is inferred that
the Br values are comparatively lesser in the samples around the bay.
Organic bromide is generally formed during the chlorination of sea-
water due to the fact that 81 mg/L of bromide is present in seawater
and bromide has a lesser oxidation potential than chlorine [69].
4.2. Mole ratio Cl/Br to Cl
The Cl/Br ratios are also used to determine the origin and evolution
of groundwater, surface water and brines in oil gas exploration [70,71].
The ratio also helps in the determination of pollution due to surface
derived diffusive anthropogenic compounds [72,73]. It is estimated by
Fontes and Matray [63] and Edmunds [74] that there exists a negligible
to lesser variation in the ratio of groundwater during the process of
saline evapoconcentration.
In industrial zones along with the combustion of hydrocarbons and
fuel in the urban region Cl/Br ratio is lesser than that of the seawater
[1]. Seawater/marine influence on groundwater reflects the ratio will
almost resemble that of the seawater, 650. The salinity leached from the
garbage and solid urban waste increases the Cl/Br ratio between 750
and 1000 [60]. As Cl precipitates, Br is held in solution and shows a
mole ratio of about 655 in residual brine [75,76,117]. Taberner et al.
[76] investigated that the variations in the ratio are also noticed when
Br replaces Cl ion in precipitated minerals.
Lower ratios (Fig. 5) around 450 of sample AGL 11 show the pos-
sibility of the impact of septic waste [77]. This lesser value accom-
panied by higher values of NO3 confirms the source of groundwater
contamination. Similarly, the lower value of the ratio in AGL 1 is not
associated with the higher nitrate indicating the contamination by vo-
latile hydrocarbons from the combustion of automotive fuels or Br-
based halocarbons, as this location is being monitored for H2S asso-
ciated with hydrocarbons. The adsorption due to organic materials and
the dilution of freshwater or organic adsorption [78] also result in the
variation of this ratio. The groundwater samples of Zone 1 have a
value < 650 (AGL 2, AGL 6, AGL 9 and AGL 11) were collected along
the coast bordered by open sea and the samples that have a value > 800
(AGL 4, AGL 5, and AGL 16) are collected from the shore bordered by
Bay, but sample AGL 12 of this category, which is collected from the
19
H. Bhandary et al. Desalination 436 (2018) 15–27

Mole rao of Cl/Br to Cl in mg/l

2200

GW SW
2000 Leaching of gypsum containing halite

1800

1600

1400
mole rao of Br/Cl

1200

1000

Leached from solid garbage ZONE 3

800

Sea water line for Kuwait

600

400
ZONE 1

200

0
10000 100000
Cl values in mg/L

Fig. 5. The relationship of the mole ratio of Cl/Br and Cl (mg/L) in seawater and the groundwater samples.

southern part is proximate to desalination plant, representing zone 3. ratio indicate the impact of desalination plants, in the samples with
Those samples which near the sea water composition belongs to Zone 2. relatively higher chloride and lesser bromide than the seawater. These
are represented by samples AGL 18, AGL 14, AGL 17 and AGL 12, re-
flecting that there is a predominant process that increases the con-
4.3. Mole Br/Cl versus 1/Cl
centration of Cl compared to Br, which may be due to the effluent from
the desalination plants. It is also interesting to note that these locations
The study on the bromide ions in groundwater has helped in un-
are distributed in the south of Kuwait and along the northern border of
derstanding the sources of salinity. The study on the Br/Cl ratio was
Kuwait where the desalination plants are located. As inferred earlier
attempted by Dittmar [118] and identified that the seawater ratio was
these samples also represent the regions with higher EC. Further higher
nearly constant as 0.003473 ± 0.000012, and the average value of Br/
ratios of Br/Cl reflect the influence of Sulfide in groundwaters. This
Cl ratio in Kuwait seawater observed in this study is
represented by samples AGL 1 and AGL 13, predominant with the in-
0.003293731 ± 0.00003546. Similar to Cl and Br plots, this is also
fluence of hydrocarbons. Samples AGL 1 and AGL 13 show high Cl and
classified into zones (Fig. 6). The figure depicts the distribution of
low Na, with relatively higher saturation index of halite. The con-
samples in three different zones with respect to Cl representing higher
centration of hydrogen sulfide and the TDS content suggested non-an-
chloride regions as Zone 3, the least as Zone 1 and those similar to sea
thropogenic origin of the sulfide in the groundwater of Kuwait [56].
water as zone 2.
Samples of Zone 1 with lesser Cl values than that of the sea water are
The samples of zone 3 are represented by two different patterns with
also further differentiated with lesser Br/Cl values and higher Br/Cl
respect to Br/Cl ratio with a clear demarcation. The samples with lesser

Br/Cl rao Vs 1/Cl

3
ZONE 3 ZONE 2 ZONE 1
Chloride is greater
2.5
than sea water
1 7 Chloride is lesser
than sea water
Relavely higher Bromide
Bromid
zone than sea water Relavely higer Bromide
zone than sea water
2
13 9 2
10-3Br/Cl (molar)raio

GW
1.5
14 18 SW
17
10 16
12 4
1
Chloride is lesser
than sea water
5
Chloride is great
greater Relavely lesser Bromide
0.5 8 zone than sea water
15
Relavely lesser Bromide
Br

0
1E-08 0.0000001 0.000001 0.00001
1/Cl (mg /L)

Fig. 6. The relationship of mole ratio of milli mole Br/Cl mole ratio and 1/Cl (mg/L) in seawater and the groundwater samples.

20
H. Bhandary et al. Desalination 436 (2018) 15–27

2.5
01

10 -3 *Br/Cl (mole rao)

11
Hydrocarbon
influenced
samples
2
09 13
02

06
03
1.5 SW
18
07 14 GW
17
16 10
04 12
1
Samples from Bay
05
15
08 0.5

0
-6 -5 -4 -3 -2 -1 0
Saturaon in dex of Halite

Fig. 7. Behaviour of halite saturation to Br/Cl ratios in groundwater and seawater samples.

values. Those with less Br/Cl values reflect the normal origin of the
brines is due to the evaporation from the saline water beyond saturation
resulting in brine with Br/Cl and low Na/Cl ratio relative to seawater
[79]. This condition was noted in samples AGL 1, AGL 2, AGL 9, AGL 11
and AGL 13. The samples of zone 1 with higher Br/Cl ratio are re-
presented proximate to the bay represented by samples AGL 4, AGL 5,
AGL 8, AGL 15 and AGL 16. Zone 2 is represented by the samples along
the coast of the open sea with ratio similar to that of the sea water
composition.
decreasing trend of this ratio in the groundwater samples till it reaches
the seawater salinity [81], but for the samples with EC greater than the
seawater, there is an increase in the ratio (Zone 3). Most of the samples
of Zone 3 near the Bay show the increasing trend (AGL 17, AGL 14 and
AGL 1) but the samples AGL 10 and AGL 12 are from the southern part
of the study area. The rest of the groundwater samples show decreasing
trend with salinity, Zone 1. This may mainly be due to the fact that the
pH is one of the predominant parameters that control the mobility of Sr
[82,116].

4.4. Halite saturation versus Br/Cl

4.6. Mole ratios

The halite saturation of the surface and the groundwater shows that
there again similar groupings of samples compared to the seawater
composition like the earlier plots, which significantly unravels the
different processes, into three different zones. In general, the solution
becomes enriched with bromine when it approaches the halite satura-
tion as the Cl will prefer Na to saturate and result in NaCl [74].
Fig. 7 shows that there are two different processes in which the
groundwater samples proximate to the bay are enriched to seawater
composition which is reflected by variation in slope. One process may
be due to the normal seawater contamination and the other one due to
the influence of brine effluents. There is a clear differentiation of hy-
persaline groundwaters due to the natural influence at locations AGL 1
and AGL 13.
4.5. Sr/Ca to EC
The ratio of Sr/Cl in seawater ranges from 1.55 mmol/mol to
4.13 mmol/mol with an average of 3.66 mmol/mol. The average of Sr
reported in the sea is 7.64 ± 0.5 mg/kg and that of Ca is
405.87 ± 27.49 mg/kg [80]. It is noted that the average value of Sr is
lesser, and that of Ca is higher in these ocean regions. This variation of
concentration brings down the ratio to 3.66 mmol/mol compared to the
reported average value of 8.61 mmol/mol [80].
The average concentration of Sr in Kuwait's seawater reported in
this study is 4.61 ± 0.91 mg/L and that of Ca is 689 ± 202.59 mg/L.
This variation is mainly governed by the interaction of parameter such
as pH, temperature, DO, and TDS ([57]c). There is a definite trend
noted in the relationship of this ratio to EC (Fig. 8). There is a general
The mole ratio of NO3, Mg, Li, Sr, B, Mn and V to that of chloride ion
has been studied to understand the relationship of the groundwater
samples to that of the seawater samples and to know their spatial
variations (Fig. 9a, b,c). The ratios compared to chloride ion shows
basically three different trends
1. Decrease of the ratio with Chloride (NO3, Mg, B and Sr)
2. Decrease of the ratio till sea water composition then increase (Li and
V)
3. No definite trend (Mn)
The variation is noted in the samples of Zone 3, with higher
chlorine. But there is no much variation in the samples of Zone 1 and
Zone 2.
The Zone 3 is represented by groundwater samples with hypersa-
line/brine condition (AGL 13, AGL 18, AGL 17, AGL 14 and AGL 12),
Most of these samples are distributed along the coast proximate to bay
and sample AGL 12, in the southern part of the study area. AGL 12 had
highest EC and the Li ratio was comparatively higher than that of the
other hypersaline samples.
The decrease of halide ratio with Li and V with increase in chloride
concentration was noted until it is similar to the seawater ratio then it
gradually increases in hypersaline groundwater. The ion ratio of Li and
V shows that there is an increase of this ratio with an increase in the
mole concentration of chlorine along the bay, and this was more than
the seawater ratio. Moreover, the ratio signifies the differences between
the groundwater samples proximate to the Bay and open sea. This also
signifies the relationship of ions in regions proximate to desalination

21
H. Bhandary et al. Desalination 436 (2018) 15–27

Chart Title
14

12

Zone 2
10
Zone 3

Zone 1 Hydrocarbon
SW GW
8 influenced
Sr/Ca rao

17
7 14
6
1 Influence of
10
desalinaon
plants
4 3 18
12
13

0
0 20000 40000 60000 80000 100000 120000 140000
Electrical conducvity in ms/cm

Fig. 8. The relationship of the mole ratio of Sr/Ca and EC in seawater and the groundwater samples.

plants (AGL 17, AGL 18, AGL 13 and AGL 12). dissolution and saturation of these complexes are governed by pH and
There is a clear demarcation of the groundwater samples proximate salinity [89]. Discrete accumulation of the organic matter is often noted
to the Bay and to the open sea. The groundwater samples near to Bay in the marine or fluvial originated sediments in the solid phase with
show an increase in the V/Cl ratios with variations in salinity reflecting minerals such as pyrite, siderite and Fe(II) silicates. These minerals will
a lesser increase in Li/Cl ratios (Fig. 10). But the groundwater samples act as reducing agents when they are brought in contact with the
proximate to open seacoast show an increase in both V and Li to oxygen of nitrate [90–93]. The aquifer matrix significantly influences
chloride ratio indicating additional sources of Li in the groundwater the amount of these reductants, while environmental conditions, such
samples near the sea coast, or the salinity of Kuwait bay has decreased as pH and microbial activity, are the key factors that govern their re-
the ratio of Li to chloride ions, which in turn reflect the variations in the activity [92,94]. This process is represented by samples AGL 1, AGL 2,
geochemical character of the samples. AGL 8, AGL 10, AGL 11, AGL 12, AGL 13 and AGL 16 (Table 3) along
the eastern coastal region and a few samples near the Bay. The impact
of microbial activity was noted in the earlier studies carried out in this
4.7. Statistical analysis
region by Mukhopadhyay et al. [56].
Factor 3 describes a significant proportion (9%) of total variance
There are five factors extracted by varimax rotation with Kaiser
with high positive loadings of nitrate and phosphate and less significant
Normalization, representing a total data variance of 83%. The first
correlation with bicarbonate. Samples AGL 1, AGL 2, AGL 7, AGL 10,
factor with 40% of Total Data Variance (TDV) is represented by EC,
AGL 11 and AGL 17 mainly represent the Factor 3 (Table 3). Samples
TDS, Na, K, Mg, SO4, Cl, Br, B and Li (Table 3). The association in-
AGL 1, AGL 2 and AGL 7 are near urban area and thus may be influ-
dicates the hypersalinity of groundwater. B is generally associated with
enced by anthropogenic impacts. The main anthropogenic sources of N
saline waters in the coastal aquifers. The dissolved B and Li are asso-
and P in groundwater are commercial fertilizer, manure and waste-
ciated with groundwaters of elevated salinities [83,84]. These elements
water (including on-site sewage systems) [90,95]. Atmospheric de-
are reported in the marine coastal carbonate aquifers [84]. It is also
position is an additional source of N [95–97]. In general, agricultural
reported that the closed desert basins are favorable settings for brine,
lands and sewage plumes contribute the largest quantity of nitrate and
which are associated with these elements [85–87].
phosphate to the shallow groundwater of the aquifer. Inorganic dis-
Factor 1 is represented by AGL 1, AGL 3, AGL 7, AGL 10, AGL 12,
solved PO4 behaves as reactive phosphorous found in oxic sandy soils
AGL 14, AGL 17 and AGL 18, of which all the samples except AGL 10
[98] and in some septic system plumes [99]. Oversaturated or under-
and AGL 12 are located near the bay (Table 3). The desalination plants
saturated water with respect to calcite comes from the mixture of
are located near the sampling locations AGL 14, AGL 17 and AGL 1.
groundwater and seawater in this zone. Particularly in limestone
Similarly the sample location 12 has a desalination plant located along
aquifers, undersaturation states and the resulting calcite dissolution
the southern part of Kuwait. To avoid the mineral scaling and biological
increases bicarbonate concentration, which can greatly increase the
growth and prevent the membrane life, large volumes of chemical
porosity and permeability of the aquifer [90,100,101]. But the samples
compounds are added during the post treatment and pretreatment
AGL 10, AGL 11 and AGL 17 represent the places where oxic ground-
process. These compounds also help in the enhancement of flocculation
waters encounters anoxic bottom sediments, and high NO3 and low PO4
or prevention of foaming [88]. Hence, it is inferred that predominantly
groundwater meets seawater with high dissolved NH4, PO4 and Fe2+,
the process of desalination governs these brine groundwaters.
which causes the removal of seawater NH4 and groundwater NO3 in the
Factor 2 is represented by the positive loadings of Ca, Sr and Fe with
mixing zone by nitrification and denitrification, respectively. PO4 is
strong negative loadings of pH (TDV 16%). It reveals the release of
released from organic matter and from the reduction of Fe-oxides, thus
these cations in the acidic environment. As discussed earlier in Ca/Sr
accumulated in the groundwater [102].
distribution, the geochemical behavior is inferred to be governed by
Factor 4 is represented by Sr and V with a negative representation of
pH. The process of the dissolution of siderite and formation of Fe and
total organic carbon (TOC) (Table 3). The seawater intrusion along the
calcium carbonates are reflected in this factor, as precipitation,

22
H. Bhandary et al. Desalination 436 (2018) 15–27

1 Cl in moles
0 .
0.2 .
0.4 0.6 0.8 1 1.2
. 1.4
. 1.6
. 1.8

ZONE 1 ZONE 2 ZONE 3 SW NO3/Cl

0.1 GW NO3/Cl

SW B/Cl

GW B/Cl
mole raos of NO3/Cl, B/Cl, Sr/Cl

0.01 SW Mg/Cl

GW mg/cl

SW Sr/Cl

0.001 GW Sr/Cl

0.0001

0.00001

0.001 Cl in moles
0 0.2
. .
0.4 0.6 8
0.8 1 1.2
. 1.4
. 11.6 1.8

ZONE 1 ZONE 2 ZONE 3

0.0001
mole raos of Li/Cl, V/Cl

SW Li/Cl

GW Li/Cl

SW V/Cl
0.00001

GW V/Cl

0.000001

0.0000001

Fig. 9. a. Mole ratios of ions (NO3, Mg, B and Sr) to chloride in groundwater and seawater with variation in Cl.
b. Mole ratios of ions (Li and V) to chloride in groundwater and seawater with variation in Cl.
c. Mole ratio of ions Mn to chloride in groundwater and seawater with a variation in Cl.

coastal aquifers can increase the organic carbon oxidation rate [103], irrespective of pH. Oil lake of Kuwait has been reported to have a
which is ascribed to the salt enhanced hydrolysis of solid organic matter higher impact on groundwater resources with V [106]. The amount of
upon salinization; it was ascribed to the increased ionic strength that organic matter, as reflected by nonvolatile organic carbon, varies con-
weakens the divalent bond of adsorbed organic matter. The change of siderably. A moderately positive correlation was noted between Sr
the geochemical environment of the aquifer due to large scale extrac- contents and the organic matter in the groundwater [107]. Hence, it is
tion results in the decline of water level, even such shifts in the equi- inferred that this factor represents the signatures of organic matter in
librium of mineral phases, which may increase or decrease V con- groundwater and it is represented in samples AGL 1, AGL 5, AGL 7, AGL
centration in water. The dissolved V in adsorbed organic compounds 9, AGL 10, AGL 11, AGL 14, AGL 15, AGL 16, AGL 17 and AGL 18,
forms relatively weak complexes [104,105]. The concentration is where most of the samples are represented near the Bay except the
higher in oxic and alkaline groundwater than in anoxic groundwater samples AGL 9, AGL 10 and AGL 11 which are represented in the

23
H. Bhandary et al. Desalination 436 (2018) 15–27

9c 0.0001 Cl in moles
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

ZONE 1 ZONE 2 ZONE 3

0.00001

mole ratio of Mn/Cl

SW Mn/Cl
0.000001
GW Mn/Cl

.0000001

1E-08

1E-09

Fig. 9. (continued)

southern part of Kuwait's coast. in oil ash derived from thermal power plants. It is interesting to note
Factor 5 is represented by Mn with a TDV of 8% (Table 3), this is that all five processes act at the same places in AGL 1, similarly four
mainly reported to be due to the metal contamination from the oil ash, factors in AGL 7, AGL 10 and AGL 17, three factors in AGL 11, AGL 14
which predominantly contains Mn [108,109]. The release of Mn is and AGL 18 and two in AGL 2, AGL 8, AGL 12, AGL 13 and AGL 16
governed by pH variation in groundwater at low saline regions and it is (Table 3B). At the sample location AGL 1, all these five factors play a
inferred to be from the oil ash generated from power plants. They are significant role with more impact of factors 2, 5 and 3. But the samples
represented by the sample numbers AGL 1, AGL 6, AGL 7, 8 AGL, 13, near the open sea coast show the predominance of one factor or a
AGL 14, AGL 17 and AGL 18, as inferred by the thermal power plants combination of two, except samples AGL 10 and AGL 11. There is a
located near the sample locations AGL 1, AGL 13, AGL 14 and AGL 17. representation of 4 factors in samples AGL 7, AGL 10 and AGL 17; three
In general, the representation of the samples from five major pro- factors in AGL 11, AGL 14 and AGL 18. In general, it is observed that
cesses can be summarized as the impact of hypersaline brines mainly more combination of processes are noted in the groundwater samples
due to desalination plants, followed by pH governed dissolution, an- along the Bay than along the open sea coast. It is to be noted that de-
thropogenic signature, organic influence and the dissolution of metals salination effluents, discharge is nearly brine and if there is a lack of

6
0.0001
0 0.00002 0.00004 0.00006 0.00008 0.0001 0.00012 0.00014

6
15
Groundwater
samples 16 2
along the
Kuwait Bay
0.00001
5 4

11
9
V/Cl

17
7
18,14 8
10
0.000001
13 1 3

12

0.0000001
Li/cl

va/clsw va/clgw

Fig. 10. Ratios of Li /Cl to V/Cl in groundwater and seawater.

24
H. Bhandary et al. Desalination 436 (2018) 15–27

Table 3
Rotated Component Matrix of the Groundwater Samples.

A. Rotated component matrix

Component

1 2 3 4 5

EC 0.958 0.246 −0.036 0.015 0.034

pH −0.043 −0.826 −0.299 −0.002 0.150
TDS 0.958 0.221 −0.052 −0.016 0.001
HCO3 −0.041 0.325 0.456 −0.333 0.371
Na 0.892 0.149 −0.090 0.127 0.259
K 0.951 0.076 −0.077 −0.073 0.007
Ca 0.462 0.772 −0.070 0.136 0.010
Mg 0.971 0.040 −0.109 0.043 0.147
SO4 0.900 −0.064 −0.243 0.022 0.103
Cl 0.959 0.175 −0.124 0.001 0.135
Br 0.863 0.400 −0.058 −0.011 0.234
PO4 −0.383 −0.080 0.782 −0.227 0.091
NO3 −0.101 −0.007 0.845 0.095 −0.150
TOC 0.257 0.014 −0.023 −0.820 0.025
Rn −0.150 −0.129 0.377 0.123 −0.775
Ra226 0.189 0.825 −0.101 −0.147 0.214
Fe 0.015 0.766 −0.171 −0.364 0.233
B 0.791 0.159 −0.109 0.212 0.225
Li 0.814 −0.049 −0.082 −0.084 −0.449
Mn 0.277 0.020 0.190 0.179 0.763
Sr 0.254 0.673 0.006 0.533 −0.027
Va 0.370 −0.166 −0.180 0.720 0.146
TDV 40 16 9 8 8

Representation of factor score for each samples

Samples Factor 1 Factor 2 Factor 3 Factor 4 Factor 5

1 0.115 2.527 0.439 0.042 0.597

2 0.056 0.845
3 0.826
4 0.007
5 0.296
6 0.912
7 0.208 0.781 0.599 2.498
8 0.255 0.292
9 0.152
10 0.417 0.492 0.246 0.637
11 0.022 3.422 0.412
12 1.881 0.026
13 2.396 0.943
14 1.377 0.508 0.735
15 0.879
16 0.053 2.011
17 1.504 0.009 1.006 0.209
18 1.301 0.822 0.455

water circulation in the open sea, it develops anoxia in water and
thereby reducing DO. In general, the discharge water conductivity
range is around 65,800 μs/cm or above with pH slightly less than the
seawater [31]. The excess brine discharge develops a hypersaline layer,
which sinks towards the seabed by the virtue of its higher density,
which affects the marine organisms ([110]: [111]). Further the varia-
tion of pH induces the dissolution of ions and the influence of organic
substances in groundwater. The tidal fluctuation exposes the land sur-
face more along the Bay and has helped the infiltration of hypersaline
brines into the groundwater. The gentle bathymetry with shallow wa-
ters in the Bay has also aided the process. Moreover, the leakage from
the effluent pipeline has also influenced the infiltration into the
groundwater.
5. Conclusion
The geochemical analysis of groundwater and the surface water
samples collected reveals that a few groundwater samples represent
hypersaline/brine conditions and a few samples, slightly higher than
the seawater composition. It is also interesting to note that higher Ca is
observed in the seawater samples. Most of the groundwater samples
show Na-Ca-Cl type of Piper facies and they plot above the seawater
samples indicating the trend of evolution of hypersaline condition. The
variations of Ca and Sr are mainly governed by pH and salinity of
groundwater. It is understood that the bromide concentration in
groundwater show a significant variation in the samples collected
proximate to the Bay and that of open sea. There was a decrease in ratio
of NO3/Cl, Mg/Cl, B/Cl, Sr/Cl towards the increase of salinity. But there
was a rise and fall of Mn/Cl ratio observed with an increase of salinity
and the vice versa was observed in Li/Cl and V/Cl ratio of the
groundwater samples. The ratio of the ions to halides helped under-
stand that there are three different groups of groundwaters: A)
groundwater less contaminated with seawater, represented by most of
the groundwater samples collected near the open sea; B) groundwater
contaminated equally by seawater represented by the groundwater
samples collected proximate to the southern part of the Bay; and C)

25
H. Bhandary et al.
hypersaline/brine groundwater are represented near the desalination
plants. The groundwater samples collected along the bay reflect higher
concentration of ions than those collected along the open seacoast,
which is mainly due to lesser concentration and circulation/ flushing in
the Bay water, with more tidal range and gentle bathymetry. Li/Cl and
V/Cl show significant representation of the samples in different groups
as; near the Bay, proximate to the open sea and hypersaline ground-
waters near the desalination plants. It is inferred that the impact of the
desalination effluents affects the coastal aquifers and make them more
saline, though there are other natural processes such as H2S enriched
groundwater, anthropogenic processes and pH governed dissolution,
which affect the coastal groundwater chemistry of the Kuwait aquifers.
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.desal.2018.02.004.
Acknowledgement
The authors would like to express their gratitude to the Kuwait
Institute for Scientific Research (KISR), Kuwait, for the financial assis-
tance and to Water Research Center of KISR, for their support in im-
plementation of the study in both lab and field through WM068C. The
authors would also like to thank IAEA for their inkind support extended
for this study though TC project KUW7006.
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