Environ Monit Assess (2023) 195:251

https://doi.org/10.1007/s10661-022-10874-3

An integrated approach to address the temporal variation

of geochemistry in groundwater of an arid region
Dalal Sadeqi

Received: 20 February 2022 / Accepted: 17 December 2022 / Published online: 31 December 2022
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022

Abstract Kuwait is characterized with an arid climate of sulfates like gypsum and anhydrite were determined.
and scarce freshwater sources. Variation in groundwater The increase in calcium in most of the wells facilitated
quality with space and time leads to sustainable devel- the saturation index of calcium sulfates relatively more
opment of the region. Evaluating the chemical proper- than calcium carbonate minerals. The principal com-
ties of groundwater is of prime importance to ensure ponent analysis was conducted for the data of 2004 and
the longevity of this important source of water. In this 2018; it extracted two main components accounting for
study, the geochemical data for the years 2004 and 2018 the variability of the data; the main components indicate
were examined for 6 wells in the freshwater zones of geogenic influences and anthropogenic pollution such
Northern Kuwait. The aim of this study is to examine as agriculture. The study indicates that there is no major
the geochemical variations, if any that occurred on the variation observed in groundwater chemistry during
only existing freshwater aquifer in Kuwait. The chemical the 15 years, as the chemical changes which occurred
properties examined in this study include total dissolved are minimal and do not require immediate remediation
solids, chloride, nitrate, bicarbonate, calcium, electric measures. Hence, if the current groundwater extraction
conductivity, sulfate, sodium, potassium, magnesium, rate remained with no extensive land use development, it
and pH. The variation of the electrical conductivity in would sustain the water quality of the region.
this region indicates an improvement in three wells
located in the northern to central region of the study area Keywords Hydrochemistry · Process · Saturation
as values decreased from 1210 to 956 (μS/cm); how- index · Water management · Kuwait
ever, the electrical conductivity has deteriorated in the
remaining three wells located in the central to southern
part of the study area as values increased from 791 to Introduction
1401 (μS/cm). The geochemical facies of the ground-
water were determined, indicating a migration of the Kuwait is characterized with an arid climate and scarce
groundwater facies towards more chloride dominant freshwater sources. Therefore, sustainable use of water
field in 2018. The saturation states of carbonates like has become increasingly important, especially in arid
aragonite, calcite, dolomite, and magnesite and those areas that lack an efficient amount of water resources,
and if water management techniques are not taken into
consideration in Kuwait, this could eventually encoun-
D. Sadeqi (*) ter a challenge in the foreseeable future.
Water Research Center, Kuwait Institute for Scientific
Rainfall and groundwater are the only available water
Center, Kuwait City, Kuwait
e-mail: [email protected] resources in Kuwait. The average annual rainfall in Kuwait

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 251 Page 2 of 22 Environ Monit Assess (2023) 195:251

is 112 mm per year (WBCCKP, 2021), and the majority conductivity (EC) surpasses the WHO standards indicated
of the groundwater available is in brackish form. Further- that the groundwater in the basin is not suitable for drink-
more, there are only two fresh groundwater regions avail- ing; however, it was determined that the water can be used
able in northern Kuwait, which are Al-Raudhatain and for agricultural purposes.
Umm Al-Aish (Hadi & Al Ruwaih, 2008). Many approaches have been applied to study the hydro-
The quality of the groundwater depends on the geo- chemical processes of groundwater and to investigate any
logical environment and on anthropogenic activities. One changes in groundwater over the years. Papatheodorou
of the main anthropogenic effects on groundwater is over et al. (2007) have used a multivariable statistical approach
extraction leading to lower groundwater levels and dete- on the groundwater data of different seasons, and it was
riorated water quality (Al-Khatib & Al-Najar, 2011). found that the aquifers were affected by intensive seawater
Moreover, water contained in aquifers holds a great intrusion. While Khazaei et al. (2006) used a radial and
importance especially in the times of scarcity, as recharge Durov diagram to study the time and space chemical vari-
rates to the aquifer have an indirect relationship to time of ation of the groundwater, the study utilized groundwater
rainfall and runoff making groundwater a significant and data of 25 years and it was concluded that human impacts
renewable source of supply in dire needs. The ground- on the aquifer increased the EC and NO3 − concentra-
water system offers a great alternative to water storage, tion. Moreover, there was an increase in the EC, total
which far exceeds the surface water storage such as dams. dissolved solids (TDS), and chloride (Cl−) concentration
Dams require a high cost in civil works and have adverse which was carried out by Hajalilou and Khaleghi (2009)
effects on the environment and the ecology. During the who adapted the cluster analysis and Piper diagram to
time of uncertainty due to climate change, the weather- study the geochemical variation of the groundwater for
ing events related to droughts and floods are likely to a 15-year time interval. It was also concluded from the
occur more frequently, and the events of rainfall espe- study the cause of increase was due to the existence of
cially in arid and semi-arid countries will be unpredict- fine sediments in the aquifer zone. Esteller et al. (2011)
able, by making groundwater a great and secure resource relied on maps generated by using SURFER v.6 and Arc.
in times of acute scarcity. View, multivariate statistical analysis and a principal com-
Many studies have investigated the hydrochemical pro- ponent analysis (PCA) for the historical data to establish
cesses that govern the fresh groundwater in arid regions. relationships between variables and to identify the causes
The quantity of this resource is limited due to high evapo- of high concentration of ions in the aquifers.
ration rates and limited recharge sources such as rain and Few studies have been conducted in Kuwait to under-
surface water. Therefore, the quality of this rare resource stand the geochemical process that governs the ground-
should come with high importance. Musaed et al. (2020) water chemistry, types, and genesis. Al-Ruwaih (1996)
analyzed the physiochemical parameters of the ground- studied the hydro chemical data of the groundwater in Al
water in Wadi Nisah south of Riyadh in Saudi Arabia, and Sulaibia area, which is located in the South of Kuwait,
reported that the nitrate (NO3 −) concentration exceeds for a 10-year time interval by using Durov diagram, fre-
that of the World Health Organization (WHO) stand- quency analysis, and radial imagery, and inferred that
ards; also few of the wells monitored are characterized the salinity and hardness of the aquifers have steadily
as to have high salinity hazard and the water is only suit- increased. The geochemical processes of the groundwa-
able for irrigation. Similarly, Iqbal et al. (2018) studied ter aquifers of Al-Wafra area, an agricultural land in the
the groundwater in the Liwa Area, United Arab Emirates south of Kuwait, were investigated, and the results signi-
(UAE), and found high concentration of NO3 − and sulfate fied that the aquifer is a closed system. The study has also
(SO4 −) due to anthropogenic reasons, It was also found used hierarchical cluster analysis and has concluded that
that the salinity hazard is high according to the US salin- the groundwater is separated into geochemical provinces
ity hazard diagram which concludes that the water is not based on TDS values (Saleh et al., 1999). Al-Ruwaih and
suitable for irrigation in that area. The Maan Basin in Jor- Ben-Essa (2004) studied the aquifer system in Al-Shagaya
dan was investigated by Al-Kashman and Jaradat (2013) field to understand the geological and hydrochemical pro-
to assess the quality of the fresh groundwater and its suit- cesses, which control the quality of the groundwater and
ability for drinking and irrigation. The study inferred that have reported that the groundwater has similar character-
bicarbonate (HCO3 −) and calcium (Ca2+) were the main istics to that of marine and continental waters. Also, the
sources of salinity in the groundwater. The high electric geochemical characteristics of Al-Raudhatain region were

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Environ Monit Assess (2023) 195:251 Page 3 of 22 251

explored using inverse and mass balance models to inves- to 142.5 mm with an average of 97.62 mm (WBCCKP,
tigate the interaction between the solid and liquid phases 2021). The groundwater levels were measured by previ-
of the aquifer. The study has inferred that evaporation and ous studies, and in 2009, it was indicated that the maxi-
dissolution are the main processes controlling the dis- mum groundwater level was 8.48 masl and the minimum
solved solids. The results of the study were derived based was 6.68 masl (Akber et al., 2009). In 2020, the maxi-
on a 2-year data (Hadi et al., 2007). The processes and mum groundwater level was 7.03 masl and the minimum
origins of the hypersaline/brine groundwater in coastal was 4.2 masl (Chidambaram et al., 2020). The results
aquifers of Kuwait were examined by calculating the ratio clearly indicate an average of 2 m decline in the ground-
of ions to halides such as N
­ O3/Cl and Mg/Cl. The results water level for a period of 10 years from 2009 to 2020.
implied that desalination plants had a heavy influence on All the groundwater available in Kuwait is located in
the hyper salinity of the aquifers (Bhandary et al., 2018). the Dammam limestone Aquifer and in the Kuwait Group.
Chidambaram et al. (2020) analyzed the major ions and Fresh groundwater is available as lenses floating above
isotopes to reveal the age and the source of recharge of the brackish water of Kuwait Group (Hadi et al., 2006).
the groundwater system in Kuwait. These studies have not The Kuwait Group is subdivided into Ghar, Lower Fars,
addressed the long-term variation in the geochemistry of and Dibdibba (Al-Rawdan et al., 1998). Al-Raudhatain
the fresh groundwater in the northern part of Kuwait. basin occurs in the saturated beds of the Dibdibba forma-
Consequently, the main objective of the study is to tion (Hadi et al., 2006). The Stratigraphy of the Kuwait
investigate the hydrochemical processes that govern group mainly consists of gravelly sand, sandy gravel, cal-
the fresh groundwater in Al-Raudhatain region from careous and gypsiferous sand, calcareous silty sandstone,
2004 to 2018. Several geochemical approaches Such sandy limestone, marl, and shale (Hadi et al., 2006).
as standard geochemical plots, saturation status of dif- The geological fence diagram of the Kuwait Group
ferent minerals, and multi variable statistical methods aquifer is presented in Fig. 1. The top layers are mostly
were used to Explain and identify the sources and pro- covered with silt and sand. The bottom layers are predom-
cesses of composition of the groundwater during the inantly covered by clay, sand, and silt. The middle layers
15-year time interval. Therefore, this study is of great of the Kuwait Group aquifer have various gradations of
importance specifically since it will assist in develop- gravel, sand, silt, and clay minerals.
ing a sustainable management plan for Al-Raudhatain The Dibdibba formation is differentiated into upper,
basin, which is one of only two fresh groundwater middle, and lower aquifers (Mukhopadhyay et al., 2016).
aquifers in Kuwait. The upper aquifer which has the fresh water repository
is characterized with a thickness of 12–35 m, and as
observed, it is composed of gravelly sand, Gypsiferous
Study area cement, and calcareous cement. Even though the lower
aquifer has a thickness of 12–18 m, the lithology of the
Al-Raudhatain well field is located approximately between aquifer mainly consists with sandstone made of chalky
latitudes 29° 40′N and 29° 59′N and longitudes 47° 20′E carbonate cement. Moreover, it consists of two parts: the
and 47° 44′E (Hadi et al., 2006). The basin has a surface upper layer which hold brackish water and a lower layer
area of 670 ­km2. There are 12 streams to the watershed which holds saline water (Hadi et al., 2006). The middle
from all directions towards the main depression of the aquifer is considered to be a leaky layer between the upper
wellfield. The highest elevation in the drainage basin is and lower aquifers. As the lithology of the watershed was
136 m above sea level (masl) in the western part, and the intensively studied by Parsons Corporation (1963–1964),
lowest point lies in the drainage depression of the basin it was found that the formation consists of sandstones,
with an altitude of 38 masl (Hadi et al., 2006). The fresh siltstones, and conglomerates (Mukhopadhyay et al.,
water in the basin has a TDS of less than 1000 mg\l (Hadi 2016). The depth to the water table ranges from 23 to
& Al Ruwaih, 2008). Al-Raudhatain is the largest of four 46 m depending on the surface land elevation (Hadi & Al
playas identified in the catchment located in northern Ruwaih, 2008).
Kuwait (Al-Sulaimi et al., 1997). Kuwait is located in the discharge zone, with all the
Rainfall is the main source of recharge in Kuwait aquifers having a hydraulic gradient towards the north
(Hadi & Al-Ruwaih, 2008); therefore, rainfall rate during and east. The groundwater flow rate in Al-Raudhatain
the 15-year time interval of the study ranged from 53.3 region ranged from 4 to 44 m/year (Akber et al., 2009).

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 251 Page 4 of 22 Environ Monit Assess (2023) 195:251

Fig. 1  Three dimensional geological fence diagram of the subsurface lithology

Previous studies estimated the hydraulic conductivity Al-Raudhatain oil fields are located on the southeast
of the Al-Raudhatain region decrease with depth and of Al-Raudhatain basin. The significance of the close
that an average estimate of the hydraulic conductivity proximity of the oil fields to the study area is that trace
measured of wells around the study area is 5.2 m/day levels of hydrocarbon accumulation are expected in
(Mukhopadhyay et al., 2007). The transmissivity of Al- Kuwait’s Groundwater. Moreover, the 1990 Gulf War
Raudhatain field is 800 ­m2/day (Akber et al., 2009). resulted in the combustion of 613 oil wells causing in
The Al-Abdali agricultural farms are located adja- discharge of crude oil on the ground surface and a total
cent to the study area. The groundwater in Al-Abdally volume of oil burnt was about 240 × ­ 106 ­m3 (Akber
area is shallow and it has been subjected to excessive et al., 2009). The resulted pollution was spread over the
extraction for agriculture and related purposes. There area of about 1722 ­km2. The spilled oil was gathered in
are about 1012 farms in Al-Abdali covering an area 300 oil lakes. Most of the oil spilled was recovered and
of 180 ­km2. The groundwater extraction is executed exported. Nevertheless, about 2 × ­105 ­m3 of crude oil was
through more than 1436 pumping wells and 79 hand- left behind and it was subjected to extreme weathering.
dug wells (Al-Qallaf et al., 2011). Previous studies have Because Al-Raudhatain region is located with a close
indicated that due to the heavy groundwater extraction vicinity to the crude oil contaminated ground, the by-
in the area, the water quality has deteriorated and the products of combustion and seawater which were used as
water table has declined (Hadi et al., 2006). a fire extinguishing method hold a continuous threat to

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Environ Monit Assess (2023) 195:251 Page 5 of 22 251

the aquifers in the northern region (Mukhopadhyay et al., standard procedure for quality assurance–quality control
2008). Beside, previous studies confirm the presence of (QA/QC) to guarantee careful handling of the samples.
polycyclic aromatic hydrocarbons (PAH) in wells P01, Major ions such as sodium (Na+), potassium (K +), Ca2+,
P02, and P03, which are integrated in the current study magnesium ­(Mg2+), Cl−, SO4 −, HCO3 −, NO3 −, TDS,
(Akber et al., 2009). EC, and pH were measured using the standard methods
for examining water and wastewater (APHA, 1998).
Spatial representation of the EC data for the year 2004
Materials and methods and the year 2018 was conducted by using SURFER 22.0.
SURFER is a software used to transform the XYZ data
The wells were selected based on availability of the ana- into contour maps (Bresnahan & Dickenson, 2002).
lytical values of the samples for each time period 2004 Piper diagram consists of major cations and anions,
and 2018. All wells represent Al-Raudhatain fresh which are represented separately in triangles and later
groundwater field (Fig. 2). The samples for each of the they are projected in the diamond shape, so it was utilized
wells were collected randomly throughout the year. Sam- as a useful tool for demonstrating the dominance of ions
ple collection for all the wells were done following a in the water (Al-Khatib & Al-Najar, 2011). Therefore,

Fig. 2  Sampling wells of

the study area

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 251 Page 6 of 22 Environ Monit Assess (2023) 195:251

a clear understanding of the chemistry of water will be the coefficient is to + 1 the more positive the relation-
reached (Piper, 1944). In this study, AquaChem 4.0 is the ship is and vice versa (Saha et al., 2019).
software used to distinguish the water type of the aquifer Factor analysis is a multivariate technique which has
and plot the Piper diagram for the chemical data repre- been used widely to understand the hydrochemical pro-
senting 2004 and 2018. cesses. Although correlation analysis indicates the rela-
Although saturation indices (SI) define how satu- tionship between two ions, it does not convey the rela-
rated the water is in regard to specific minerals (Ball & tionship between multiple ions which behave similarly.
Nordstrom, 1991), it indicates that the water has a ten- Therefore, PCA is utilized to give the eigenvalues and the
dency to dissolve or precipitate a set of minerals. When percentage of variance by each factor (Ako et al., 2013).
SI is zero, the water is considered to be at equilibrium, In this study, terms such as strong, moderate, and
and it is under saturated when SI is less than zero; con- weak are assigned to loading values of 0.75, 0.75–0.5,
sequently, the minerals have the tendency to dissolve. 0.5–0 respectively. The loading values are the rate of
Moreover, when the SI is above zero, subsequently the correlation between the main extracted components and
water is considered to be supersaturated and the min- the variables.
eral has the tendency to precipitate (Ball & Nordstrom,
1991). In this study, the saturation states of carbonates
like aragonite (­SIAr), calcite (­SIc), dolomite (­SID), and Results and discussion
magnesite ­(SIm) and those of sulfates like gypsum ­(SIg)
and anhydrite (­SIAn) were examined using PHREEQC Chemical analysis
V. 3 which is designed to achieve an extensive array of
aqueous geochemical calculations (Parkhurst & Appelo, The results of the geochemical analysis are presented
2013). Using PHREEQC V. 3, the saturation state of in Tables 1 and 2. Moreover, the maximum, minimum,
carbonates and sulfates were determined. Equation (1) and average of these results for the years 2004 and
is used to calculate the SI, where IAP is the Ion activ- 2018 are also illustrated in the box and whiskers graphs
ity product and ­Ksp is the solubility product (Parkhurst as shown in Figs. 3 and 4. These graphs were plotted
& Appelo, 2013). using SURFER.
( ) It is evident from the tables below that in 2004, order+
IAP
SI = log (1) of dominance of cations is Na+ > Ca2+ > ­Mg2+> K
Ksp
which remained the same for 2018. The anion domi-
The correlation coefficient matrix is a significant test nance is SO4 − > HCO3 − > Cl− > NO3 − for 2004; how-
that indicates the relationship between two independ- ever for 2018, the anion dominance order changed to
ent parameters of water. PCA is the method used in this SO4 − > Cl− > HCO3 − > NO3 − which indicate an intru-
study to measure the dependence of two variables. The sion of brackish to saline water from the layers beneath
correlation coefficient ranges from − 1 to + 1, the closer the fresh water lenses.

Table 1  Quality parameters of Al-Raudhatain groundwater aquifer in 2004 (Akber et al., 2009)
Station ID EC pH TDS Na+ K+ Ca2+ Mg2+ Cl− SO4 − HCO3 − NO3 −
(µS/cm) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)

P01 821 7.58 657 90 1.5 57.8 6.6 64 138 143 12.3
P02 702 7.56 562 64.7 1.8 66.5 6.7 72 121 141 13.2
P03 1210 7.8 968 178 1.8 43 5.6 106 234 139 19.8
P04 791 7.53 633 59.8 2.8 76 6 63 151 119 46.2
P06 4990 7.32 3992 701 1.8 407 45.7 784 1610 100 49.7
P07 3540 7.62 2832 503 1.9 234 48 186 1581 88 34.8

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Environ Monit Assess (2023) 195:251 Page 7 of 22 251

Table 2  Water quality parameters of Al-Raudhatain groundwater aquifer in 2018 (Chidambaram et al., 2021)
Station ID EC pH TDS Na+ K+ Ca2+ Mg2+ Cl− SO4 − HCO3 − NO3 −
(µS/cm) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)

P01 860 7.88 650 116 5 67 9 107 208 120 13.7

P02 545 8.02 415 55 5 51 6 18 120 144 12
P03 956 7.86 670 149 5 48 6 110 183 137 30
P04 1401 7.81 1130 110 11 214 15 165 489 93 21
P06 5200 7.53 3972 708 6 452 42 725 1694 100 57
P07 3420 7.78 2666 535 5 222 35 183 1540 90 44

Al-Raudhatain fresh water lenses float on top of The high value of the chemical parameters in wells
a brackish water aquifer, and both of them are sepa- P06 and P07 is due to the fact that Al-Raudhatain fresh
rated by a leaky layer. water lenses float on top of a brackish water aquifer,

Fig. 3  Box and whiskers plot indicating the maximum, minimum, and average of all the samples from 2004

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 251 Page 8 of 22 Environ Monit Assess (2023) 195:251

Box and Whisker Plot

10000.0
Legend
Max.
75 percentile
Median
25 percentile
Min.
1000.0
Concentrations (mg/l)

100.0

10.0

1.0
Na Ca Mg Cl HCO3 SO4 pH TDS Cond K NO3
Parameters

Fig. 4  Box and whiskers plot indicating the maximum, minimum, and average of all the samples from 2018

and both of them are separated by a leaky layer. Fur- which also is attributed to the agricultural activities that
thermore, the geographical topography of the area indi- are located with a close proximity to the study area.
cates the two aquifers (fresh and brackish water) blend It can be concluded from Table 3 that the average
sharply in some areas and gradually in other areas. values of the chemical parameters in the Al-Raudhatain
Additionally, these two wells fall outside the freshwa- basin for the years 2004 and 2018 fall in the range of
ter lense boundary of Al-Raudhatain basin (Hadi et al., international average values of chemical parameters of
2006), indicating that it is a closed system and the sur- groundwater in arid regions.
face recharge of the wells is scarce.
Furthermore, it is evident that the NO3 − values in Spatial analysis
wells P04, P06, and P07 are close to the limit of 50 mg/l
(WHO, 2003) set by the WHO for drinking water. Pre- The EC value is a measure of the concentration of the
vious studies have indicated that presence of NO3 − is ions from dissolved salts and inorganic material in
endorsed by a lithological source (Hadi et al., 2006), the water (Singaraja et al., 2018). Using the SURFER

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Environ Monit Assess (2023) 195:251 Page 9 of 22 251

Table 3  Average values of the chemical parameters in arid regions (Al-Kashman & Jaradat, 2013; Iqbal et al., 2018; Musaed et al.,
2020)
Country EC pH TDS Na+ K+ Ca2+ Mg2+ Cl− SO4 − HCO3 − NO3 −
(µS/cm) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)

The Maan Basin, Jordan 784 7.83 530 71.6 8.63 74.1 37.2 89.6 87.2 216 38.2
Liwa Area, UAE 1479 6.5 863 2923 9 705 317 5671 2357 87.5 -
Wadi Nisah, Saudi Arabia 3445 7.07 2158 218 127 316 61.6 489 663 167 116

software, the spatial maps for 2004 (Fig. 5) and 2018 exceed weak acids and the prevalence of S ­ O4 and Cl ions,
(Fig. 6) have been established using the EC values. It has therefore signifying the influence of calcite, gypsum, and
been concluded that the quality of the groundwater has anhydrite dissolution and silicate weathering (Rashid
improved for the wells located in the north since the EC et al., 2020).
values have decreased in that region. However, the EC The Piper diagram also specifies that for wells P04
values have increased for the middle to the south region and P02, the alkaline earths exceed alkalies for 2004 and
of the study area which include wells P04, P06, and P07. 2018. It is an indication of the dissolution of carbonates
This indicates that the fresh rainwater recharge in that present in the aquifers. Rashid et al. (2020) also observed
area is less effective because it was evident from the pre- similar results where alkaline earth water dominates over
vious studies that EC is expected to increase away from alkalis, attributing to the dissolution of carbonates and
the center of the main depression of Al-Raudhatain basin the abundance of alkaline earths in Kuwait’s aquifer.
(Hadi et al., 2006). Furthermore, the anthropogenic pol- The Piper diagram however indicates that the alkalies
lution resulting from agriculture could be affecting this exceed the alkaline earths for the other wells (P01, P03,
area more significantly. P06, P07), indicating the dissolution of silicates, ion
exchange, or seawater intrusion.
Hydrochemical facies and water type Thus, considering the main lithology of the aquifer, the
minerals involved in the salinization process of groundwa-
A diamond-shaped field of the Piper trilinear diagram ter in Kuwait could be quartz ­(SiO2), carbonate minerals
is used to distinguish the groundwater types (Fig. 7). such as calcite ­(CaCO3) and dolomite [CaMg(CO3)2], and
From the chemical analysis of wells P02 and P04, it is sulfate minerals such as C­ aSO4.2H2o, anhydrite (­CaSO4)
inferred that water type has changed in the time interval and halite (NaCl) (Rashid et al., 2020).
of 15 years as indicated in Table 4. For well P02, the
Piper diagram relatively shows that HCO3 −, has slightly Saturation indices
increased and is located near Al-Raudhatain Drinking
Water Bottling Plant; besides in 2006, it presented a In 2004, ­SIAn values ranged from −0.44 to −1.78 with
6 m decrease in the groundwater level due to constant an average of −1.33. ­ SIAr values ranged from −0.07
extraction of the groundwater for the production of to −0.18 and the average was −0.13. ­SIc values ranged
bottled fresh water (Akber et al., 2009). However, the from 0.07 to −0.04 and the average was 0.02. S ­ ID values
quality of the well in 2018 has improved because of ranged from −0.77 to −1.38 and the average was −1.11.
the fresh water recharge. Since the salinity of the water For ­SIg, the values ranged from −0.22 to −1.56 and the
increases with depth, the quality of water in P04 has average was −1.11. The ­SIm in 2004 has a maximum
declined with prevailing ­SO4 and Cl, which suggests value of −0.87 l, a minimum value of −1.38, and an
intrusion of the brackish/saline water from the lower average of −1.15.
aquifers (Akber et al., 2009). In 2018, the ­SIAr had a maximum value of 0.30, a
The Piper diagram illustrates the hydro chemical facies minimum value of −0.02, and an average of 0.14. The
of the water in 2004 and 2018. All the wells indicate that ­SIm had an average of −0.91, a maximum of −0.78, and
strong acids exceed weak acids. The results of a previous a minimum of −1.01. Calcite values ranged from 0.44
study conducted on brackish water aquifers located in the to 0.13 and the average was 0.28. S ­ ID values ranged
central and south of Kuwait also infer that strong acids from −0.37 to 0.86 and the average was −0.60. In regard

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 251 Page 10 of 22 Environ Monit Assess (2023) 195:251

Fig. 5  EC contour map

for the samples collected
in 2004

to ­SIg values, it ranged from −0.17 to −1.64 mg/l and the concentration, all wells are under saturated with regard to
average was −0.98. ­SIAn ranged from −0.39 to −1.86 mg/l ­SID and ­SIm.
with an average of −1.2. In 2018, the SI for the carbonates increases (Fig. 9); it
The trend of and the SI of all carbonate minerals is evident that both ­SIAr and S­ IC minerals have attained
including ­SIAr, ­SIc, ­SID, and ­SIm is decreasing (Fig. 8). saturation with the increase of HCO3 − which indicate an
All the wells involved in this study illustrate under increase in both Ca2+ and M ­ g2+ values in the groundwa-
saturation with the increase of , which could be caused by ter aquifer. The order of the saturation index of the car-
the unavailability of and M ­ g2+, due to cation exchange bonates has remained the same with respect to time.
or due to precipitation of both cations (Chidambaram The precipitation of Calcite might have occurred
et al., 2012). The SI of all the carbonates in order is because of groundwater extraction leading to a loss
­SIc > ­SIAr > ­SID > ­SIm. Calcite has attained saturation as of Carbon Dioxide ­(CO2) due to reduction of pressure
the concentration of reached 140 mg/l. Though aragonite or due to mixing of different water sources (fresh and
is nearing the saturation state with the increase of HCO3 − brackish water).

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Environ Monit Assess (2023) 195:251 Page 11 of 22 251

Fig. 6  EC contour map

for the samples collected
in 2018

The weathering of the limestone leads to the release additionally evident that P04 has a higher SI value
of Ca2+ and CO3 2− that combines with the existing because Ca concentration has increased by 182%. The
SO4 − in the aquifer and tries to attain the saturation of SI for both anhydrite and gypsum is closer to reaching
sulfate minerals equilibrium with no major change in SO4 − concentra-
tion observed in other samples of the wells.
2H2 O + Ca + SO4 → CaSO4 + 2H2 O
It has been apparent that for both well P06 and P07, the
It is evident that in 2004 and 2018 as illustrated saturation is near equilibrium due to the high concentra-
in Figs. 10 and 11 respectively that the SI of the sul- tion of SO4 − and Ca2+ in comparison to the other wells.
fates increased with the rise of SO4 − regardless of As indicated in Fig. 12, the ­SIc and ­SIAr decreased
the time period. It has also been noted that S ­ IAn and as the Ca2+/ ­Mg2+ ratio increased. The carbonate
­SIg are reaching near saturation with the increase of minerals of magnesium such as magnesite and dolo-
SO4 −. The figure also illustrates that ­SIAn < ­SIg. It is mite also decrease with the increase of the ratio. The

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 251 Page 12 of 22 Environ Monit Assess (2023) 195:251

Fig. 7  Piper diagram illus-

trating the water chemistry
in the groundwater aquifers

SI of the sulfates (anhydrates and gypsum) increased studies that the dissolution of gypsum and anhydrite is the
with the increase of the ratio. Therefore, the affinity source of ­SO4 in the groundwater (Rashid et al., 2020).
of Ca2+ present in the aquifer is towards sulfates more It is evident from Fig. 14 that ­SIc and S ­ IAr show
than the carbonates. over saturation in all the wells of this study, which
The sulfate minerals such as gypsum and anhydrite further supports the increase of Ca2+ ion concentra-
show a significant increase with the increasing ratio, tion in the aquifer as well as magnecite which shows
which indicate that the concentration of ­ SO4 in the a drastic decreasing trend as calcium increases. The
groundwater is high (Fig. 13). It is evident from previous relationship between ­SID and ­SIm demonstrates the
unavailability of ­Mg2+. The increase of ­SIAn and ­SIg
further supports the affinity of Ca2+ towards the sul-
Table 4  Water type of the samples collected for 2004 and 2018 fates more than the carbonates.
Well ID Water type Figure 15 indicates that as SO4 − ∕HCO3 − ratio
increases, both ­SIc and ­SIAr reached oversaturation and the
2004 2018
SI of the sulfates is near equilibrium as the ratio increases.
P01 Na-Ca-SO4-HCO3-Cl Na-Ca-SO4-Cl-HCO3 The SI for the rest of the carbonates did not display a sig-
P02 Ca-Na-SO4HCO3-Cl Ca-Na-SO4-HCO3 nificant change with the increase of the SO4 − ∕HCO3 −
P03 Na-Ca-SO4-Cl-HCO3 Na-Ca-SO4-Cl-HCO3 ratio. Therefore, the affinity of Ca2+ is towards the sul-
P04 Ca-Na-SO4-HCO3-Cl Ca-Na-SO4-Cl fates more than the carbonates.
P06 Na-Ca-SO4-Cl Na-Ca-SO4-Cl The graph below (Fig. 16) indicates that P06 and P07
P07 Na-Ca-SO4 Na-Ca-SO4 have the highest values for Ca2+ and SO4 − because P06

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Environ Monit Assess (2023) 195:251 Page 13 of 22 251

Fig. 8  Variation of SI of
carbonates in respect to
­HCO3 for samples collected
during 2004

and P07 fall on the outskirts of the freshwater lenses of are oversaturated and ­SID, ­SIMg, ­SIg, and ­SIAn are under
Al-Raudhatain region. saturated. Therefore, it is signified that the availability of
Is it observed that wells P04, P06, and P07 exhibit an the ions for saturation of dolomite, magnesite, anhydrite,
increase in their chemical parameters during the 15-year and gypsum is scarce. Rashid et al. (2020) inferred similar
time interval. The saturation statuses of these wells indi- results to brackish groundwater samples with significant
cate over saturation of S ­ IAr and S­ Ic and under saturation increase in TDS values with time. The saturation status of
with respect to S
­ ID, ­SIMg, ­SIg, and S­ IAn. Furthermore, the these wells imply an over saturation with respect to S ­ IAr,
chemical parameters show a decreasing trend in wells ­SIc, and ­SID, and under saturation in ­SIg and ­SIAn. A simi-
P01, P02, and P03. Consequently, the saturation status lar trend was observed from the aquifers with decreasing
of these wells showed a similar trend, where ­SIAr and ­SIc TDS values, where ­SIg and ­SIAn are under saturated.

Fig. 9  Variation of SI of
carbonates in respect to
HCO3 − for samples col-
lected in 2018

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 251 Page 14 of 22 Environ Monit Assess (2023) 195:251

Fig. 10  Variation of SI of
sulfates in respect to SO4 − for
samples collected in 2004

Coefficient correlation the cation exchange dependency. The high correlation

between Ca2+ and Cl− signifies the hardness of the water.
The correlation coefficient for the chemical parame- The ions Cl-Na+, ­Ca2+, and M­ g2+-Ca2+ are positively
ters of the groundwater in 2004 is presented in Table 5 correlated (> 0.5), indicating salinization caused by the
which shows that the EC has a strong correlation with enrichment of certain salts ­(CaCl2, ­MgCl2, and ­Na2SO4)
Na+, Ca2+, ­Mg2+, Cl−, SO4 −, and NO3 −. TDS holds a (Chidambaram et al., 2018). A common source implies
great correlation with Na+, Ca2+, ­Mg2+, Cl−, SO4 −, and ­ a+, ­Ca2+, and ­Mg2+ with Cl
the positive correlation of N
NO3 −; both (EC and TDS) relationships constitute the (Tables 5 and 6) (Kim et al., 2003). This correlation also
major cation and anions existing in the groundwater. represents secondary salt dissolution, leaching, and saline
The high correlation between EC and Na+ indicates that water intrusion, but identifying the individual process
Na+ contributes more to the salinity than other ions. The is complex due to the significance of each process and due
strong correlation between Na+ and Ca2+, together with to the interplay of each process (Briz-kishore & Murali,
the strong relationship between Na+ and ­Mg2+, indicates 1992). The correlation coefficient for the chemical

Fig. 11  Variation of the SI of

the sulfates in respect to SO4 −
for samples collected in 2018

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Environ Monit Assess (2023) 195:251 Page 15 of 22 251

Fig. 12  Variation of the SI

of the carbonates and sulfates
in respect to Ca/Mg ratio for
samples collected in 2004

parameters of the groundwater in 2018 is presented in year 2004. EC and Na+ persist to have a great correlation,
Table 6 as it shows that the EC has a strong correlation which indicate that Na+ is the main ion that contributes
with Na+, Ca2+, ­Mg2+, Cl−, SO4 −, and NO3 −. TDS posi- to the salinity of the groundwater. All the strong correla-
tively correlates with Na+, Ca2+, ­Mg2+, Cl−, SO4 −, and tions between the major ions persist such as Na+ and Cl−
NO3 −; both these relationships constitute the major cat- demonstrating modern saline intrusion (Selvakumar et al.,
ion and anions present in the groundwater similar to the 2017). However, the correlation between K + and NO3 −

Fig. 13  Variation of the

SI of the carbonates and
sulfates in respect to ­SO4/
HCO3 ratio for the samples
collected in 2004

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 251 Page 16 of 22 Environ Monit Assess (2023) 195:251

Fig. 14  Variation of the SI

of the carbonates in respect
to Ca/Mg ratio for samples
collected in 2018

became negative which implies that the use of fertilizers on EC, TDS, Na+, Ca2+, ­Mg2+, Cl, SO4 −, and NO3 −.
in the Al-Abdali Farms has been controlled. EC and TDS loading values control the mineralization
of the aquifer. The overall processes explained by the
Factor analysis loading factors are taken place in only well P06 and P07
(Table 9). The loading factor for each of the following
Table 7 illustrates that the two main components in 2004 ions Na+, Ca2+, ­Mg2+, Cl, SO4 −, and NO3 − could be con-
can explain 89.7% of the total variance. The loading of tributed to anthropogenic or natural process. Anthropo-
vaimax rotated factor matrix for two-component model is genic activities to the wells include influence of oil lakes
illustrated in Table 8. Component 1 has a strong loading which resulted from the combustion and spills of the oil

Fig. 15  Variation of the SI

of the carbonates in respect
to SO4 −/HCO3 − ratio for the
samples collected in 2018

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Environ Monit Assess (2023) 195:251 Page 17 of 22 251

Fig. 16  Variation of ­SO4/

HCO3 ratio to Ca/Mg ratio
for the year 2004 And 2018

wells during the Gulf War; these wells were observed in surface; however, below the surface the concentration
the eastern part of the main depression of Al-Raudhatain decreases rapidly (Mukhopadhyay et al., 2007). Natural
region, or the pollution could be from the seawater used processes include weathering of plagioclase, feldspar,
as a distinguishing measure which contaminated the fypsum, calcite, albite, and marl (Hadi et al., 2006).
ground soil leading to possible contamination of the Component 2 contains a high loading from NO3 − and K +
aquifer. In previous studies, it has provided evidence of which are taken place in wells P04 and P06 (Table 9) and
the presence of petroleum hydrocarbon concentration it indicates a diffusion of contaminants from the applica-
in the soil and groundwater of Al-Raudhatain region. It tion of nitrogen, phosphorus, and potassium (NPK) ferti-
is apparent from the results that the petroleum hydro- lizers which might have reached the groundwater aquifer
carbons exist with a high concentration on the ground due to a reverse in the hydraulic gradient, as well as the
Table 5  Matrix of the correlation coefficient of hydro chemical data for the year 2004
EC pH TDS Na K Ca Mg Cl SO4 HCO3 NO3

EC 1
pH −0.57 1
TDS 1** −0.57 1
Na 0.99** −0.52 .99** 1
K −0.18 −0.11 −0.18 − 0.22 1
Ca 0.98** −0.73 .98** 0.96** −0.11 1
Mg 0.95** −0.48 .95** 0.95** −0.15 0.91* 1
Cl 0.89* −0.74 .89* 0.88* −0.17 0.93** 0.72 1
SO4 0.97** −0.47 .97** 0.97** − 0.15 0.92** 0.99** 0.75 1
HCO3 −0.84* 0.43 −0.84* −0.82* −0.24 −0.80 −0.92** −0.57 −0.91* 1
NO3 0.65 −0.60 0.65 0.61 0.61 0.7 0.59 0.63 0.61 −0.78 1

Bold values signify a positive correlation between the parameters

**
Correlation is significant at the 0.01 level (2-tailed)
*
Correlation is significant at the 0.05 level (2-tailed)

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Table 6  Matrix of the correlation coefficient of hydro chemical data for the year 2018
EC pH TDS Na K Ca Mg Cl SO4 HCO3 NO3

EC 1
pH −.92** 1
TDS 1** −0.92** 1
Na 0.99** −0.87* 0.98** 1
K −0.04 −0.16 −0.02 −0.18 1
Ca 0.94** −0.94** 0.94** 0.87* 0.27 1
Mg 0.98** −0.86* 0.99** 0.97** 0.001 0.91* 1
Cl 0.91* −0.95** 0.9* 0.85* 0.06 0.93** 0.82* 1
SO4 0.97** −0.84* 0.97** 0.97** −0.04 0.88* 0.1** 0.78 1
HCO3 −0.66 0.7 −0.68 −0.61 −0.50 −0.72 −0.75 −0.48 −0.74 1
NO3 0.95** −0.89* 0.94** .096** −0.11 0.84* 0.91* 0.84* 0.92** −0.56 1

Bold values signify a positive correlation between the parameters

**
Correlation is significant at the 0.01 level (2-tailed)
*
Correlation is significant at the 0.05 level (2-tailed)

natural processes such as weathering of clay minerals of KCl piles up in pore spaces and is reabsorbed by soil,
and the presence of nitrogen-containing rocks in the solid forming salts, particularly in arid and semi-arid environ-
phase of the aquifer system (Hadi et al., 2006). Potassium ments, the use of KCl as a fertilizer has been identified as
is detected in minimal amounts in freshwater compared a major driving force in the salinization of groundwater
to Na+ (Hem, 1985), which could be derived from ion and soil (Bhuvaneswari et al., 2017, 2020). However, the
exchange processes (Chidambaram, 2000). Alkali feld- irrigation trend has a greater influence on salt seepage
spar weathering in the sedimentary formations leads to underground water from the surface than the leaching
to an increase in Na+ and K + in groundwater (Thivya of fertilizers. An optimal fertilizer utilization by a suit-
et al., 2013). Moreover, potassium chloride (KCl) is sup- able irrigation system in a vegetable crop production can
plied to the plants as a major nutrient as potash fertilizer decrease the chance of environmental degradation (Li &
(Manning et al., 2010) and is essential for the metabo- Qian, 2018). Because the repetitive fertilizer applications
lism in plant. Furthermore, the usage of KCl has a sig- do have a disconcerting compounding impact of such
nificant impact on the irrigation water and soil salinity, pollutants (Hariprasad & Dayananda, 2013; Yargholi
where Cl is taken up as a micronutrient and K + is uti- & Azarneshan, 2014), which creates a complicated sce-
lized by the plant as a macronutrient. While the surplus nario because of the combination of these pollutants that

Table 7  Total variance Component Initial eigenvalues Rotation sums of squared loadings
explained for the year 2004
Total % of variance Cumulative % Total % of variance Cumulative %

1 8.23 74.81 74.8 8.02 72.9 72.9

2 1.63 14.86 89.6 1.84 16.8 89.7
3 0.88 7.98 97.6
4 0.25 2.24 99.885
5 0.01 0.12 100
6 4.07E−16 3.70E−15 100
7 2.71E−16 2.46E−15 100
8 −4.60E−17 − 4.18E−16 100
9 −2.13E−16 − 1.93E−15 100
10 −3.68E−16 − 3.35E−15 100
11 −5.73E−16 −5.21E−15 100

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Environ Monit Assess (2023) 195:251 Page 19 of 22 251

Table 8  Variable loading on the components for 2004 Table 11  Variable loading on the components for 2018
Variable Component Variable Component
1 2 1 2

EC 0.99 0.05 EC 0.99 0.07

pH −0.60 −0.34 pH −0.92 −0.24
TDS 0.99 0.05 TDS 0.99 0.09
Na 0.99 −0.002 Na 0.99 −0.06
K −0.23 0.97 K −0.11 0.98
Ca 0.98 0.13 Ca 0.91 0.35
Mg 0.96 0.05 Mg 0.97 0.12
Cl 0.89 0.06 Cl 0.89 0.11
SO4 0.97 0.05 SO4 0.96 0.09
HCO3 −0.82 −0.41 HCO3 −0.63 −0.66
NO3 0.61 0.78 NO3 0.96 −0.04

Table 9  Factor score for 2004 metals due to the usage of K + fertilizer, despite the fact
Well ID Factor A Factor B that they serve as a nutrient source (Pan et al., 2010).
By using Pearson’s correlation analysis in Table 10
P01 −0.54542 −0.94232 clarifies that the two main components describe a por-
P02 −0.62959 −0.47032 tion of the gross variance among the chemical param-
P03 −0.56158 −0.60326 eters for the year 2018. These two components justify
P04 −0.75437 1.86984 93.4% of the total variance. The first loading compo-
P06 1.64502 0.17289 nent, which explains 78.6% of the total variance, had
P07 0.84594 −0.02684 a strong loading on EC, TDS, Na+, Ca2+, ­Mg2+, Cl−,
SO4 −, and NO3 − (Table 11). The contribution process
could be due to the weathering of gypsum and cal-
is more dangerous than the impact of a solitary pollutant cium bearing minerals and saline water intrusion. The
(Haiyan & Stuanes, 2003; Khan et al., 2018). Moreover, loading factor for Na is due to anthropogenic activities
Loganathan et al. (1995) and Chen et al. (2017) con- such as groundwater abstraction. These previous pro-
firmed pollutants of Cadmium (Cd) and some few heavy cesses as perceived from Table 12 are mostly present

Table 10  Total variance Component Initial eigenvalues Rotation sums of squared loadings
explained for the year 2018
Total % of variance Cumulative % Total % of variance Cumulative %

1 8.85 80.5 80.5 8.65 78.6 78.6

2 1.42 12.9 93.4 1.62 14.7 93.4
3 0.52 4.73 98.1
4 0.12 1.08 99.2
5 0.09 0.83 100
6 5.77E−16 5.25E−15 100
7 3.70E−16 3.36E−15 100
8 −7.43E−17 −6.75E−16 100
9 −2.73E−16 −2.48E−15 100
10 −3.27E−16 −2.97E−15 100
11 −4.79E−16 −4.35E−15 100

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 251 Page 20 of 22 Environ Monit Assess (2023) 195:251

Table 12  Factor score for 2018 Moreover, a high positive correlation remained the same
Well ID Factor A Factor B for all ions in the 15-year time interval except for the cor-
relation between K + and NO3 −, which had a correlation
P01 −0.59817 −0.29657 of 0.610 in 2004 but changed to a negative correlation
P02 −0.86205 −0.72149 of − 0.113 in 2018. Dissolution of the aquifer formation
P03 −0.4924 −0.71994 was determined as the predominant process governing the
P04 −0.49227 1.95812 major ion concentration in the groundwater samples.
P06 1.6837 −0.02427 In conclusion, the changes that occurred in the 15-year
P07 0.76119 −0.19585 time interval does not cause any concern, as it will not
demand any current remediation to the groundwater.
Continuous monitoring of fresh groundwater is of great
in well P06 and P07, which is similar to the year 2004. importance because it represents a management technique
The second loading component explains 14.7% of the to maintain a sustainable quality and quantity of such rare
variability and is correlated to K +, which can con- resource in Kuwait.
tribute to leaching of agricultural effluents due to the
inverse hydraulic gradient or due to natural processes Acknowledgements I would like to extend my gratitude to
Kuwait Institute for Scientific Research (KISR) for their guidance
of saline water intrusion from the lower ground layers.
and support in completing this project. I would also like to express
The factor score for 2018 indicates that this process is my appreciations to Dr. Khalid Hadi, Dr. Yousef Al Wazzan,
mainly present in P04 (Table 12). and Dr. Sabarathinam Chidambaram for the encouragement and
expertise which made this study possible. An express of grati-
tude is also extended to Ms. Amjad Al-Rasheedi for her help and
efforts in developing the subsurface lithology diagram.
Conclusions
Author contribution All the stages necessary for this research
The statistical analysis of the hydrochemical data of the study was done solely by Dalal Sadeqi.
study area revealed that Ca2+ for well P06 has increased
and Ca2+, Cl−, and SO4 − for P04 has also increased in Funding KISR has provided the total funds for this research study.
the 15-year time interval. The contour maps revealed
Data Availability The data supporting the finding of the
that in 2018, the EC values increased for P04, P06, and
study are available upon request from the corresponding author.
P07, but decreased for P01, P02, and P03 which indi-
cate a recharge of freshwater for these wells. Declarations
Examination of saturation states of the well water
indicated that the increase of Ca2++ in the observation Ethics approval I hereby declare that I have accomplished all
wells during 15 years’ period was due to weathering the work done for this research study. I authorize the Environ-
mental Monitoring and Assessment Journal to reproduce this
of rocks. It further confirmed that the affinity of Ca2+
study by photocopying or by other means. I comprehend that the
was towards sulfate minerals (­SIAn and S ­ Ig) than the research study will be available for the public.
carbonate minerals. Furthermore, it suggests that since
­SIg ­(CaSO4·2H2O) > ­SIAn ­(CaSO4) then the tempera- Conflict of interest The author declares no competing interests.
ture of the aquifer is within a normal range of 25 ℃, as
a higher temperature would lead the water molecules
to be lost and with that ­SIg < ­SIAn. It is also evident References
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