Assessment of groundwater quality scenario in respect of fluoride and nitrate contamination in and around Gharbar village, Jharkhand, India

Journal Pre-proof Assessment of groundwater quality scenario in respect of fluoride and nitrate contamination in and around Gharbar village, Jharkhand, India

Raju Thapa, Srimanta Gupta, Harjeet Kaur, Raju Baski PII:

S2589-7578(19)30013-7

DOI:

https://doi.org/10.1016/j.hydres.2019.09.002

Reference:

HYDRES 9

To appear in:

HydroResearch

Received date:

10 August 2019

Revised date:

19 September 2019

Accepted date:

26 September 2019

Please cite this article as: R. Thapa, S. Gupta, H. Kaur, et al., Assessment of groundwater quality scenario in respect of fluoride and nitrate contamination in and around Gharbar village, Jharkhand, India, HydroResearch(2019), https://doi.org/10.1016/ j.hydres.2019.09.002

This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

© 2019 Published by Elsevier.

Journal Pre-proof Assessment of groundwater quality scenario in respect of fluoride and nitrate contamination in and around Gharbar village, Jharkhand, India *

Raju Thapa ([email protected]), Srimanta Gupta (srimantagupta @yahoo.co.in), Harjeet Kaur ([email protected]) and Raju Baski ([email protected]) Department of Environmental Science, The University of Burdwan, West Bengal

Corresponding author: [email protected]

Jo ur

na

lP

re

-p

ro

of

*

Journal Pre-proof Abstract Present study deals with the identification of geochemical processes and the probable mobilization mechanism responsible for the release of fluoride (F-) and nitrate (NO3-) in groundwater. For this purpose 50 groundwater samples are collected from the Gharbar and its adjacent villages of Jharkhand. The order of abundance of anion and cation in the groundwater sample are HCO3-> Cl-> SO42 -> NO3-> F-> Br- and Ca2+> Na+> Mg2+> K+ respectively. F- concentration ranges from 0.01 to 18.55 mg/L and the NO3- concentration ranges from 34.10 to 319.10 mg/L where majority of the water samples exceeds the permissible limit of F- (1.5 mg/L) and NO3- (45 mg/L). Alkaline aquifer condition accelerates

of

the mobilization of F- in groundwater due to enhanced rate of weathering of fluoride-bearing

ro

minerals whereas anthropogenic activities play a major role in NO3- contamination of the study area. Saturation index (SI) indicates under-saturation of fluorite and calcite in the

-p

majority of water samples. Principal component analysis reveals 3 principal components explaining 72.33% of the data variance and indicates anthropogenic sources of contamination

re

of NO3- and geogenic sources of contamination for F-.

Jo ur

na

village; Jharkhand

lP

Keywords: Fluoride; Nitrate; Hydrogeochemistry; weathering; Saturation index (SI); Gharbar

Journal Pre-proof 1. Introduction Fluoride (F-) in drinking water is essential for bone development and dental caries but on the other hand it also causes dental and skeletal fluorosis (Collier, 1980; Edmunds and Smedley, 2005; WHO, 2011). Globally, about 25 nations with 200 million people are suffering from the dreadful fate of dental and skeletal fluorosis (Edmunds and Smedley, 2005; WHO, 2011; Ayoob and Gupta, 2006; Su et al., 2013). Numerous researchers have reported the occurrence of higher F- concentration in drinking water from all around the globe (Brunt et al., 2004; Edmunds and Smedley, 2005; Ayoob and Gupta, 2006; Chae et al., 2007; Guo et al., 2007; Reddy et al., 2010; Patolia and Sinha, 2017; Thapa et al., 2017a, 2017b; Kabir et al., 2019;

of

Kalpana et al., 2019; Kimambo et al., 2019; Su et al., 2019; Yadav et al., 2019).

ro

Fluoride is the 13th most abundant element in the earth crust occurring basically in fluoridebearing minerals such as fluorite (CaF2), biotite [K(Mg,Fe)3AlSi3O10F2], fluor-apatite

-p

[Ca5(PO4)3F] etc. (Deshmukh et al., 1995; Shah and Danishwar, 2003; Thapa et al., 2017c; Jia et al., 2019). Several factors such as underlain geology, aquifer material, water-rock

re

interaction, pH, temperature, solubility and availability of F- etc influence the enrichment of F- in groundwater (Gosselin et al., 1999; Shah and Danishwar, 2003; Meenakshi et al., 2004;

lP

Paul et al., 2019). Generally, high F- groundwater has Na-HCO3 water type with alkaline pH and lower Ca2+ (Dhiman and Keshari, 2006; Rafique et al., 2009; Su et al., 2013).

na

Nitrate (NO3-) pollutant in drinking water is one of most widespread pollutants in World (Reddy et al., 2009; Thapa et al., 2018a). Application of fertilizer (NPK, urea) in agricultural

Jo ur

field, organic manure, unlined drainage and sewerage lines unplanned disposal of the animal and human waste could results in higher percolation of NO3- in sub-surface water bodies (Jack and Sharma 1983). When NO3- in drinking water is high serious health related problems can arise especially in children and young livestock. The presence of F- in groundwater of Gharbar village has been reported earlier (Patolia and Sinha, 2017) where, F- as high as 14.9 mg/L is reported. However, the presence of NO3- in the groundwater has never been reported so far. In addition detail geochemical study in demarcating the geochemical processes responsible for the release of F- and NO3- in groundwater has not been addressed so far. Present research work is carried out with an objective to evaluate the spatial distribution patterns of F- and NO3- in the study area and to evaluate the probable mechanism of F- and NO3- mobilisation. Saturation Index (SI) is used to understand the saturation of F- in the groundwater of the study area. Principal component analysis (PCA) is applied to highlight the most influential sources contributing to the F- and NO3- concentration in groundwater. The outcome of the present research will provide a

Journal Pre-proof thorough investigation in the micro-scale level giving important information of the study area. 1.1. Study area Gharbar, Birsinhpur and Kalipur village, located about 20 km from Dhanbad district of Jharkhand, India (Fig. 1) lying within 23° 39′ 18″ N to 23° 39′ 58″ N latitude and 86° 33′ 10″ to 86° 32′ 10″ E Longitude are considered as study area for the present research work. Gharbar, Birsinhpur and Kalipur village occupies an area of 3.75, 3.68 and 1.88 sq. km respectively. In the study area, groundwater occurs in both unconfined and confined conditions. The unconfined condition occurs at shallow depths of all litho units of

of

Gondwanas and Achaeans (Fig. 2). Under confined to semi-confined condition groundwater

ro

occurs in deep-seated fractures that are disconnected with the top weathered zone. The shallow aquifer consists of the weathered mantle and shallow fracture. In shallow aquifers,

-p

the weathered mantle thickness varies from 5 - 25 mbgl. The recent and sub-recent alluvium (older and newer) is the main porous formation. The drainage systems in the study area are a

re

part of the Damodar sub-basin. Rainwater is the principal source of groundwater recharge in the study area and the Indian Meteorological Department (IMD), Dhanbad shows 1306 mm

lP

of rainfall. The study area experiences sub-tropical in nature characterized by very hot summer from March and May, well-distributed rainfall from June to September, and cold and

2. Materials and methods

na

dry winter from December to February (CGWB, 2013).

Jo ur

Extensive water sampling was carried out with an objective to cover the Gharbar and its surrounding villages (Fig. 1). Altogether fifty (50) groundwater samples were collected on December, 2019 (post-monsoon) following the standard sampling protocol laid down by WHO (2011).

2.1. Physicochemical analysis of groundwater samples Physical parameters such as pH, Electrical conductance (EC), Total dissolved solids (TDS) were measured using portable multi-parameter analyzer in the field itself. Major cation and anion were analysed in ion chromatography (IC, Dionex Integrion HPIC model no. 17050089) in the Department of Environmental Science, The University of Burdwan. The ionic balance error (IBE) was estimated to estimate the precision of ions measurement. The IBE value was within the desirable limit of ±10% (Domenico and Schwartz, 1998; Jabal et al., 2014). The spatial interpolation of water samples was carried out in ArcGIS 10.1 platform and analysis of dominant water type was carried out in AquaChem-2012 software. 2.2. Principal component analysis (PCA)

Journal Pre-proof Principal component analysis (PCA) was performed to understand an insight of the underlying hydrogeochemical and their possible sources i.e., natural or anthropogenic sources influencing the groundwater (Chen et al. 2007; Praus 2007; Salifu et al. 2012). PCA, scatter plots and basic descriptive statistics were performed on high F- samples using the statistical software package XL-STAT 12. 2.3. Saturation index (SI) In order to perform the saturation index assessment Aquachem-12 software with Phreeqc modelling extension was used. The saturation indices (SI) was calculated using the following equation (eq. 1): 𝐼𝐴𝑃 𝐾𝑡

)

of

SI = log (

(eq. 1)

ro

Where, IAP is the chemical species dissociated in solution and Kt represents the equilibrium solubility product of the mineral. The SI value of any mineral phase is positive when the

-p

groundwater is oversaturated with respect to that particular mineral and SI value is negative

re

when the groundwater is under-saturated. When groundwater is over-saturated mineral show a tendency to precipitate and when the groundwater is under-saturated mineral dissolution

3. Results and discussion

na

3.1. Hydrogeochemistry

lP

continues until the equilibrium is reached.

Physico-chemical analysis along with detail descriptive statistics of the samples represented

Jo ur

in Table 1, reveals the order of abundance of anion and cation as HCO3- > Cl- > SO42 -> NO3> F- > Br- and Ca2+ > Na+ > Mg2+ > K+ respectively. 3.2. Factors influencing F- in groundwater 3.2.1. Physical parameters

The pH, EC and TDS ranges from 6.60 to 8.60, 130 to 830 µs/cm and 400 to 1080 mg/L respectively (Table 1). TDS in majority of the samples i.e., 34 samples (68% of the total sample) are observed above the WHO permissible limit of 600 mg/L and only 2 samples (4% of the total sample) have pH above 8.5. All samples have EC within the permissible limit of 1500 µs/cm. A very strong positive correlation is observed between F- and pH (r = 0.81) (Table 2) in the study area and similar type of observations have been reported by earlier researchers (Rafique et al., 2009; Wang et al., 2009; Su et al., 2013). pH shows moderate negative correlation with NO3- (-0.42). 3.2.2. Cation and anions

Journal Pre-proof Na+ in water sample ranges from 92.37 to 1028.30 mg/L in the study area where 39 samples (78%) have concentration beyond the permissible limit of 200 mg/L. Ca 2+ concentration in the study area ranges from 10.22 to 181.09 mg/L and all 50 samples (100%) are well within the WHO permissible limit of drinking water (WHO, 2011). K+ and Mg2+ range from 11.74 to 29.2 mg/L and 02 to 33.20 mg/L respectively. A moderate positive correlation are observed between F- and K+ (r = 0.35) and F- and Na+ (r = 0.30) (Table. 2). Cation such as Mg2+ and Ca2+ show moderate negative correlation with F- r = -0.55, and -0.30 respectively. The negative correlation of F- with Ca2+ and Mg2+ may be attributed to the lower solubility of above ions from aquifer media (Ncube, 2002) along with the prior CaCO3 precipitation from

of

groundwater samples (Reddy et al., 2010; Jabal et al., 2014). Observations similar to our studies have been reported by several researchers in different regions of the globe (Chae et

ro

al., 2007; Kantharaja et al., 2007; Jabal et al., 2014). Mg2+ and Ca2+ show strong positive

-p

correlation with NO3- with r = 0.71 and 0.76 respectively and similar correlation has been reported by Chiu et al., 2011.

re

F- in water samples ranges from 0.21 to 18.55 mg/L where 60% of samples (30 samples) are beyond the WHO permissible limit of 1.5 mg/L (WHO, 2011). Cl- in the study area ranges

lP

from 16.78 to 1178.71 mg/L where about 24% of the total samples i.e., 12 samples have concentration beyond the permissible limit. The NO3-, SO42- and PO43- ranges from 34.10 to

na

319.10, 13.32 to 201.91 mg/L and 0.01 to 7.29 mg/L respectively. In 76% of water samples (38 samples) the HCO3- concentration is beyond the WHO permissible limit of 250 mg/L.

Jo ur

The HCO3-, SO42- and Cl- show a negative correlation with F- and all the anions indicate a weak correlation with F- (Table 2). 3.2.3. Water type

Calcium is the dominant cation in all the groundwater samples. The groundwater samples are categorized into three groups based on F- concentration (WHO, 2011) i.e., low (F- < 1.5 mg/L) and high (F- > 1.5 mg/L) where, 20 and 30 samples fall under the low and high category respectively (Fig. 3). According to Piper diagram (1953), the groundwater samples are categorized into different types i.e., Ca-Mg-HCO3, Na-Cl, Na-HCO3-Cl, Ca-Mg-Cl-SO4, and Ca-Mg-SO4 where Na-HCO3-Cl is dominant water type within high F- samples and CaMg-HCO3 is the dominant water type in low F- water samples (Piper 1944). 3.3. Geochemical processes operating in the aquifer In an underground aquifer weathering of carbonate minerals, silicate minerals, ion exchange phenomena, evapotranspiration and dissolution of evaporates are the prime geogenic sources of the dissolved cations and anions. To understand the occurrence of various geochemical

Journal Pre-proof processes in the aquifer, a series of ionic ratios are reported very useful by several researchers (Hounslow, 1995; Elango et al., 2003; Srinivasamoorthy et al., 2014; Dedzo et al., 2017). 3.3.1. Evaporation Generally, when evaporation is the major process contributing to the ions concentration in groundwater there is an overall increase in the concentration of all the ions in groundwater. In the present study, the molar F-/Cl- ratios of the majority of samples have a value greater than 0.02 (typical unpolluted rainfall value) suggesting that there is no role of evapotranspiration (Currell et al., 2011; Kumar and Kumar, 2015). Among the samples analysed, 84% of samples have Na+/ Cl- ratio > 1:1 equiline (Fig. 4a) suggesting the role of silicate weathering

of

in release of Na+ probably via following reactions (Stallard and Edmond, 1983; Srinivasamoorthy et al., 2014; Dedzo et al., 2017) (eq. 2):

ro

2NaAlSi3O8 + 9H2O + 2H2CO3 = Ai2Si2O5(OH)4 + 2Na+ + 2HCO3- + 4H4SiO4

(eq. 2)

-p

Similarly, in the plot of Na+ vs Cl-, majority of the points fall below 1:1 equiline which indicates weathering processes as major processes occurring in the aquifer in comparison to

re

evaporation process (Srinivasamoorthy et al., 2014). In addition, if evapotranspiration contributes to groundwater ions concentration that plot of Na+/Cl- vs EC gives a horizontal

lP

line but there is no such indication. The dominance of HCO3- ions along with Na+/Cl- ratio > 1 indicates that the role of silicate weathering in the release of Na+ in groundwater as the

na

interaction of feldspar minerals with water and carbonic acid releases HCO3– ions (Meybeck, 1987; Elango et al., 2003; Srinivasamoorthy et al., 2014). The high value of (Na+ + K+) vs Cl-

Jo ur

ratio also indicates the role of silicate weathering in releasing the alkali metals. 3.3.2. Weathering processes

All the water samples are plotted in Gibbs (1970) diagram (Fig. 4b – 4c) where it shows that sediments–water interaction in comparison to precipitation and evaporation are the main source of ions in groundwater. The plot of (Ca2++Mg2+)/TZ+ lies above and away from 1:1 equiline indicating the contribution of weathering processes (Fig. 4d) (Dedzo et al., 2017). The plot of (HCO3- + SO42-) vs (Ca2+ + Mg2+) as represented in (Fig. 4e) indicates excess of HCO3- and SO42- over alkaline earth elements i.e., Ca2+ and Mg2+ suggesting, the role of silicate weathering (Hounslow, 1995; Srinivasamoorthy et al., 2014; Dedzo et al., 2017) The most stable silicate mineral phase can be identified using mineral stability diagrams. The stability and weathering products of K2O–H2O–Al2O3–SiO2 system and NaO–H2O–Al2O3– SiO2 system is represented in Fig 4(f) and 4(g) respectively. This plot works on the assumption that the Al3+ released is preserved in products and pH, Na+, K+ and dissolved silica controls the relative stability between minerals (Appelo and Postma, 2005). All the

Journal Pre-proof samples indicate that the most likely stable mineral in aquifer is kaolinite. Hydrolysis of some alumino-silicate minerals leads to the abundances of HCO3-, Ca2+ and Mg2+ in groundwater (Dedzo et al., 2017). Silicate minerals via weathering processes can results in the formation of clay mineral kaolinite. Some examples are as follows (eq. 3-6): CaAl2Si2O8 (Anorthite) + 2CO2 + 3H2O = Al2Si2O5(OH)4 + Ca2+ + 2HCO3-

(eq. 3)

2KMg3AlSi3O10(OH)2 (Biotite) + 14CO2 + 15H2O = Al2Si2O5(OH)4 + 2K+ + 6Mg2+ + 4H4SiO4 + 14HCO3-

(eq. 4)

2NaAlSi3O8 (Albite) + 2CO2 + 11H2O = Al2Si2O5(OH)4 (Kaolinite)+ 2Na+ + 4H4SiO4 + 2HCO3-

(eq. 5) +

+

of

2K(AlSi3)O8 (K-feldspar) + 2H + 9H2O = Al2Si2O5(OH)4 + 2K + 4H4SiO4

(eq. 6)

ro

At higher pH, as the ionic radii of OH- ion and F- ion are similar, OH- ion can replace the Fion in the aquifer material with clay minerals and fluoride-bearing minerals such as biotite,

-p

fluorite and muscovite resulting in release of F- from aquifer material in groundwater (Saxena and Ahmed, 2003; Sreedevi et al., 2006; Thapa et al., 2018b; Su et al., 2019). The possible

re

reactions involved in release of F- in groundwater from biotite, fluorite and muscovite are

lP

represented in eq. (7), eq. (8) and eq. (9) respectively (Xiao et al., 2015): KMg3[Al3Si3O10]F2 + 2OH− = KMg3[AlSi3O10][OH2] + 2F− −

−

na

CaF2 + 2OH = Ca(OH)2 + 2F

KAl2[AlSi3O10]F2 + 2OH− = KAl2[AlSi3O10][OH2] + 2F−

(eq. 7) (eq. 8) (eq. 9)

Jo ur

EC (r=0.2), TDS (r = -0.12) shows very weak correlation with F- (Table 2) and similar observation have reported by several researchers (Perel'man, 1977; He et al., 2013). 3.4. Saturation index (SI)

The presence of F- in groundwater is regulated by several factors such as degree of saturation of fluorite, calcite, HCO3-, Na+ and Ca2+ ions in groundwater (Saxena and Ahmed, 2003; Mamatha and Rao, 2010; Uppin and Karro, 2013; Thapa et al., 2018). The results of Saturation index (SI) calculated using PHREEQC (Parkhurst and Appelo, 1999) indicates that majority of the sample falls under the unsaturated zone of calcite and fluorite (only 9 samples falls in F- saturated zone) which indicates that under the normal field condition more F- can be dissolved in the groundwater (Fig. 5) (Kumar and Kumar, 2015). At higher pH, Ca2+ is removed from groundwater due to CaCO3 precipitation facilitating rapid and higher fluorite dissolution (Alamry, 2009; Rafique et al., 2008). So, the undersaturation of F- in the study area may be attributed to calcite saturation, subsequently increasing F-/Ca2+ ratio and reducing the calcium activity by facilitating further fluorite dissolution (Rafique et al., 2008).

Journal Pre-proof 3.3.3. Nitrate To understand the source of NO3- in groundwater a series of ionic plots has been implemented. The NO3- in water sample show a moderate positive correlation with TDS, Mg2+, Ca2+, Cl-, SO42- and moderate negative correlation with pH (Table 2) reflecting higher NO3- contamination with increased mineralization of water sample (Reddy et al., 2009). Plot of NO3- vs K+ (Fig. 6a) indicates almost all samples falling above 1:1 equiline which indicates fertilizer as one of the main source of NO3- (Dutta et al. 1997; Reddy et al., 2009). The bivariate scatter of NO3- vs SO42- (Fig. 6b) also indicates the contribution from similar sources such as application of NPK fertilizers in agricultural field (Jalali 2009; Srivastava and

of

Ramanathan 2018). Suthar et al., (2009) highlighted the correlation between NO3- vs SO42- as an indication of point source contamination such as sewage, fertilizer, animal waster etc.

ro

Similarly the high coefficient of determination (R² = 0.81) between SO42- and Cl- (Fig. 6c)

-p

suggests anthropogenic activities such as extensive use of fertilizers, unpaved drainage systems and gaseous particulate deposits from nearby industrial plant as the source of both

re

SO42- and Cl- in groundwater (Rajmohan and Eango, 2006).

lP

3.5. Principle Component Analysis (PCA)

Table 3 represents the result of PCA performed with the 15 geochemical parameters

na

measured from 50 groundwater samples in Gharbar and its adjacent villages, Jharkhand. With the implication of PCA, 50 water samples were categorized into three major principal components (PC) (PC1, PC2 and PC3) explaining approximately 72.33% of the total

Jo ur

variance. The correlation between the principal components and the value physic-chemical variables is established with the help of principal component loading (Praus, 2007; Salifu et al. 2012). The most important process controlling groundwater chemical composition is represented by the first PC with highest eigenvalue and accounting for the maximum variance (Yidana et al., 2010; Salifu et al. 2012). PC1 explaining approximately 40% of variance is mainly influenced by TDS, Mg2+, Ca2+, Cl-, NO3-, PO42- and SO42-. Positive loading of NO3-, PO42- and SO42- indicates that in regions where PC1 is predominant, anthropogenic sources are the major contributor in groundwater chemicals composition. PC2 explains approximately 20% of total variance and indicates major positive loading of pH, EC, Na+ and F- suggesting that F- occurrence is influenced by pH, Eh and Na+ which is further corroborated to pH dependent and silicate weathering. Alkaline aquifer conditions facilitates replacement of Fion with OH- ion in the aquifer material resulting in higher F- in the groundwater (Saxena and Ahmed, 2003; Sreedevi et al., 2006; Thapa et al., 2018). The strong positive factor loading of

Journal Pre-proof Na+ and F- suggests enrichment of F- by minerals releasing Na+ such as weathering of silicate minerals. However, PC2 also indicates that evaporation is not a dominant factor influencing F- concentrations in groundwater as factor loading of Cl- is non-significant (Srinivasamoorthy et al., 2014; Dedzo et al., 2017). PC3 explains 12.24% of total variance with major positive loading HCO3 and negative factor loading of K+.

4. Conclusions The study area, Gharbar, Birsinhpur and Kalipur village is underlain by a gneissic complex of Archean age, which contains mainly hornblende and biotite as fluoride-bearing minerals. The

of

analysis of groundwater sample shows that groundwater has high bicarbonate ions and higher

ro

pH. The order of abundance of anion and cation are HCO3- > Cl- > SO42 -> NO3- > F- > Br- and Ca2+ > Na+ > Mg2+ > K+. The concentration of F- varying from 0.01 to 18.55 mg/L, is much

-p

higher than the recommended limit of 1.5 mg/L for drinking purpose. Similarly, in 33 samples (74%) HCO3- concentration is beyond the permissible limit of 45 mg/L. F- accretion

re

in groundwater from the dissolution of fluoride-bearing minerals is accelerated by the

lP

alkaline aquifer conditions. The main source of F- in the study area is silicate weathering as highlighted by a series of ionic ratios. Because of the continuous intake of higher concentration of fluoride-bearing water, the local public suffers from the skeletal and dental

na

fluorosis. There is no major difference found in F- concentration in groundwater samples taken from wells in the agricultural field and domestic bore wells. This indicates that

Jo ur

fertilizers did not play a role in the distribution of F- in groundwater. Hence, the major source of F- concentration in water is geogenic. The relationship of NO3- with K+ and SO42- indicates fertilizers, unlined domestic sewage and organic manure as the main source of NO3contamination in the study area. As there is no other source of drinking water in Gharbar and surrounding village, improvement in groundwater quality can be done by identifying bore wells with high F- and NO3- concentration and avoiding consumption of water from those wells. Proper management of drainage system (as the drainage system the study area is open and unlined), judicial use of fertilizers along with the implementation of crop rotation can be an effective tool in combating the existing problem. Awareness is also very necessary regarding the health effects of high F- and NO3- concentration as majority of the population is tribal community population with very low literacy rate. Rainwater harvesting can also be adopted using percolation tanks and recharge pits which may be helpful in diluting the

Journal Pre-proof concentrations of F- and NO3- in the study area. After filtration, the recharge of rainwater through the existing wells can also be planned to improve the groundwater quality. Acknowledgement The authors would like to acknowledge DST, Govt. of India for providing financial support to setup a sophisticated laboratory in the department of Environmental Science under FIST programme.

Conflict of interest

of

There is no potential conflict of interest.

ro

References

Alamry, A.S., Study about the Fluorosis in Selected Villages of Taiz Governorate. Final Draft Report

prepared

for

NWRA,

Yema,

2009,

pp.71.

-p

Mission

https://www.academia.edu/404179/Study_about_the_Fluorosis_in_Selected_Villages_of_Tai

re

z_ Governorate

Appelo, C.A.J., Postma, D., Geochemistry, Groundwater and Pollution. 2nd edition. CRC

lP

Press, New York, 2005.

Ayoob, S., Gupta, A.K., Fluoride in drinking water: A review on the status and stress effects,

na

CRIT. REV. ENV. SCI. TEC., 2006, vol. 36, pp. 433–487. Brunt, R., Vasak, L., Griffioen, J., Fluoride in ground water: probability of occurrence of

Jo ur

excessive concentration on global scale. Report sp, International Groundwater Resources Assessment Centre (IGRAC), 2004.

CGWB, Ground Water Information Booklet, Dhanbad District, Jharkhand State, Central Ground

water

Board,

Ministry

of

Water

Resources,

Govt.

of

India,

2013.

http://cgwb.gov.in/District_Profile/Jharkhand/Dhanbad.pdf Chae, G.T., Yun, S.T., Mayer, B., Kim, K.H., Kim, S.Y., Kwon, J.S., Kim, K., Koh, Y.K., Fluorine geochemistry in bedrock groundwater of South Korea, Sci Total Environ, 2007, vol. 385, no. 1–3, pp. 272-283. Collier, D.R., Fluorine: An essential element for good dental health, J. Public Health Dent., 1980. vol. 40, no.3, pp. 296–300. Currell, M., Cartwright, I., Raveggi, M., Han, D., Controls on elevated fluoride and arsenic concentrations in groundwater from the Yuncheng Basin, China, App.l Geochem., 2011, vol. 26, no. 4, pp. 540–552. https://doi.org/10.1016/j.apgeochem.2011.01.012.

Journal Pre-proof Chen, K.P., Jiao, J.J., Huang, J.M., Huang, R.Q., Multivariate statistical evaluation of trace elements in groundwater in a coastal area in Shenzhen, China. Environ. Pollut., 2007. Vol. 147, pp. 771–780. http://www.sciencedirect.com/science/article/pii/S0269749106005318. Chiu, H.F., Tsai, S.S., Chen, P.S., Wu, T.N., Yang, C.Y., Does calcium in drinking water modify the association between nitrate in drinking water and risk of death from colon cancer?, J Water Health., 2011, vol. 9, issue 3, pp. 498-506. doi: 10.2166/wh.2011.006. Dedzo, G.K., Yambou, E.P., Saheu, M.R.T., Ngnie, G., Nanseu-Njiki, C.P., Detellier, C., Hydrogen evolution reaction at PdNPs decorated 1:1 clay minerals and application to the electrocatalytic determination of p-nitrophenol, J. Electroanal. Chem., 2017, vol. 801, no. 49-

of

56.

Gondwana Geol Mag., 199, vol. 5, no. 9, pp.1-20.

ro

Deshmukh, A.N, Wadaskar P.M., Maple, D.B, Fluorine in Environment: A Review,

-p

Deveral, S.J., Geostatistical and principal component analysis of ground chemistry and soilsalinity data, San Joaquin Valley, California. Regional characterization of water quality.

re

Proceeding of Baltimore Symposium, 1989. IAHS, p. 182.

Dhiman, S.D., Keshari, A.K., Hydrogeochemical evaluation of high-fluoride groundwaters: a

lP

case study from Mehsana District, Gujarat, India, Hydrolog. Sci. J., 2006, vol. 51, no. 6, pp. 1149-1162, DOI: 10.1623/hysj.51.6.1149

na

Domenico, P.A., Schwartz, F.W., Physical and Chemical Hydrogeology, second ed. John Wiley & Sons, New York, 1998.

Jo ur

Dutta, P.S., Deb, D.L., Tyagi, S.K., Assessment of ground water contamination from fertilizers in Delhi area based on O18, NO3 and K composition. Journal of Contaminant Hydrology, 1997, vol. 27, pp. 249–262. Edmunds, W.M., Smedley, P.L., Fluoride in natural waters. In: Selinus, O. (Ed.), Essentials of Medical Geology. Elsevier Academic Press, London, 2005, pp. 301-329. Elango, L., Kannan, R., Kumar, M.S., Major ion chemistry and identification of hydrogeochemical processes of groundwater in part of Kancheepuram district, Tamil Nadu, Environ. Geosci., 2003, vol. 10, no. 4, pp.157–166. https://doi.org/10.1306/eg100403011. Gosselin, D.C., Headrick, J., Harvey, F.E., Tremblay, R., McFarland, K., Fluoride in Nebraska's ground water, Ground Water Monit R., 1999, vol. 19, no. 2, pp. 87–95. Guo, H., Wang, Y., Geochemical characteristics of shallow groundwater in Datong basin, northwestern China. J. Geochem. Explor, 2005, vol. 87, pp. 109–120.

Journal Pre-proof Guo, Q., Wang, Y., Ma, T., Ma, R., Geochemical processes controlling the elevated fluoride concentrations in groundwater of the Taiyuan Basin, Northern China., J. Geochem. Explor., 2007 , vol. 93 pp. 1-12. He, J., An, Y.H., Zhang, F.C., Geochemical characteristics and fluoride distribution in the groundwater of the Zhangye Basin in Northwestern China, J. Geochem. Explor., 2013, vol. 135, pp. 22–30. Hu, S., Luo, T., Jing, C., Principal component analysis of fluoride geochemistry of groundwater in Shanxi and Inner Mongolia, China. J Geochem Explor. 2013, vol. 135, pp 124–129. http://dx.doi.org/10.1016/j.gexplo.2012.08.013

of

Hounslow, A., Water quality data: analysis and interpretation, 1st edn. CRC Lewis, Boca

ro

Raton, 1995.

Jabal, M.S.A., Abustan, I., Rozaimy, M.R., Al-Najar, H., Fluoride enrichment in groundwater

-p

of semi-arid urban area: Khan Younis City, southern Gaza Strip (Palestine), J. Afr. Earth Sci. 2014, vol. 100, pp. 259–266. http://dx.doi.org/10.1016/j.jafrearsci.2014.07.002

re

Jabal, M.S.A., Abustan, I., Rozaimy, M.R., Al-Najar, H., Fluoride enrichment in groundwater of semi-arid urban area: Khan Younis City, southern Gaza Strip (Palestine), J. Afr. Earth Sci.,

lP

2014, vol. 100, pp. 259–266. http://dx.doi.org/10.1016/j.jafrearsci.2014.07.002. Jalali, M., Geochemistry characterization of groundwater in an agriculture area of Razan,

na

Hamadan, Iran; Environ. Geol., 2009, Vol. 56, pp. 1479–1488. Jia, H., Qian, H., Qu, W., Zheng, L., Feng, W., Ren, W., Fluoride Occurrence and Human

Jo ur

Health Risk in Drinking Water Wells from Southern Edge of Chinese Loess Plateau. Int J Environ Res Public Health., 2019, vol. 16, issue 10, pp. 1683. doi: 10.3390/ijerph16101683 Kabir, H., Gupta A.K., Tripathy, S., Fluoride and human health: Systematic appraisal of sources, exposures, metabolism, and toxicity, Crit Rev Env Sci Tec., 2019. DOI: 10.1080/10643389.2019.1647028

Kalpana, L., Brindha, K., Elango, L., FIMAR: A new Fluoride Index for identification of sites to mitigate geogenic contamination by managed aquifer recharge, Chemosphere, 2019, doi: https://doi.org/10.1016/j.chemosphere.2018.12.084. Kantharaja, D., Lakkundi, T., Basavanna, M., & Manjappa, S., Spatial analysis of fluoride concentration in groundwaters of Shivani watershed area, Karnataka state, South India, through geospatial information system, Environ. Earth Sci., 2007, 65(1), 67–76. doi: 10.1007/s12665-011-1065-1 Kimambo, V., Bhattacharya, P., Mtalo, F., Mtamba, J., Ahmad, A., Fluoride occurrence in groundwater systems at global scale and status of defluoridation – State of the art,

Journal Pre-proof Groundwater

for

Sustainable

Development,

2019,

9,

100223.

https://doi.org/10.1016/j.gsd.2019.100223 Kumar, A., Kumar, V., Fluoride contamination in drinking water and its impact on human health of Kishanganj, Bihar, India, Res. J. Chem. Sci. 2015, vol. 5, no. 2, pp. 76–84. http://www.isca.in/rjcs/ Archives /v5/i2/13.ISCA-RJCS-2015-018.pdf. Mamatha, P., Rao, S.M., Geochemistry of fluoride rich groundwater in Kolar and Tumkur Districts of Karnataka, Environ. Earth Sci., 2010, vol. 61, no. 1, pp. 131–142 https://doi.org/10.1007/s12665-009-0331-y Meenakshi, Garg, V.K., Kavita, Renuka, Malik, A., Groundwater quality in some villages of

of

Haryana, India: focus on fluoride and fluorosis, J. Hazard. Mater., 2004, vol. 106B, pp. 85–

ro

97.

Meybeck, M., Global chemical weathering of surficial rocks estimated from river dissolved

-p

loads, Am. J. Sci., 1987, vol. 287, pp. 401–428. https://doi.org/10.2475/ajs.287.5.401 Ncube, E.J., The Distribution of Fluoride in South Africa Groundwater and the Impact

re

Thereof on Dental Health. Master Thesis, University of Pretoria, South Africa, 2002. http://www.repository.up.ac.za/bitstream/handle/2263/26112/dissertation.pdf?sequence=1

lP

Parkhurst, D.L., Appelo, C.A.J., User's guide to Phreeqc (version 2) — a computer program for speciation, batch-reaction, one dimensional transport and inverse geochemical calculation.

pp. 312.

na

USGS waterresources investigation report 99-4259, Denver: U.S. Geological Survey, 1999,

Jo ur

Patolia, P., Sinha, A., Fluoride contamination in Gharbar Village of Dhanbad District, Jharkhand, India: source identification and management. Arab. J. Geosci. 2017, 10:381. https://link.springer.com/article/10.1007/s12517-017-3164-0 Paul, R., Brindha, K., Gowrisankar, G., Tan M.L., Singh, M.K., Identification of hydrogeochemical processes controlling groundwater quality in Tripura, Northeast India using evaluation indices, GIS, and multivariate statistical methods, Environ. Earth Sci., (2019) 78:470. https://doi.org/10.1007/s12665-019-8479-6 Perel'man, A.I., Geochemistry of Elements in the Supergene Zone. (Translated from Russian). Israel Program for Scientific Translations, Jerusalem, 1977. Praus, P., Urban water quality evaluation using multivariate analysis. Acta Montanistica Slovaca, 2007. Vol. 12, issue 2, pp 50–158. www.actamont.tuke.sk/pdf/2007/n2/11praus.pdf. Rafique, T., Naseem, S., Bhanger, M.I., Usmani, T.H., Fluoride ion contamination in the groundwater of Mithi sub-district, the Thar Desert, Pakistan, Environ. Geol. 2008, vol. 56, no. 2, pp. 317–326. https://doi.org/10.1007/s00254-007-1167-y.

Journal Pre-proof Rafique, T., Naseem, S., Usmani, T.H., Bashir, E., Khan, F.A., Bhanger, M.I., Geochemical factors controlling the occurrence of high fluoride groundwater in the Nagar Parkar area, Sindh. Pakistan, J. Hazard. Mater., 2009, 171, 424–430. Rajmohan, N., Elango, L., Hydrogeochemistry and its relation to groundwater level fluctuation in the Palar and Cheyyar river basins, southern India; Hydrol. Process, 2006, vol. 20, 2415–2427. https://doi.org/10.1002/hyp.6052 Reddy, A., Reddy, D., Rao, P., Prasad, K.M., Hydrogeochemical characterization of fluoriderich groundwater of Wailpalli watershed, Nalgonda District, Andhra Pradesh, India, Environ. Monit. Assess, 2010, vol. 171, pp. 561–577.

of

Reddy, A.G.S., Kumar, K.N, Rao, D.S., Rao, S.S., Assessment of nitrate contamination due

ro

to groundwater pollution in north eastern part of Anantapur District, A.P. India. Environ Monit Assess., 2009, Vol. 148, pp. 463–476. DOI 10.1007/s10661-008-0176-y

-p

Salifu, A., Petrusevski, B., Ghebremichael, K., Buamah, R., Amy, G., Multivariate statistical analysis for fluoride occurrence in groundwater in the Northern region of Ghana. J Contam

re

Hydrol, 2012. Vol. 140–141, pp 34–44. http://dx.doi.org/10.1016/j.jconhyd.2012.08.002 Saxena, V.K., Ahmed, S., Inferring the chemical parameters for the dissolution of fluoride in

lP

groundwater, Environ. Geol., 2003, vol. 43, no. 6, pp. 731–736. https://doi.org/10.1007/ s00254-002-0672-2.

na

Senthikumar, G., Ramanathan, A.L., Nainwal, H.C., Chidambaram, S., Evaluation of the hydro geochemistry of groundwater using factor analysis in the Cuddalore coastal region,

Jo ur

Tamil Nadu, India. Indian j. mar. sci. 2008. Vol. 37, issue 2, pp 181–185. http://nopr.niscair.res.in/bitstream/123456789/1882/1/IJMS%2037(2)%20181-185.pdf Shah, M.T., Khan Danishwar, S., Potential fluoride pollution and its source of contamination in the drinking water of Naranji area, N.W.F.P., Pakistan, Environ. Geochem. Hlth., 2003, vol. 4, pp. 475-481.

Sreedevi, P.D., Ahmed, S., Made, B., Ledoux, E., Gandolfi, J.M., Association of hydrological factors in temporal variations of fluoride concentration in a crystalline aquifer in India, Environ. Geol., 2006, vol. 50, no. 1, 1–11. DOI: 10.1007/s00254-005-0167-z. Srinivasamoorthy, K., Gopinath, M., Chidambaram, S., Vasanthavigar, M., Sarma, V.S., 2014. Hydrochemical characterization and quality appraisal of groundwater from Pungar sub basin,

Tamilnadu,

jksus.2013.08.001.

India,

JKSUS,

vol.

26,

pp.37–52.

https://doi.org/10.1016/j.

Journal Pre-proof Srivastava, S.K., Ramanathan, A.L., Geochemical assessment of fluoride enrichment and nitrate contamination in groundwater in hard-rock aquifer by using graphical and statistical methods. J. Earth Syst. Sci., 2018, vol. 127:104. https://doi.org/10.1007/s12040-018-1006-4 Stallard, R.F., Edmond, J.M., Geochemistry of the Amazon river. The influence of geology and weathering environment on the dissolved load, J. Geophys. Res., 1983, vol. 88, pp. 9671– 9688. https://doi.org/10.1029/JC088iC14p09671 Su, C.L., Wang, Y.X., Xie, X.J., Li, J.X., Aqueous geochemistry of high-fluoride groundwater in Datong Basin, Northern China, J. Geochem. Explor., 2013, vol. 135, pp. 79– 92.

of

Su, H., Wang, J., Liu, J., Geochemical factors controlling the occurrence of high-fluoride

ro

groundwater in the western region of the Ordos basin, north western China. Environ Pollut. Vol. 252 (2019): pp. 1154 - 1162

-p

Suthar, S., Preeti, B., Sushma, S., Pravin, K.M., Arvind, K.N., Nagraj, S.P., Nitrate contamination in groundwater of some rural areas of Rajasthan, India. J. Hazard. Mater.

re

2009, vol. 171, issue 1–3, pp. 189–199. https://doi.org/10.1016/ j.jhazmat.2009.05.111 Thapa, R., Gupta, S., Guin, S., Kaur, H., Sensitivity analysis and mapping the potential

vulnerability

models,

Water

Sci.,

2018a,

vol.

32,

issue

1,

pp.

44–66.

na

doi:10.1016/j.wsj.2018.02.003

lP

groundwater vulnerability zones in Birbhum district, India: A comparative approach between

Thapa, R., Gupta, S., Gupta, A., Reddy, D.V., Kaur, H., Geochemical and geostatistical

Jo ur

appraisal of fluoride contamination: An insight into the Quaternary aquifer, Sci. Total Environ., 2018b, vol. 640–641, pp. 406–418. https://doi.org/10.1016/j.scitotenv.2018.05.360. Thapa, R., Gupta, S., Kaur, H., Delineation of potential fluoride contamination zones in Birbhum, West Bengal, India, using remote sensing and GIS techniques. Arab. J. Geosci. 2017b, vol. 10, issue 527, pp. 1–18. https://doi.org/10.1007/s12517-017-3328-y Thapa, R., Gupta, S., Reddy, D.V., Application of geospatial modelling technique in delineation of fluoride contamination zones within Dwarka Basin, Birbhum, India, GSF, 2017a, vol 8, issue 5, pp. 1105-1114. https://doi.org/10.1016/j.gsf.2016.11.006. Thapa, R., Gupta, S., Reddy, D.V., Kaur, H., An evaluation of irrigation water suitability in the Dwarka river basin through the use of GIS based modeling, Environ Earth Sci., 2017c, 76:471. DOI10.1007/s12665-017-6804-5 Uppin, M., Karro, E., Determination of boron and fluoride sources in groundwater: Batch dissolution of carbonate rocks in water. Geochem. J., 2013, vol. 47, no. 5, pp. 525-535. https://doi.org/ 10.2343/geochemj.2.0274

Journal Pre-proof WHO: World Health Organization., Guidelines for Drinking-water Quality, 2011, https://apps. Who.int /iri s/bitstream/handl e/10665/44584/9789241548151_eng.pdf Xiao, J., Li, F., Zhong, Q., Bao, H., Wang, B., Huang, J., Zhang, Y., Separation of aluminum and silica from coal gangue by elevated temperature acid leaching for the preparation of alumina and SiC. Hydrometallurgy, 2015, vol.155, pp.118–124. Yadav, K.K., et al., Fluoride contamination, health problems and remediation methods in Asian groundwater: A comprehensive review. Ecotox Environ Safe., 2019, Vol. 182, 109362. https://www.sciencedirect.com/science/article/pii/S0147651319306839 Yammani, S.R., Reddy, T.V.K., Reddy, M.R.K., Identification of influencing factors for

of

groundwater quality variation using multivariate analysis. Environ Geol., 2008. Vol. 55, pp

ro

9–16. doi:10.1007/s00254-007-0958-5.

Yidana, S.M., Ophori, D., Yakubo, B.B., Hydrochemical evaluation of the Voltaian system-

-p

The Afram Plains area, Ghana. J Environ Manage., 2008. Vol. 88, pp 697-707.

Jo ur

na

lP

re

https://doi.org/10.1016/j.jenvman.2007.03.037.

Journal Pre-proof List of Tables: 1. Table 1. Results of physicochemical analysis of water sample 2. Table 2. Pearson correlation matrix among the physicochemical parameters of water samples 3. Table 3. Factor loading of the principal components along with Eigen value, percentage and cumulative percentage variance explained

List of Figures:

of

1. Fig. 1 Location map of the study area in the Dhanbad, Jharkhand. 2. Fig. 2 Hydrogeolocial details of the study area

ro

3. Fig. 3 Piper plot representing the composition of groundwater of the study area 4. Fig. 4 (a) Gibbs diagram (anions) (b) Gibbs diagram (cation) (c) (Ca2++Mg2+) vs total cation

-p

(tz) (d) (Ca2+ + Mg2+) vs (HCO3- + SO42-) (e) Na+ vs Cl- (f) stability and weathering products

re

of K2O–H2O–Al2O3–SiO2 system (g) Stability and weathering products of NaO–H2O–Al2O3– SiO2 system (g) [(Na+ + K+) - Cl-] vs [(Ca2+ + Mg2+) - (HCO3- + SO42 -)]

lP

5. Fig. 5 Saturation Index of fluorite and calcite

Jo ur

na

6. Fig. 6 scatter plots (a) NO3- vs K+ (b) NO3- vs SO42- (c) SO42- and Cl-

Journal Pre-proof Table 1. Detail of physicochemical results of water samples.

Gharbar brahmantola

S4

Gharbar well

S5

Gharbar brahmantola

S6

Gharbar brahmantola

S7

Gharbar brahmantola

S8

Gharbar brahmantola

S9

Gharbar brahmantola

S10

Gharbar brahmantola

S11

Gharbar brahmantola

S12

Gharbar bouri tola

S13

Gharbar bouri tola

S14

Gharbar bouri tola

S15

Gharbar bouri tola

S16

Gharbar bouri tola Gharbar bandtand

S18

Gharbar bandtand

S19

Gharbar bandtand

Jo ur

S17

S20

Gharbar bandtand

S21

Gharbar bandtand

S22 S23 S24 S25 S26 S27 S28 S29 S30

Birsingpur school kadadih Birshingpur manjhi tola Birshingpur harimandir Birshingpur bouri tola

Birshingpur manjhidi Birshingpur main di Birshingpur road side Birshingpur rajak tola 1 Birshingpur depth bouring

428. 3 165. 2 341. 9 724. 0 984. 7 1028 .3 813. 1 565. 8 478. 6 453. 7 751. 2 260. 9 368. 3 573. 7 366. 7 718. 0 214. 8 191. 8 272. 9 124. 1 166. 5 299. 3 150. 9 241. 9 126. 6 832. 2 255. 3 159. 7 638. 2 643. 9

K+ 13. 2 11. 7 30. 3 15. 8 13. 8 15. 2 14. 7 14. 2 16. 9 14. 2 14. 6 14. 1 14. 9 15. 3 14. 2 13. 8 13. 3 15. 1 14. 7 12. 8 16. 1 12. 4 13. 6 14. 4 13. 5 14. 5 13. 9 15. 3 15. 1 12. 9

Mg

Ca2

2+

+

7.7 2.8 2.0 7.3 11. 4 12. 8 12. 0 17. 2 8.9

18. 6 13. 2 26. 8 15. 7 21. 6 27. 0 48. 8 74. 5 22. 8 15. 6 19. 5 35. 1 114 .6 158 .6 105 .0 23. 2 68. 7 33. 0 20. 4 29. 2 24. 3 15. 7 32. 7 20. 2 21. 5 18. 2 33. 6 52. 0 16. 5 14. 9

4.5 9.2

10. 9 20. 1 29. 2 23. 0 3.9 11. 4 10. 7 8.9 12. 3 11. 3 4.8 14. 5 8.1 9.0 8.7 11. 7 9.4 5.8 6.1

F4.3 16. 7 18. 5 8.7 5.3 4.1 5.0

Cl305 .3 177 .3 49. 1 135 .8 316 .3 438 .7 202 .3 377 .8 166 .4 116 .3 230 .7 131 .9 405 .3 390 .4 335 .0 251 .3 147 .6 121 .4 90. 8 149 .9 107 .2 111 .2 170 .7 123 .8 88. 0 263 .8 117 .8 86. 5 80. 8 102 .2

of

S3

820. 0 470. 0 400. 0 790. 0 1010 .0 1020 .0 950. 0 930. 0 680. 0 550. 0 870. 0 650. 0 980. 0 1080 .0 900. 0 690. 0 660. 0 620. 0 490. 0 560. 0 610. 0 430. 0 670. 0 540. 0 440. 0 850. 0 680. 0 500. 0 710. 0 400. 0

Na+

ro

Gharbar brahmantola

560 .0 520 .0 460 .0 680 .0 820 .0 830 .0 750 .0 640 .0 570 .0 530 .0 730 .0 500 .0 630 .0 690 .0 640 .0 720 .0 500 .0 480 .0 450 .0 430 .0 490 .0 450 .0 130 .0 480 .0 410 .0 820 .0 550 .0 460 .0 700 .0 710 .0

TDS

-p

S2

EC

re

Gharbar brahmantola

p H 7. 1 8. 6 8. 6 7. 6 7. 1 7. 2 7. 2 6. 9 7. 1 7. 6 7. 2 7. 1 6. 6 6. 7 6. 8 7. 8 7. 0 7. 0 7. 3 6. 8 6. 9 7. 1 6. 9 7. 1 7. 2 6. 8 6. 9 7. 0 7. 1 7. 2

lP

S1

Location

na

Sample No.

0.4 2.4 7.4 6.1 3.0 1.7 1.3 1.8

11. 6 0.9 2.4 3.7 4.2 1.3 4.5 0.4 0.2 1.4 5.3 7.3 1.2 5.3 5.2

HC O312.2 353. 8 97.6 97.6 500. 2 341. 6 317. 2 524. 6 366. 0 439. 2 231. 8 427. 0 378. 2 195. 2 353. 8 219. 6 97.6 329. 4 231. 8 341. 6 353. 8 402. 6 158. 6 317. 2 292. 8 366. 0 463. 6 341. 6 366. 0 463. 6

SO

NO

24

78. 1 53. 4 24. 3 80. 4 111 .9 139 .5 87. 5 127 .8 50. 9 42. 3 85. 7 56. 6 118 .6 201 .9 178 .9 77. 2 65. 1 60. 1 45. 5 48. 8 48. 3 20. 8 64. 6 39. 3 32. 8 63. 4 57. 6 36. 1 39. 7 48. 8

PO

3

39. 1 49. 7 34. 1 78. 1 69. 7 50. 4 43. 5 45. 2 48. 6 43. 7 43. 6 44. 1 121 .4 319 .1 202 .3 45. 2 44. 4 52. 3 44. 7 69. 3 45. 1 45. 1 128 .9 74. 4 42. 6 72. 5 104 .4 57. 4 65. 3 76. 6

24

6.2 6.4 1.3 2.3 6.6 7.3 2.4 6.2 6.7 3.2 4.2 3.3 5.9 4.3 5.8 1.2 3.2 4.2 1.2 2.5 5.7 3.5 3.6 6.2 1.5 5.2 5.7 2.3 3.2 3.2

Journal Pre-proof

S34 S35 S36 S37 S38 S39 S40 S41

Simpathor school Simpathor manjhi than Siompathor anganbari Simpathor kashinath malakar Simpathor subodh malakar Simpathor manjhi kulhi Simpathor road side Simpathor bhola kumar Simpathor hari mandir

S42

Asanbani school

S43

Asanbani road side

S44

Asanbani road side 2

S45

Asanbani village

S46

Kalipur hari mandir

S47

Kalipur upar kulhi

S48

Kalipur majhi kulhi

S50

Mean

Jo ur

S49

Gharbar sanjay sarkar Gharbar tapas mukhargi

Standard deviation Minimum Maximum

K+

654. 9 361. 6 160. 5 191. 1 92.4 204. 1 238. 0 610. 7 241. 2 208. 2 127. 6 457. 2 207. 8 255. 1 228. 6 262. 3 296. 4 666. 5 792. 9 643. 7 404. 8 250. 4

12. 9 19. 7 15. 3 15. 2 12. 8 14. 1 13. 3 13. 2 15. 0 15. 5 14. 7 13. 9 15. 4 14. 4 14. 4 14. 8 12. 9 13. 6 15. 2 12. 6 14. 7

92.4 1028 .3

Mg

Ca2

2+

+

6.2 6.7 14. 1 11. 5 9.0 12. 7 17. 0 6.4 16. 7 12. 8

2.6 11. 7 30. 3

10. 2 18. 8 31. 9 18. 4 29. 4 58. 6 181 .1 19. 1 46. 3 35. 8 37. 1 18. 6 26. 7 21. 9 33. 2 41. 8 31. 7 17. 7 116 .3 19. 9 39. 1 36. 3 10. 2 181 .1

8.6 8.2 8.7 9.3 7.9

14. 3 9.6 9.0 20. 2 3.4 10. 6 5.2 2.0 29. 2

4.0

8.4 82. 9 208 .5 341 .0 159 .9 100 .4 70. 4 46. 7 74. 5 71. 3 191 .9 163 .2 589 .4 63. 6 105 .1 294 .5 142 .0 174 .9 122 .0

HC O3183. 0 268. 4 231. 8 341. 6 268. 4 280. 6 317. 2 292. 8 488. 0 427. 0 317. 2 329. 4 390. 4 292. 8 317. 2 366. 0 353. 8 841. 8 475. 8 134. 2 326. 0 134. 5

0.2 18. 5

8.4 589 .4

12.2 841. 8

F2.2 3.2 0.9 1.0 1.0 1.4 1.3 5.6

Cl156 .5 16. 1 65. 9

of

S33

490. 0 550. 0 670. 0 470. 0 460. 0 720. 0 1020 .0 730. 0 790. 0 660. 0 560. 0 720. 0 600. 0 610. 0 490. 0 750. 0 710. 0 830. 0 850. 0 860. 0 689. 8 182. 5 400. 0 1080 .0

Na+

ro

S32

Birshingpur rajak tola 2

490 .0 500 .0 540 .0 440 .0 420 .0 580 .0 690 .0 700 .0 610 .0 540 .0 480 .0 660 .0 540 .0 550 .0 480 .0 630 .0 620 .0 770 .0 780 .0 765 .0 582 .3 136 .3 130 .0 830 .0

TDS

-p

Birshingpur well

EC

re

S31

p H 7. 5 7. 2 6. 9 7. 1 7. 0 6. 9 6. 6 7. 2 7. 0 7. 3 6. 9 7. 1 7. 0 7. 1 7. 1 6. 9 6. 9 7. 2 7. 3 7. 4 7. 1 0. 4 6. 6 8. 6

lP

Location

na

Sample No.

0.3 0.4 0.3 3.4 0.6 2.3 2.9 1.9 0.5 1.2 2.5

13. 0 3.7

SO

NO

24

50. 0 29. 7 40. 8 13. 3 32. 2 68. 3 109 .8 49. 8 37. 4 32. 9 30. 2 42. 3 38. 8 69. 2 40. 7 174 .0 60. 0 57. 9 118 .8 58. 0 66. 8 41. 5 13. 3 201 .9

PO

3

74. 3 41. 0 63. 2 34. 1 42. 7 122 .2 284 .6 74. 0 117 .2 107 .7 56. 5 93. 2 61. 1 59. 5 57. 1 126 .3 77. 4 90. 5 52. 4 37. 6 77. 5 56. 6 34. 1 319 .1

24

6.1 4.3 3.1 4.2 1.3 5.9 3.2 2.3 4.2 1.3 3.3 3.5 2.1 3.2 2.1 4.5 3.3 4.1 5.1 4.1 3.9 1.7 1.2 7.3

Journal Pre-proof Table 2. Pearson Correlation matrix among the physicochemical parameters of water samples

Tds Na+ K+

Mg2+ Ca2+

Na+

K+

Mg2+

Ph Ec 1.00 0.02 1.00 0.38 0.70 1.00 0.16 0.81 0.57 1.00 0.40 0.10 0.15 0.01 1.00 0.61 0.13 0.61 0.03 0.11 1.00 0.41 0.20 0.56 0.04 0.02 0.80

Ca2

F-

+

1.0 0 0.2 9

0.20 0.12 0.81 0.29 0.34 0.55

Cl-

0.24 0.46 0.69 0.39 0.16 0.54

HCO3-

0.19 0.28 0.11 0.12 0.20 0.16

CO32-

0.12 0.08 0.16 0.24 0.02 0.14

NO3-

0.42 0.14 0.48 0.06 0.10 0.71

0.7 6

SO42-

0.28 0.48 0.76 0.40 0.11 0.71

0.6 5

PO42-

0.17 0.27 0.41 0.29 0.16 0.27

0.1 2

Jo ur

na

lP

re

-p

F-

Values in bold are different from 0 with a significance level alpha=0.05

HC O3-

Cl-

CO

NO

23

SO

3

PO

24

24

of

Ec

TD S

ro

Variabl es Ph

0.5 2 0.0 2 0.0 0

1.0 0 0.0 5 0.2 6 0.0 4 0.2 9 0.1 0 0.0 9

1. 00 0. 02 0. 22

1.0 0 0.3 2

1. 00

0. 43

0.0 5

0. 06

1. 00

0. 90

0.0 2

0. 26

0. 59

1. 00

0. 47

0.1 9

0. 07

0. 11

0. 41

1. 00

Journal Pre-proof Table 3. Factor loading of the principal components along with Eigen value, percentage and cumulative percentage variance explained. Principal Components PC3 -0.327 0.248 0.026 0.220 -0.608 -0.161 -0.404 -0.369 -0.123 0.641 -0.347 -0.216 0.294 1.591

39.778

20.319

12.242

39.778

60.097

72.338

of

PC2 0.602 0.679 0.307 0.808 0.205 -0.375 -0.262 0.743 0.275 -0.035 -0.305 0.205 0.238 2.641

-p

re lP

% of variance explained

PC1 -0.574 0.525 0.862 0.348 -0.255 0.843 0.764 -0.377 0.804 0.207 0.708 0.890 0.467 5.171

ro

Groundwater chemical parameters pH EC TDS Na+ K+ Mg2+ Ca2+ FClHCO3NO32SO42PO42Eigen value

Jo ur

na

Cumulative % of variance explained

Journal Pre-proof Highlights  occurrence of high fluoride in drinking water of the study area  Maximum mobilization of fluoride associated with Na-HCO3 water type  Chemical weathering along with ion-exchange bear the blue print of fluoride release  Inverse geochemical modelling indicates under-saturation of fluoride

na

lP

re

-p

ro

of

Alkaline aquifer condition accelerates the F- accumulation in groundwater

Jo ur



Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6