Physics and Chemistry of the Earth 126 (2022) 103109

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Physics and Chemistry of the Earth

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Impact of anthropogenic and geological factors on groundwater

hydrochemistry in the unconfined aquifers of Indo-Gangetic plain
Anant Gautam a, S.C. Rai a, *, S.P. Rai b, Kripa Ram c, Sanny c
a
Department of Geography, Delhi School of Economics, University of Delhi, Delhi, 110007, India
b
Department of Geology, Banaras Hindu University, Varanasi, Uttar Pradesh, 221005, India
c
Institute of Environment and Sustainable Development, Banaras Hindu University, Varanasi, Uttar Pradesh, 221005, India

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

Keywords: This study attempts to analyze the impact of anthropogenic activities and geological factors on the hydro­
Anthropogenic activities geochemical characteristics of groundwater of the Bist-Doab region of Punjab, India. Various bivariate plots,
Irrigation return flow PCA, HCA, and Piper trilinear were employed to analyze hydrogeochemical processes and the association be­
Hydrogeochemical processes
tween the physicochemical parameters. The results reveal the dominance of Ca2+- Mg2+ - HCO3− type of
Rock-water interaction
Saturation index
groundwater at most of the places, attributed to the chemical weathering of carbonate and silicate minerals
present in the geological setting. The process of urbanization, industrialization, over-extraction of groundwater,
application of NPK fertilizers, and discharge of urban and industrial wastes were found to be responsible for
altering groundwater chemistry. The bivariate plot of (SO42− + HCO3− ) vs. (Ca2+ + Mg2+) reveals that both the
process of ion exchange and reverse ion-exchange have contributed to the hydrochemistry of groundwater in the
region. Analysis of saturation index revealed the predominance of calcite and dolomite minerals in characterizing
groundwater in an unconfined aquifer setting in the area. The findings conclude that although geogenic factors
attribute hydro-chemical characteristics to the groundwater; anthropogenic activities accelerate the pace of rock-
water interaction in the aquifer environment. Controlling rapidly growing region-centric developmental activ­
ities may act as a boon for the conservation of groundwater resources in the region.

1. Introduction from intensively cultivated soils to groundwater (Foster and Chilton,

2003). Apart from it, leaching from disposal sites has also become a
The pace of rapid industrialization, urbanization, and unsustainable prominent source of groundwater contamination (Burri et al., 2019).
development, especially in developing countries have led to more de­ Once contaminated, it is not easy to restore the aquifer, escalating the
pendency on groundwater to meet their daily needs, leading to its pollution impact (Bouderbala, 2017). However, there is a possibility of
quantitative and qualitative decline (Das and Nag, 2015; Rai, 2011; restoration when left undisturbed for a long geological time, depending
Sarkar et al., 2017). The development of agriculture is a key factor in upon the geological environment and flow path of the underground
developing economies like India where agriculture is the main source of water (Singhal and Gupta, 2010).
sustenance for the majority of the population, especially in rural areas The hydro-chemical characteristics of groundwater are largely
where about 80% population depends on groundwater for their do­ determined by the regional geology and aquifer characteristics (Datta
mestic or agricultural needs (Jain et al., 2010). But, the imprudent and Tyagi, 1996; Mallick et al., 2018). Hydrogeochemical processes
groundwater extraction without continuous recharge has led to the such as weathering, dissolution, ion-exchange reaction, the longer
continuous depletion in groundwater table (Kamra et al., 2002; Gautam residence time of water, etc. largely influence the physicochemical
et al., 2020), which has become a threat to the sustainability of agri­ characteristics of groundwater in an aquifer environment (Raghunath
cultural production. The radical shift of intensive near-monoculture of et al., 2002). The hydro-chemical nature of groundwater is also affected
more water-consuming individual crops has created a high risk of by chemical reactions taking place between water and minerals present
elevated rates of nutrients, salt, and leaching of fertilizers and pesticides along the flow path, intermixing of water, chemical characteristics of

* Corresponding author.
E-mail addresses: [email protected] (A. Gautam), [email protected] (S.C. Rai), [email protected] (S.P. Rai), [email protected]
(K. Ram), [email protected] (Sanny).

https://doi.org/10.1016/j.pce.2022.103109
Received 26 July 2021; Received in revised form 10 January 2022; Accepted 12 January 2022
Available online 14 January 2022
1474-7065/© 2022 Elsevier Ltd. All rights reserved.
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

recharged water, geochemical formations, and rock-water interactions effluents have also played a significant role in attributing
(Singh et al., 2017). However, in recent decades, anthropogenic activ­ hydro-chemical character of groundwater, especially in an unconfined
ities such as excessive extraction of groundwater, higher application of aquifer ecosystem (Singh et al., 2008; Scheiber et al., 2020).
fertilizers and pesticides, poor management and open dumping of gar­ Alluvial Plains of North India have been formed by the sediments
bages/sewages, and untreated discharge of domestic and industrial eroded from the Himalayan rivers. Due to the geographical advantages

Fig. 1. Location and geomorphological features of the Bist-Doab region of Punjab, India (modified from Gautam et al., 2021).

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

of fertile soil for agriculture, a perennial source of water in rivers and The thickness of the first aquifer varies throughout the study area
aquifers, plain land for permanent settlement, moderate climatic con­ ranging between 72 m and 94 m. The average thickness has been found
ditions, and historical and cultural significance, the northern Indian as 72 m, 76 m, 81 m, and 94 m in Hoshiarpur, SBS Nagar, Jalandhar, and
plain has been comparatively more populous than other parts of the Kapurthala districts, respectively (Singh, 2014). The thickness is
country. To fulfill the needs of this growing population, the region has increasing as one moves towards the west and south-west. This aquifer
undergone rapid advancement in agricultural and industrial production has been separated by the underlying aquifer by an extensive and thick
in the recent past (Anindita Sarkar et al., 2017; Kumar et al., 2019). But, clay layer which varies from 16 m to 32 m. The second aquifer composed
the era of the green revolution in the 1960s initiated the quantitative of sequences of sand and clay layers has been estimated to be about 250
and qualitative degradation in groundwater of the region due to m from the confining layer (Singh, 2014). The presence of thick allu­
excessive extraction of groundwater for irrigation of paddy-wheat vium and high drainage density provides a suitable environment for a
monoculture, and intensive use of chemical fertilizers, pesticides, and rich hydrogeological character in the area.
insecticides by the farmers (Kaur and Vatta, 2015).
The significant impact of advancement in agricultural and industrial 2.2. Database and sampling design
production has been extensively felt in north-western parts of the Indo-
Gangetic plain i.e., Punjab, Haryana, and Western Uttar Pradesh The hydrochemistry of the groundwater of the region has been
(Sharma et al., 2016), which is growing at an accelerated pace of in­ analyzed based on 148 groundwater samples collected in June–July
dustrial, urban and agricultural development. The negative impact of 2019 during the paddy season, as farmers run the tube-wells continu­
these developments has not only altered the hydrochemistry of ously to irrigate their land which provided the correct groundwater
groundwater in parts of Punjab but has also degraded the groundwater samples. Tube wells (n = 132) were preferred over other wells as the
quality (Lapworth et al., 2014; Gautam et al., 2021). Therefore, the extraction of groundwater from tube wells dominates the source of
present study attempts to analyze the geochemical evolution and pro­ irrigation in the region. However, at a few places, groundwater samples
cesses (natural or anthropogenic) governing the chemical composition from hand-pump (n = 16) were also collected where there was a power
of groundwater of the Bist-Doab region of Punjab. cut for electric tube-wells to function. The screening depth of the
sampled handpumps was found to be below 30 m; whereas, tube wells
2. Materials and methods recorded screening depth between 30 m and 304 m. Depth-wise distri­
bution of samples include <80 m (n = 104), 80–150 m (n = 31) and
2.1. Study area >150 m (n = 13). Groundwater at a depth beyond 150 m was found
mainly in the Siwalik belt (Fig. 1). The grid sampling technique was used
Covering an area of 9022 km2, the Bist-Doab region of Punjab, India for sample collection as it facilitates the groundwater samples from all
extends between 30o04′ and 30o51′ N and 74o57′ and 76o40’ E. The over the region uniformly. The size of grids was uniformly taken as 15 x
study area is bounded by Rivers Beas and Satluj in the northwest and 10 km. At least one sample was collected from each grid. Two ground­
south respectively, and Siwalik hills in the east. Administratively, the water samples were collected (one from shallow depth and the other
region is divided into 4 districts viz., Jalandhar, Kapurthala, Hoshiarpur, from intermediate-depth) in a few grids where there was a large varia­
and Shaheed Bhagat Singh (SBS) Nagar district, and 30 blocks (Fig. 1). tion in the depth of tube wells. Utmost care was taken in collecting the
The study area is one of the three major regions of the state of Punjab, groundwater samples, as temperature and other physical parameters are
demarcated by the river boundaries i.e., the land south of river Satluj is subject to change with time in an open environment. About 10–15 min
known as Malva, between rivers Ravi and Beas is known as Majha (Bari- of a free flow of water was allowed before collecting the water samples.
Doab), and between rivers Beas and Satluj as Doaba (Bist-Doab). The This led to the flow-out of long-standing groundwater in the pipes of the
climate of the region is moderate with summer and winter temperatures tube-wells and hand pumps. The collected samples were stored in an
around 30 ◦ C and 12 ◦ C, respectively. icebox, carried to the laboratory, and kept at 4 ◦ C for further chemical
The land surface of the Bist-Doab region has altitudinal variations analysis.
which range from 164 m to 735 m above mean sea level (MSL). The Demographic data such as population density, level of urbanization,
overall slope and aspect of the region are from north-east to south-west and industrialization have been collected from secondary sources i.e.,
and east to west. The geomorphic structures found in the region have government publications. The data relating to tube well density in the
been truly shaped by erosion and landform formation; grouped under six region, use of tube wells for irrigation, and application of fertilizers by
major geomorphic units: (i) Siwalik hills, (ii) plateau, (iii) alluvial fan, the farmers were collected through primary sources using field investi­
(iv) piedmont plain, (v) alluvial plain, and (vi) flood plain (Fig. 1). The gation and personal interviews with the farmers (n = 94) in the region.
small hilly stretch of rocky formations in north-eastern parts of the Bist-
Doab region i.e., Siwalik hills are composed of friable gray micaceous 2.3. Physico-chemical analysis
sandstone, brown, red, and purple clay, and conglomerate in the periods
between the late to early Pleistocene. Hills with the highest point at 735 The temperature, potential of hydrogen (pH), and electrical con­
m from mean sea level are about 10 km wide along the eastern boundary ductivity (EC) of each groundwater sample were measured in-situ with
line of the study area. The areas parallel to Siwalik foothills have an the help of a digital thermometer, pH, and EC meter, respectively. The
average elevation of 400 m whereas, the alluvial tracts are below 300 m laboratory analysis of collected groundwater samples has been carried
from MSL. The alluvial plain is almost homogenous but the slope is to­ out in the Institute of Environment and Sustainable Development
wards west and south-west. Geologically, the sediments in the region (IESD), Banaras Hindu University, Varanasi. The major cations and an­
have accumulated during the late to early Pleistocene period on the ions were analyzed with the help of ion-chromatography (model: Dionex
metamorphic and igneous bedrock of pre-Cambrian origin. Most of these IC 5000+, Thermo-Fischer Scientific, USA). A mixture of 4.5 mM
have been covered with sand, silt, loam, clay, and kankar. The thickness Na2CO3 and 0.8 mM NaHCO3 was used as an eluent for analysis of an­
of alluvium deposits has been reported highest in this part of the Bist- ions and an Anion Self Regeneration Suppressor (ASRS) is used to sup­
Doab region i.e., about 4.5 km near Dasuya in North Hoshiarpur. Near press the conductivity. For cations, 30 mM of Methanesulphonic acid
Adampur of Jalandhar district (central Bist-Doab region), this thickness (MSA) was used as an eluent, and conductivity is suppressed by Cation
is about 2.523 km. Hydrologically, the area is rich in the surface as well Self Regeneration Suppressor (CSRS). The anions and cations are sepa­
as groundwater resources with a flow from north-east to south-west. rated using analytical columns, Ion Pac AS23 and CS16, respectively.
Broadly, two groups of aquifers have been found in the Bist-Doab re­ The detailed analytical procedure for water-soluble inorganic constitu­
gion of Punjab with hydraulic gradient towards west and south-west. ents has been described by Ram and Sarin (2010). Field blanks are also

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

analyzed simultaneously to obtain blank concentrations of anions and ranges between 469 and 836 persons living per sq. km.
cations. All the reported concentrations of cation and anions are blankly The present study has also calculated the population concentration
corrected. The analysis of bicarbonate was done with the help of an index (Hoover Index) to analyze the distribution pattern of population in
Auto-Titrator (Metrohm, Switzerland; model: 877 Titrino Plus). The the region. It ranged between 1.3 for Kapurthala and SBS Nagar districts,
accuracy of chemical analysis of groundwater samples have been and 6.36 for Jalandhar, which comprises most of the central and south-
checked by calculating the ‘ion-balance error’ by the following formula: central parts of the region. High population concentration mainly in the
central and south-central parts has put extra pressure on the existing
TZ + − TZ −
Ion − balance error (%) = ( + ) × 100 groundwater resources. It should be noted that all these cities are along
TZ + TZ −
the national highway connecting Chandigarh and Jalandhar. The road
Where TZ+ and TZ− are the sum of cations and anions, respectively. For distance between Nawanshahr and Phagwara is 36 km and Phagwara to
the present study, the ‘ion-balance error’ in most of the groundwater Jalandhar is 23 km only. Within the next few years, these cities along
samples has been found below ±10%, showing analytic precision. with Kapurthala (18 km west of Jalandhar) are expected to be a large
However, a few groundwater samples showed a percentage error be­ urban corridor that will engulf one-third of the Doaba region. These
tween +10% and +15%. The same percentage of error has also been developments continue to make the surface impervious for water infil­
reported in Purushottam et al. (2011) and Lapworth et al. (2014) in their tration and recharge, leading to a decline in the groundwater table.
study for groundwater of the Bist-Doab region. This justifies the present Apart from these, agricultural activities play a dominant role in the
analysis of groundwater in the study area. quantitative and qualitative deterioration of groundwater in the region.
Field investigation revealed the presence of tube wells every 100–200 m
in most of the agricultural farms in the region, estimating the tube well
2.4. Hydro-chemical processes and statistical analysis
density of more than 30 per km2 in Jalandhar, Kapurthala, and SBS
Nagar districts of the region. Farmers have often reported not switching
Gibbs Plot, Chloro-Alkali indices, and various bivariate plots have
off the tube well motor for days altogether in the irrigation season of
been used to illustrate various processes attributing hydro-chemical
paddy crops. As the government provides scheduled free electricity of 8
character to the groundwater of the region. The degree of relationship
h each day for irrigation, the tube wells get automatically switched off
between various physicochemical parameters was analyzed with the
and on (Field investigation). This practice accelerates the amount of
help of a correlation matrix using Pearson’s correlation coefficient (r) in
groundwater extraction in the region.
MS Excel 2016. Apart from it, Principal Component Analysis (PCA) and
Higher applications of chemical fertilizers in the field have also
Hierarchical Clustering Analysis (HCA) were carried out using the ‘SPSS
played a significant role in groundwater quality deterioration in the
Software package’ to investigate the association between physico-
region. Farmers’ responses (n = 94) on the use of chemical fertilizers
chemical components of groundwater and to identify the processes
through unstructured interviews have been summarized in Table 1.
controlling the geochemistry. On one hand, PCA transforms the multi­
About 80% of the farmers use 600–800 kg/ha of urea per year on their
dimensional data into fewer dimensions while preserving trends and
farms. Whereas, about 90% of the farmers use 100–250 kg/ha of dia­
patterns (Tran et al., 2019); and on the other, HCA is a widely used tool
mmonium phosphate (DAP) per year. Apart from these vital chemical
to cluster several parameters into the same sample or between the
fertilizers, about 60% of the farmers use zinc and Sulphur, and 41% use
samples (Molekoa et al., 2019). The result of HCA is analyzed using a
iron in their farms to increase crop productivity. These chemicals get
dendrogram, in which, the horizontal axis represents the distance or
mixed with precipitation or irrigation-return flow and infiltrate to the
dissimilarity between clusters and the vertical axis represents the
surface contaminating the groundwater resources of the region.
groundwater samples.

2.5. Saturation index 3.2. Major ions and hydrogeochemical processes

The saturation index has been calculated to investigate the thermo­ The analytical results of groundwater samples have been summa­
dynamic control of minerals on the hydrochemistry of groundwater rized in Table 2. The overall chemical characteristics of groundwater
(Chidambaram et al., 2012; Ledesma-Ruiz et al., 2015). Saturation samples of the region were recorded in the order of Ca2+ (48.9%) > Na+
indices (SI) of groundwater samples were calculated using the equation
below (Appelo and Postma, 2004): Table 1
Amount of chemical fertilizers used per hectare by the farmers (n = 94) in
IAP cultivated land of the Bist-Doab region of Punjab, India (percent given in
SI = Log
Ktsp(T) parenthesis).
Chemical fertilizers Amount (Kg/ha) No. of farmers
Where IAP is the ion activity product and Ktsp(T) is the equilibrium sol­
ubility product of the mineral. The negative value of SI suggests Urea 400–500 7 (7.44)
500–600 12 (12.77)
groundwater is under sub-saturation while the positive value suggests
600–700 53 (56.38)
the oversaturation or supersaturation of groundwater concerning min­ 700–800 22 (23.41)
erals. When SI is ~0 ± 0.50, the condition is said to be saturated. In the DAP 50–100 11 (11.7)
present study, the PHREEQC model has been used to calculate SI con­ 100–150 42 (44.68)
cerning various minerals. 150–200 17 (18.09)
200–250 24 (25.53)
Zinc Nil 40 (42.55)
3. Results and analysis 3–4 16 (17.02)
4–5 32 (34.05)
3.1. Influence of anthropogenic activities 5–6 6 (6.38)
Sulphur Nil 40 (42.55)
3–4 13 (13.83)
Bist-Doab occupying just 18% of the geographical area contains 4–5 35 (37.24)
about 60% of the urban population of the state of Punjab which is 5–6 6 (6.38)
mainly concentrated in the southern half of the region. In 2011, the level Iron Nil 59 (62.76)
of urbanization of Jalandhar district was about 52%, which is much 3–4 23 (24.47)
4–5 12 (12.77)
above the national average of 31%. The population density in the region

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Table 2 processes determining groundwater evolution and its hydro-chemical

Statistical summary of physico-chemical parameters of groundwater samples (n composition. Among anions, HCO3− was found dominant in almost all
= 148) of the Bist-Doab region of Punjab, India. the groundwater samples of the region except Nangal Ambian, Taunsa,
Physico- Min. Max. Range Mean Median SD Baloki, and Dialpur; where Cl− was dominantly recorded (Fig. 3). Sul­
chemical phate was also recorded proportionately higher in the groundwater
Parameters samples of Nakodar, Noormahal, Jalandhar East, and Jalandhar West
Temperature 20 32.30 12.30 25.35 25.10 1.63 blocks of the region. The concentration of NO3− was recorded above the
pH 6.80 8.40 1.60 7.59 7.60 0.30 permissible limit of 45 mg/l (BIS, 2012) in the groundwater samples of
EC 190 1743 + 1553 502.19 452.50 241.75
Jalandhar East, Jalandhar West, Rukra Kalan, Noormahal, Mahilpur,
Total Dissolved 133 1220 + 1087 351.53 316.75 169.23
Solid (TDS) and Hoshiarpur blocks of the study area (Fig. 4).
Total Hardness 55.24 1171.59 1116.35 337.73 294.71 178.07 The functional sources of dissolved chemical constituents in
(TH) groundwater of the area were assessed using the Gibbs plot of TDS (mg/
Bicarbonate 108.68 748.12 639.44 352.94 343.58 103.49 l) vs. (Na+/K+)/(Na+ + K+ + Ca2+) and Cl− /(Cl− + HCO3− ). The result
Fluoride 0 1.60 1.60 0.32 0.27 0.24
Chloride 1.49 1732 1730.57 51.34 10.89 211.22
exhibits that the groundwater of the area attained its chemical charac­
Nitrate 0.02 203.69 203.67 19.38 7.27 29.51 teristics predominantly due to rock-water interaction by the process of
Nitrite 0.00 5.00 5.00 0.07 0.00 0.51 weathering and dissolution (Fig. 5). Depth-wise analysis reveals that the
Bromide 0.00 0.43 0.43 0.02 0.00 0.06 groundwaters samples of below 80 m were found predominantly char­
Sulphate 1.16 701.04 699.88 35.81 13.39 73.32
acterized by rock-water interaction; whereas, the evaporation effect was
Sodium 10.40 551.14 540.74 63.48 41.77 79.44
Potassium 1.11 184.15 183.04 7.64 4.83 16.87 found characterizing the hydrochemistry of the groundwater samples
Magnesium 3.25 86.00 82.75 26.11 23.33 16.24 above 80 m depth in the shallow aquifers of Nangal Ambian and Taunsa.
Calcium 16.64 330.19 313.55 92.27 79.40 54.18

Note: All the parameters are in mg/l, except temp. (oC), EC (μS/cm) and pH (no 3.2.1. Ion-exchange
unit). Chloro Alkali Indices (CAI), proposed by Schoeller (1977) best
illustrate the mechanism of ion exchange occurring between the
(33.5%) > Mg2+ (13.9%) > K+ (5.1%) and HCO3− (76.8%) > Cl− groundwater and its host environment. It is evaluated using indices CAI
(11.2%) > SO42− (7.8%) > NO3− (4.2%) > F− (0.1%) > NO2− (0.016%) – I and CAI – II having the formuas [Cl− (Na+ + K+)/Cl− ] and [Cl− (Na+
> Br− (0.004%) (Figs. 2 and 3). However, the dominance of ions was not + K+)/(SO42− + HCO3− + CO32− + NO3− ), respectively. The result
recorded in the same order in groundwater samples all over the study shows that most of the groundwater samples from all depths have a
area. Ca2+ was found dominant in the groundwater samples of the negative ratio for both indices (Fig. 6a). This indicates an indirect
northern Bist-Doab region, south-central parts, and all over the Siwalik base-exchange reaction in which calcium and magnesium in the
hills. Whereas, Na+ was found dominant in the groundwater samples of groundwater are exchanged with sodium and potassium ions present in
the southwestern parts of the study area, Balachaur block of SBS district, the minerals of the host rock. This exchange might be due to the longer
and urban areas of Jalandhar and Phagwara. An almost equal proportion residence time of water in the alluvial aquifers in the plain areas.
of Ca2+, Na+, and Mg2+ was recorded in the groundwater samples of However, a few water samples from Taunsa (SBS Nagar) and Nangal
Adampur, Bhogpur, Umar Tanda, Bhulath blocks, and area of SBS Nagar Ambian (Shahkot, Jalandhar) from shallow depth have positive CAI–II,
district (except Balachaur block). These disproportionate ions in the indicating direct base-exchange reaction. Here, sodium in groundwater
groundwater samples are crucial in determining the hydrogeochemical from the anthropogenic sources might be replacing calcium and

Fig. 2. Spatial distribution of cations present in the groundwater samples of the Bist-Doab region of Punjab, India.

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 3. Spatial distribution of anions present in the groundwater samples of the Bist-Doab region of Punjab, India.

Fig. 4. Spatial distribution of Na+ in the groundwater samples of the Bist-Doab region of Punjab, India.

magnesium ions present in the aquifer materials. calcite and dolomite weathering, a few samples from depth above 80 m
Results show that in the bivariate plot of (SO42− + HCO3− ) vs. (Ca2+ have also been found to lie towards the left due to an excess of (SO42− +
+ Mg2+), groundwater samples from the depth below 80 m lie close to HCO3− ) over (Ca2+ + Mg2+), indicating the process of ion-exchange.
the 1:1 line (Fig. 6b). This suggests the dissolution of calcite and dolo­ These groundwater samples belong to the shallow aquifers of Sultan­
mite predominantly found in the deeper aquifer environment in the pur Lodhi and Bhulath blocks of Kapurthala district (Fig. 6b). This might
study area. However, the groundwater samples above 80 m have wide be due to the dissolution of silicate minerals viz., quartz, albite, or Na-
variations concerning the process of ion exchange throughout the study plagioclase, present in the clay particles found in the region. A few
area. Although most of the samples lie close to 1:1 line representing groundwater samples from depths above 80 m have also been found

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 5. Mechanism controlling groundwater chemistry (a) TDS vs. (Na++K+)/(Na+ + K+ + Ca+2), and (b) TDS vs. Cl− /(C/- + HCO3− ) of groundwater samples of the
Bist-Doab region of Punjab, India (after Gibbs, 1970). Groundwater samples from depth above 80 mbgl (represented by a blue colour) have been dominated by
weathering and evaporation both. But groundwater samples from depth between 80 and 150 mbgl (orange color), and below 150 mbgl (green colour) are weathering
dominant only. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 6. Biplot of (a) CAI - I vs. CAI - II, (b) (SO4− 2 + HCO3− ) vs. (Ca+2 + Mg+2), and (c) spatial distribution of biplot ratio between (SO4− 2 + HCO3− ) vs. (Ca+2 +
Mg+2) in the groundwater samples of the Bist-Doab region of Punjab, India. Groundwater samples have been represented by a blue colour (depth above 80 mbgl),
orange color (between 80 and 150 mbgl), and green colour (below 150 mbgl). (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

towards the right of 1:1 equiline due to excess of (Ca2+ + Mg2+) over present in the groundwater of the region. A moderate correlation be­
(SO42− + HCO3− ), indicating the dominance of reverse ion-exchange tween potassium and nitrite (r ~ 0.51) suggests the possible addition of
reaction in the aquifer environment (Fig. 6b). The spatial distribution chemicals from NPK fertilizers through either mixing with rainwater or
shows the prevalence of reverse ion-exchange reaction in two pockets; irrigation return flow. Apart from these, a moderate correlation also
the Kandi belt and blocks of Shahkot, Nakodar, Kapurthala, Jalandhar exists between Mg-SO4 (r ~ 0.6), and Mg-Na (r ~ 0.53), suggesting their
(East and West), and areas around Taunsa (Fig. 6c). In the Kandi belt, the common sources in the rocks present in the aquifer environment.
abundance of calcium from calcite minerals might be responsible for the
process of reverse ion exchange; whereas, in south-central regions 3.3.2. Principal Component Analysis
around Jalandhar, there is a high possibility of ion exchange between PCA is a noteworthy way the display complex relationships among
calcium from calcite and dolomite minerals and sodium from ground­ many variables and their roles. In this study, four factors account for
water. The source of sodium in groundwater might be chemical fertil­ 71% of the total variance (Table 4). With eigenvalue 4.095, PC 1 alone
izers, disposal of agricultural wastes, and leaching from sewage disposal accounts for about 25.6% of the variance. Component loading of Sul­
as the area is highly urbanized, industrialized, and intensively phate (0.829), Magnessium (0.765), and Calcium (0.631) indicates that
cultivated. the weathering of carbonate and sulphate minerals plays a significant
role in defining the chemical characteristics of groundwater in the area.
3.2.2. Weathering and dissolution High loading of EC (0.654), TDS (0.654), and TH (0.766) signifies the
The plotting of most of the groundwater samples along equiline 1:1 importance of physical parameters in determining the quality of
in a scatter plot (Ca2+ + Mg2+) vs. HCO3− indicates that the ground­ groundwater. In PC2, the component loadings of chloride (0.831), ni­
water has attained its ionic character from the weathering of carbonates trite (0.695), sodium (0.682), potassium (0.786) are dominant, signi­
minerals (Fig. 7a). Some of the samples lie between equiline 1:1 and 1:2. fying the impact of anthropogenic sources from irrigation return flow
In these samples, calcium and magnesium can be said to originate from and leaching of sewage and waste disposal on groundwater chemistry of
the dissolution of dolomite in the aquifer system. A small number of the the region.
groundwater samples are also found to have 0.5 ratios along equiline
1:2. Depth-wise analysis reveals that the groundwater samples from 3.3.3. Hierarchical cluster analysis
below 80 m depth are mostly aligned along the equiline 1:1, meaning Hierarchical Chemical Analysis (HCA) has grouped the groundwater
carbonate minerals dominate in the lithological composition of aquifers samples into three main clusters. Cluster 1 contains the maximum no. of
beyond this depth (Fig. 7a). Further, the Na+/Cl− vs Cl− scatter plot samples i.e., 111. Cluster 2 and 3 consists of 23 and 8 samples, respec­
shows that the concentration of sodium in the groundwater of the region tively (Fig. 8). Six samples from Nangal Ambian, Taunsa, Baloki, and
is due to the dissolution of plagioclase minerals (Fig. 7b). Dialpur have been left out from the ambit of these clusters due to a high
Carbonic and sulphuric acids play a significant role in enhancing level of dissimilarity in their physicochemical characteristics. The
weathering processes. In the Ca2+ vs. HCO3− scatter plot, about one- groundwater at these locations has a high influence of industrial
third of groundwater samples lie between 1:2 and 1:4 suggesting that discharge on its chemical properties. However, the nature of chemical
calcite weathering by carbonic acid is solely responsible for the discharge at these locations is not the same. This depends upon the
groundwater chemistry at these places (Fig. 7c). In the scatter plot Ca2+ constituents of wastes discharged by factories at their respective loca­
vs. SO42− , most of the groundwater sample points fall towards the cal­ tions i.e., wastes discharge of pharmaceutical units of Taunsa varies
cium axis (Fig. 7d). This indicates the source of calcium other than the from the chemical wastes from factories at Nangal Ambian.
dissolution of gypsum or anhydrite present in the area. However, a few
groundwater samples from depths above 80 m do fall along the equiline 3.4. Hydrogeochemical facies
1:1. This suggests the possibility of calcite weathering by sulphuric acid
at these places. The interpretation of hydrogeochemical facies is a useful tool to
In the (Na+ + K+) vs. TZ+ plot, most of the water samples fall beyond determine the origin of the chemical histories of groundwater. Based on
the reach of the line represented by line 1:2 (Fig. 7e), signifying less the chemically attained characteristics (concentration of major anions
impact of silicate weathering in the hydrogeochemical process in the and cations), the groundwater type of the Bist-Doab region has been
region. In (Ca2+ + Mg2+) vs. TZ+ diagram too, groundwater samples determined using Piper trilinear diagram (Fig. 9). The dominance of
between 1:2 line and 1:1 equiline indicate the dominance of carbonate most of the groundwater samples in the left quadrant of the diamond
weathering over silicate weathering (Fig. 7f). plot indicates the (Ca2+ - HCO3− ) type of groundwater in the region. The
rest of the areas show a wide variation in the chemical composition of
3.3. Association between various physicochemical parameters the groundwater. Ca2+ - Na+ - HCO3- type groundwater has been found
in the south-eastern parts, whereas, (Ca2+ - Mg2+ - SO42− ) type of
3.3.1. Correlation matrix groundwater has been observed in Nakodar and Shahkot blocks of
Association between the physicochemical parameters has been Jalandhar and Dhilwan block of Kapurthala districts. Apart from these,
illustrated with the help of the correlation matrix (Table 3). A moderate the groundwater samples from Taunsa in the SBS Nagar district are
to strong correlation has been observed between EC and most of the ions dominated by (Na+ - Ca2+ - Cl− ) type of groundwater. It must be noted
present in the groundwater, proving the fact that EC is influenced by that the groundwater samples of (Na+ - Ca2+ - Cl− ) and (Ca2+ - Mg2+ -
most of the ions present in the groundwater. Besides this, a significant SO42− ) type have an EC value higher than 900, meaning, chloride and
positive correlation between TH-Ca (r ~ 0.95), TH-Mg (r ~ 0.75), TH-EC sulphate largely control the salinity level in groundwater at these places.
(r ~ 0.69), TH-Cl (r ~ 0.6), and TH-SO4 (r ~ 0.57) shows that hardness
in groundwater depends mainly on Ca2+, Mg2+, EC, Cl− , and SO42− . 3.5. Saturation index
From correlation coefficients of EC and TH with other ions, it may be
concluded that the physical parameters depend more on the chemical The saturation index concerning a particular mineral indicates the
characteristic of the groundwater. Chloride shows a moderate to strong possibility of that mineral either dissolving, precipitating, or remaining
correlation with each of the metals i.e., sodium (r ~ 0.83), potassium (r in the state of thermodynamic equilibrium in the groundwater. In this
~ 0.63), calcium (r ~ 0.55), and magnesium (r ~ 0.48). This suggests study, the SI value for all the groundwater samples have been calculated
their common source from metal salts. As chloride is not found in concerning aragonite (CaCO3), calcite (CaCO3), dolomite (CaMg (CO3)2,
groundwater in a natural condition, an intrusion of chloride through the chrysotile (Mg3Si2O5(OH4), halite (NaCl), sylvite (KCl), fluorite (CaF2),
infiltration of meteoric waters might be a strong reason for metal salts quartz (SiO2) chalcedony (SiO2), and (j) talc (Mg3Si4O10) minerals

8
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 7. Biplot of (a) (Ca+2 + Mg+2) vs. HCO3− , (b) Na+/Cl+ vs. Cl− , (c) Ca+2 vs. HCO3− , (d) Ca+2 vs. SO4, (e) Na+ + K+ vs. TZ, and (f) Ca+2 + Mg+2 vs. TZ in the
groundwater samples of the Bist-Doab region of Punjab, India. Groundwater samples have been represented by a blue colour (depth above 80 mbgl), orange color
(between 80 and 150 mbgl), and green colour (below 150 mbgl). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web
version of this article.)

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A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Table 3
Correlation matrix of physico-chemical parameters of the groundwater samples (n = 148) of the Bist-Doab region of Punjab, India.
pH EC HCO3− F− Cl− NO2− Br− NO3− SO42- Na+ K+ Mg2+ Ca2+ TH

pH 1.00
EC − 0.11 1.00
HCO3− 0.09 0.51 1.00
F− 0.23 − 0.07 0.23 1.00
Cl− − 0.09 0.68 − 0.03 − 0.14 1.00
NO2− − 0.06 0.34 0.03 − 0.04 0.35 1.00
Br− − 0.02 0.31 0.34 0.06 0.07 0.17 1.00
NO3− − 0.13 0.28 0.12 − 0.17 0.05 − 0.05 0.14 1.00
SO4− 2 0.03 0.52 0.19 − 0.15 0.15 0.03 0.07 0.03 1.00
Na+ 0.01 0.81 0.36 0.01 0.83 0.24 0.24 0.00 0.30 1.00
K+ − 0.04 0.58 0.08 − 0.03 0.63 0.51 0.02 0.06 0.14 0.47 1.00
Mg2+ − 0.05 0.80 0.49 0.03 0.48 0.20 0.24 0.22 0.60 0.53 0.36 1.00
Ca2+ − 0.18 0.51 0.03 − 0.32 0.55 0.22 − 0.02 0.45 0.45 0.30 0.47 0.49 1.00
TH − 0.15 0.69 0.21 − 0.23 0.60 0.24 0.08 0.42 0.57 0.42 0.49 0.75 0.95 1.00

in declining the groundwater resources in the alluvial tract of Punjab.

Table 4
It must be noted that the region receives an annual rainfall of about
Component loading of various physico-chemical parameters of groundwater
750 mm per year, whereas, paddy-producing states of Bihar and West
samples (n = 148) of the Bist-Doab region of Punjab, India.
Bengal receive an annual amount of rainfall of about 1100 mm and
Parameters PC1 PC2 PC3 PC4
1850 mm per year, respectively (Indian Metrological Department,
pH 0.15 − 0.137 − 0.054 − 0.618 2020a, b, and c). Therefore, tube wells are the only alternative to meet
EC 0.654 0.575 0.42 0.103 the irrigation needs of paddy cultivation in the area. As a result, the
TDS 0.654 0.575 0.42 0.103
TH 0.766 0.33 0.002 0.453
number of tube wells increased by about 5 times from 0.3 million in
Bicarbonate 0.333 − 0.026 0.769 − 0.151 1975 to 1.419 million in 2016–17 (Agarwal et al., 2009; Statistical
Fluoride − 0.127 − 0.038 0.337 − 0.554 Abstract of Punjab, 1975; 2017). About 755 ha of areas around
Chloride 0.375 0.831 − 0.1 0.069 Jalandhar city has been demarcated as an industrial area, which is 50 ha
Nitrite − 0.144 0.695 0.116 0.141
in Nawanshahr, 35 ha in Phagwara, and 14 ha in Hoshiarpur (Micro
Bromide − 0.043 0.124 0.749 0.121
Nitrate 0.241 − 0.135 0.259 0.684 small and medium enterprises, 2016a, b, c, and d). Untreated waste
Sulphate 0.829 − 0.046 − 0.008 − 0.022 discharge from the factories, industries to the groundwater contaminate
Sodium 0.456 0.682 0.265 − 0.186 the existing groundwater resources in the region. Apart from these
Potassium 0.21 0.786 − 0.039 0.092 existing developmental processes, the proposed construction of green­
Magnesium 0.765 0.28 0.36 0.064
field expressways passing through Jalandhar and Kapurthala districts
Calcium 0.631 0.297 − 0.175 0.565
Eigenvalue 4.095 3.522 1.949 1.815 via Nakodar and Shahkot (Press Information Bureau Government of
Percentage of Variance 25.6 22.01 12.18 11.34 India, 2020) will further aggravate the problem in the southern parts of
Cumulative % of Variance 25.6 47.61 59.79 71.13 the Doaba region, as the alignment will attract more industrial and
urban setup.
As these above-mentioned anthropogenic activities increase pressure
(Fig. 10). Results indicate that a Aragonite and calcite were found with
on the existing groundwater resources, the region experienced a decline
SI values of less than 0, indicating a state of undersaturation in most of
in the groundwater table at a rate ranging between 56 and 149 cm per
the groundwater samples (Fig. 10a and b). However, these minerals are
year (Gautam et al., 2020). This decrease in groundwater resources
oversaturated (SI > 0) in central and southern parts of Jalandhar district,
creates several cascading effects, significantly altering the
northern parts of the Kapurthala district, western parts of Nawanshahr
hydro-chemical composition of groundwater. First, over-extraction of
district, and Talwara block of Hoshiarpur district. All the groundwater
groundwater and less groundwater recharge decreases the amount of
samples have been found undersaturated concerning dolomite and
universal solvent (water) in the aquifer environment, leading to the
chrysotile minerals (Fig. 10c and d) which are the probable source of
enrichment of certain chemicals in the natural composition of remaining
calcium and magnesium in the groundwater of the region. The physi­
groundwater in the region. Second, the availability of extra water (as a
cochemical parameters do not show the presence of halite, sylvite, and
result of inessential groundwater extraction for irrigation) in the
fluorite minerals in most of the aquifer environments of the groundwater
scorching heat of the summer season invites the natural process of
samples of the area. However, these minerals are found in the under­
evapotranspiration, leading to the further loss of groundwater resources.
saturated condition wherever they are present (Fig. 10e, f, and g). The
Agarwal et al. (2009) estimated an annual average evapotranspiration
groundwater samples of the region are supersaturated concerning quartz
demand of 521 mm and 273 mm in Kharif and rabi seasons, respectively.
and chalcedony (Fig. 10h and i), indicating the role of these minerals in
Third, the extra water which escapes evapotranspiration is returned to
attributing chemical character to the groundwater of the area. However,
the aquifer as irrigation-return flow through the highly permeable al­
talc is in a state of undersaturation (Fig. 10j) which implies that there is a
luvial soil present in the region. The chemical character of recharged
chance of more dissolution of silica in the groundwater of the area from
groundwater due to irrigation-return flow increases rock-water inter­
talc minerals.
action, which significantly alters the hydrochemistry of the ground­
water. This association between recharged groundwater due to
4. Discussion
irrigation-return flow and its role in further increasing rock-water
interaction has been perfectly established in the groundwater analysis
Anthropogenic activities such as a change in demographic character,
of Condomine catchment in south-eastern Queensland, Australia under a
change in land-use/cover pattern, monocropping of wheat and paddy,
similar environment (Scheiber et al., 2020). The aforementioned
change in sources of irrigation, increase in tube well density, over-
anthropogenic activities to fulfill the unending need of the fast-growing
irrigation, application of chemical fertilizers, level of urbanization,
population have not only led to a reduction in the available fresh
and industrial and infrastructural growth have significantly contributed
groundwater resources but also led to a decline in groundwater quality.

10
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 8. Dendrogram of HCA using average linkage between groundwater samples of various locations of the Bist-Doab region of Punjab.

11
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 9. Piper trilinear diagram demonstrating geochemical classification of groundwater samples in the Bist-Doab region of Punjab, India.

The first leads to changes in the physicochemical characteristics of concentration of contaminants in the groundwater.
groundwater resources, which in turn makes them unsuitable for the use Results and analysis reveal that rock water interaction has been the
of mankind. dominant mechanism attributing hydro-chemical character to the
As far as the sources of ions are concerned, the dissolution of anhy­ groundwater of the region. A similar observation has been recorded in
drite and calcite could be a probable source of higher calcium content in the analysis of the hydrogeochemical characteristics of groundwater of
the groundwater of the Kandi belt. Whereas, in Jalandhar, it could be the most of the alluvial aquifers in various parts of the globe (Sharma et al.,
dissolution of carbonates (calcite and dolomite) and kankar deposits. 2016; Lapworth et al., 2014; Scheiber et al., 2020). In alluvial aquifer
The source of sodium in groundwater of the south-central parts might be systems, the presence of salts (measures by EC) has been linked mainly
due to disposal of domestic and agricultural wastes, and leaching from to ion-exchange reaction and weathering processes in the lithological
sewage disposal as the area is highly urbanized, industrialized, and environment of groundwater (Gend et al., 2020). However, the chemical
intensively cultivated. The source of nitrate in areas around Jalandhar is processes involved in the rock-water interaction vary to a great extent
highly anthropogenic and is directly linked to the prevailing intensive over the study area. In the Kandi belt, reverse ion exchange is prominent
agricultural practices such as application of inorganic fertilizers, due to higher calcium from calcite minerals. In the groundwater around
sewage, and untreated discharge of solid wastes in the region. The water Jalandhar, the process of reverse ion exchange has been dominant due to
from irrigation-return flow along with mixed NPK fertilizers and pesti­ ion exchange between sodium from groundwater and calcium and
cides undergoes hydro-chemical reactions in the unsaturated zone magnesium from calcite and dolomite minerals present in the aquifer
which alters the chemical balance of groundwater, often leading to environment. It must be noted that in this zone, the source of sodium in
deterioration in its quality for further use by humans and plants. A groundwater is not only geogenic i.e., Na-Plagioclase, rather anthropo­
similar observation has been recorded for various agriculturally rich genic. As this zone is agriculturally active, highly urbanized, and
regions of the world, where the prevailing land-use practices and industrialized; leaching of chemical fertilizers, disposal of agricultural,
application of chemical fertilizers have largely controlled the spatial industrial, and urban wastes attribute sodium to the groundwater of the
pattern of nitrate concentration (Suther et al., 2009; Kumari and Rai, region. A similar observation has been made by Rao et al. (2015) while
2020; Marsala et al., 2020). Li et al. (2019) also reported the application assessing the hydrochemistry of groundwater in the Jalandhar district.
of NPK fertilizers in attributing nitrogen pollution in groundwater of The direct base-exchange reaction has been found prominent in the
Yinchuan plain in China. Apart from this, sewage effluent has also been groundwater of Taunsa and Nangal Ambian due to the mixing of sodium
reported as a common source of nitrate contamination, especially in a from industrial wastes in the groundwater and its reaction with calcium
growing urban settlement (Bartsaikhan et al., 2020). The addition of and magnesium present in the aquifer environment. The process of ion
inorganic pollutants in groundwater has been largely due to the point exchange was found prominent in the hydrogeochemical evolution of
source, mainly landfill sites. As most cities of the world do not have a groundwater of Sultanpur Lodhi and Bhulath block. The fact must be
proper waste disposal system, leachate contamination is among the noted that the aquifers at Sultanpur Lodhi are at the receiving end of the
major sources of altering groundwater hydrochemistry. Abiriga et al. groundwater flow from all directions, and at Bhulath, groundwater
(2020) reported that discharge of legacy pollutants and elevated inor­ fluctuation has not been observed for the last two decades (Gautam
ganic pollutants from Revdalen landfills have played a significant role in et al., 2020). Hence, it can be concluded that in an alluvial aquifer
contaminating the groundwater resources in southern Norway. How­ environment, ion-exchange reaction dominates in characterizing the
ever, the closing of the site led to a significant decrease in the hydrochemistry of groundwater having a longer residence time. The

12
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

Fig. 10. Saturation index of groundwater samples in the Bist-Doab region of Punjab, India concerning (a) Aragonite, (b) Calcite, (c) Dolomite, (d) Chrysotile, (e)
Halite, (f) Sylvite, (g) Fluorite, (h) Quartz, (i) Chalcedony, and (j) Talc minerals.

13
A. Gautam et al. Physics and Chemistry of the Earth 126 (2022) 103109

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Declaration of competing interest adaptation. Curr. Sci. 108 (4), 485–490.
Kumar, M., Ramnathan, A.L., Mukherjee, A., Salwani, R., Ranjan, S., 2019. Delineating
The authors declare that they have no known competing financial sources of groundwater recharge and carbon in Holocene aquifers of the central
Gangetic basin using stable isotopic signatures. Isot. Environ. Health Stud. https://
interests or personal relationships that could have appeared to influence doi.org/10.1080/10256016.2019.1600515.
the work reported in this paper. Kumari, M., Rai, S.C., 2020. Hydrogeochemical evaluation of groundwater quality for
drinking and irrigation purposes using water quality index in semi arid region of
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Acknowledgment Lapworth, D.J., Gopal, G., Rao, M.S., MacDonald, A.M., 2014. Intensive groundwater
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The authors are thankful to the Department of Geography, Delhi Geological Survey Open 45. Report OR/14/68.
Ledesma-Ruiz, R., Pasten-Zapata, E., Parra, R., Haster, T., Mahlknecht, J., 2015.
School of Economics, University of Delhi for providing the necessary Investigation of the geochemical evolution of groundwater under agricultural land: a
facilities to carry out the research work. The first author is also grateful case study in northwestern Mexico. J. Hydrol. 521, 410–423.
to the University Grants Commission for providing research fellowship. Li, Z., Yang, Q., Yang, Y., Ma, H., Wang, H., Luo, J., Bian, J., Martin, J.D., 2019. Isotopic
and geochemical interpretation of groundwater under the influence of
Kripa Ram thanks the Department of Science and Technology and SERB, anthropogenic activities. J. Hydrol. 576, 685–697.
Govt. of India for providing financial support under the ECRA Mallick, J., Singh, C.K., AlMesfer, M.K., Kumar, A., Khan, R.A., Islam, S., Rahman, A.,
(#ECR000490) programme and DST SPLICE- Climate Change Pro­ 2018. Hydro-geochemical assessment of groundwater quality in Aseer region. Saudi
Arabia, Water 10, 1847. https://doi.org/10.3390/w10121847, 2018.
gramme (DST/CCP/Aerosol/87/2017).
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