Elevated fluoride in groundwater of Siwani Block

Groundwater for Sustainable Development xxx (xxxx) xxx–xxx

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Research paper

Elevated fluoride in groundwater of Siwani Block, Western Haryana, India: A potential concern for sustainable water supplies for drinking and irrigation ⁎

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Shakir Alia, , Shashank Shekhara, , Prosun Bhattacharyab, Gaurav Vermac, Trupti Chandrasekhard, A.K. Chandrashekhare a

Department of Geology, University of Delhi, Delhi 110007, India KTH-International Groundwater Arsenic Research Group, Department of Sustainable Development, Environmental Science and Engineering, KTH Royal Institute of Technology, Teknikringen 10B, SE-100 44 Stockholm, Sweden c Department of Geology, Kurukshetra University, Kurukshetra 136119, India d Department of Earth Sciences, Indian Institute of Technology, Bombay, Mumbai 400076, India e Department of Geology, Adama Science and Technology University, Ethiopia b

A R T I C LE I N FO

A B S T R A C T

Keywords: Fluoride pollution Salinity Dental and Skeletal fluorosis Haryana India

Groundwater pollution is a serious health concern in north-western India. In this study, we have reported very high concentration of fluoride i.e. 18.5 and 16.6 mg/l from Sainiwas locality in Siwani block of Bhiwani district, Haryana, India. The values are much higher than the permissible limit set by WHO and BIS. The evapotranspiration in the area leads to Ca2+ precipitation, which allows an increase in F- content in the groundwater. In addition, the replacement of hydroxyl of secondary clay mineral under alkaline condition is responsible for release of F-. In absence of alternative source, the fluoride polluted groundwater in some of these localities is also used for drinking. Further, the suitability of groundwater for irrigation is also evaluated by various parameters such as Sodium Adsorption Ratio (SAR), Sodium Percentage (Na%), Kelly's Ratio (KR), Magnesium Hazard (MH) and Residual Sodium Carbonate (RSC). It emerges out that in a few localities, groundwater is not suitable for irrigation and with respect to Magnesium Hazard (MH) almost all samples are unsuitable for irrigation. This article highlights groundwater quality of Siwani block in Haryana and proposes for immediate remedial measures.

1. Introduction The North West India has emerged as a global groundwater contamination hotspot, especially with respect to overexploitation of the aquifers (Shekhar, 2006; Chatterjee et al., 2009; Sarkar et al., 2016; Saha et al., 2016). Further, the overprinting of anthropogenic footprints of the enhanced water use for various purposes is quite visible in the chemistry of the groundwater system (Bundschuh et al., 2004; Shekhar and Sarkar, 2013; Sarkar and Shekhar, 2015; Sarkar et al., 2017; Das et al., 2017). The high ingestion of fluoride in human body leads to dental fluorosis and in long term can cause skeletal fluorosis (Susheela, 1999; Edmunds and Smedley, 2001). Fluorine, one of the lightest halogen elements in the earth's crust is mobile under high temperature conditions and occurs as negative charge ions (F¯) in solution (Hem, 1985). Fluorite, biotite and phlogopite, found in various rocks and sediments are some of the geogenic

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sources of fluoride in groundwater (Handa, 1975; Hem, 1985). High alkalinity, bicarbonate concentration and electrical conductivity controls fluoride dissolution in the groundwater (Saxena and Ahmed, 2001; Ali et al., 2016). Groundwater with elevated fluoride concentrations is observed throughout the globe (Vithanage and Prosun, 2015a; Ali et al., 2016; Patel et al., 2017; Maity et al., 2018). The high level of fluoride pollution in groundwater is observed in various countries mainly Ethiopia (Ayenew, 2008; Rango et al., 2009), Kenya (Nair et al., 1984), China (Fuhong and Shuqin, 1988), India (Latha et al., 1999; Das et al., 2000; Jacks et al., 2005; Shekhar et al., 2006, 2015; Brindha et al., 2011; Shekhar and Sarkar, 2013; Ali et al., 2016; Bundschuh et al., 2017), Iran (Battaleb-Looie. et al., 2012); Argentina (Bhattacharya et al., 2006; Gomez et al., 2009; Nicolli et al., 2012), Sri Lanka (Vithanage and Bhattacharya, 2015b) and even in Brazil (Martins et al., 2018), and different parts of Africa (Bhattacharya et al., 2016; Kut et al., 2016).

Corresponding authors. E-mail addresses: [email protected] (S. Ali), [email protected] (S. Shekhar).

https://doi.org/10.1016/j.gsd.2018.05.008 Received 15 July 2017; Received in revised form 12 May 2018; Accepted 29 May 2018 2352-801X/ © 2018 Published by Elsevier B.V.

Please cite this article as: Ali, S., Groundwater for Sustainable Development (2018), https://doi.org/10.1016/j.gsd.2018.05.008


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Fig. 1. Map of the Siwani block of Bhiwani District in Western Haryana. Bottom picture shows groundwater sampling locations.

Mostly, high concentration of fluoride in groundwater is confined to arid and semi-arid zones (Ali et al., 2016). Fluoride in groundwater of Haryana has been reported since last decades especially in the districts of Jind (Meenakshi et al., 2004), Hisar (Ravindra and Garg, 2006), Gurgaon (Singh et al., 2007), Bhiwani (Garg et al., 2009) Sirsa (Mor et al., 2009) and Sonipat; (Sheikh et al., 2017). This study was conducted to evaluate fluoride concentrations in the groundwater of Siwani block of district Bhiwani covering Jhumpa, Motipura, Gaindawas, Sainiwas, Gurera, Siwani and Barwa localities (Fig. 1). Various cases of dental fluorosis were observed amongst the population in the Siwani block. Further long term ingestion of this fluoridated water may cause skeletal fluorosis. This study was conducted with the objective to understand the spatial distribution and the possible source of fluoride in the aquifers of Siwani block. Being the agriculturally dominated state, groundwater for irrigation was also evaluated for its suitability for irrigation.

India. The Siwani block of Bhiwani district lies in between 28°41′ N to 29°57′ N latitudes and E75°30′ to E75°49′ longitudes (Fig. 1). In overall the Bhiwani district in its west is bordered by the arid state of Rajasthan.

1.2. Climate The climate of Bhiwani district is tropical and summers are hot and dry and winters are cold. The hot arid summers prevails from March to June and afterwards followed by south-west monsoon upto September. The winters prevails from December and lasts upto March (Kumar, 2013).

1.3. Land use characteristics The land use land cover (LULC) of Siwani block comprises of build areas (0.01%), agricultural fields (0.31%), waste lands (67%) with negligible water bodies and forest area (Dinesh, 2014; Table 1). Most of the areas are covered with sands and the region has scanty rainfall.

1.1. Study area The Siwani block is situated in Bhiwani district of Haryana state in 2


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sampling was done during pre-monsoon season of year 2016. The groundwater samples from shallow as well as deep aquifer were collected in the plastic cans and the can was sealed thereafter.

Table 1 Land use characteristics in the study area around Siwani Block (Dinesh, 2014). S. No.

Land Use

Area (km2)

1 2 3 4 5 6

Built Agriculture Forest plantation Waste land Water bodies Total

7.1 214.0 0.30 451.1 0.08 672.86

2.2. Groundwater level data collection The groundwater level data were compiled from the CGWB database of the pre-monsoon season (2014). Based on the data, the water table contour and depth to water level map was prepared in Surfer 11 environment.

2. Material and methods

2.3. Groundwater analyses

2.1. Groundwater sampling

The samples were analyzed at the central laboratory of Central Soil Salinity Research Institute (CSSRI), Karnal in Haryana for major ions and fluoride. The pH, EC and TDS were analyzed in the laboratory using pH, EC and TDS meters. The Na and K concentration were determined from Flame Photometer, while parameters such as sulphate, fluoride

Ten groundwater samples were collected from six villages i.e. from Siwani block in Bhiwani district of Haryana. The sampling sites were identified with the help of survey of India map and google earth. The

Fig. 2. Geological map of Haryana (modified after Thussu, 2006). Fluoride concentration in mg/L is marked on the map as reported by previous workers (Table 2). 3


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Fig. 3. Subsurface cross-section along Bhiwani district comprising Siwani block (After Thussu, 2006). AB cross section line is shown in Fig. 2.

Fig. 4. Groundwater level contours (shown as black lines) and groundwater level map (shown with variation in colors) of Bhiwani district (CGWB, 2014).

diamine as buffer with NaOH solution and Solochrome Black T as an indicator and it was titrated with EDTA solution. The concentrations were calculated using Eq. (1) as per IS:3025 method:

Table 2 Fluoride concentration in groundwater of various parts of Haryana. S. No.

District

Locality/area

Fluoride concentrations (mg/L)

References

1

Jind

Jind

0.3–6.9

2

Hissar

Hissar

0.3–16.6

3

Gurgaon

4

Bhiwani

5 6 7

Sirsa Sonipat Bhiwani

Pataudi Haily Mandi Harsaru Sainiwas Motipura Mishri Sirsa Sonipat Siwani block

0.9–2.9 1.9–5.2 1.7–1.9 7.4–76 8.8–86 1.2–44 0.1–1.9 0.6–6.7 0.3–18.5

Meenakshi. et al. (2004) Ravindra and Garg (2006) Singh et al. (2007)

TH = VEDTA × NEDTA × 50 × 1000/ VSAMPLE

(1)

where, VEDTA = Volume of EDTA consumed NEDTA=Normality of EDTA VSAMPLE =Volume of sample while, for Mg2+ concentration, the Ca2+ concentrations were subtracted from the TH concentrations. Total alkalinity (TA) was determined through titration with Standard sulphuric acid solution (0.02Normality) using phenolphthalein as an indicator. The pink colour confirmed the presence of CO3 and for HCO3 methyl orange was used as an indicator and titrated. For the determination of TA concentrations in mg/L, the formula shown as Eq. (2) was used (IS: 3025):

Garg et al. (2009)

Mor et al. (2009) Sheikh et al. (2017) This study

and nitrate were analyzed using Ion Chromatograph. The Total Hardness (TH) was determined by following IS:3025 methods. The samples were analyzed with buffer solution of NH4ClNH4OH with Eriochrome Black T as indicator and titrated with EDTA solution. The Ca2+ concentration was determined using ethylene

TA = VH 2SO 4 × 50 × 1000/ VGW where, VGW- Volume of groundwater sample and 4

(2)


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Table 3 Hydrogeochemistry of groundwater of the study area during pre-monsoon. Major ions and fluoride are in mg/L. Depth is in metre; EC is in µS/cm; N D-Not detected. S.No.

Location

Latitudes N

Longitudes E

Depth

pH

EC

CO3

HCO3

Cl¯

SO4

NO3

F¯

Na

K

Ca

Mg

Water Type

1 2 3 4 5 6 7 8 9 10

Sainiwas 1 Barwa 1 Barwa 2 Siwani 2 Sainiwas 2 Motipura Siwani 1 Jhumpa Kallan Jhumpa Kallan 1 Gaindawas

28.826797 28.956837 28.955645 28.91154 28.825585 28.805423 28.9095579 28.780042 28.77182 28.862662

75.539017 75.600849 75.600849 75.6091529 75.540245 75.551698 75.5986729 75.527686 75.52892 75.595257

15.2 18.2 19.8 19.8 27.4 30.4 30.4 35 36.5 51.8

8.1 8 7.9 7.3 8.5 7.7 7.5 7.5 7.6 9.3

2400 6800 6600 3200 2000 6700 900 8000 8500 7300

0 0 0 0 60 0 0 0 0 210

510 1590 1305 735 540 450 130 525 1380 555

77 358.4 195.4 147 77.9 678.1 188.7 61.1 34.2 20

22.9 60.6 31.8 12.5 136.4 29.6 16.9 23.3 38.7 39.7

0 0 0 246.6 49.9 0 0 0 113.8 23.4

16.6 4.4 N.D 7 18.5 2.3 N.D 1.5 0.3 6.2

65.6 410.2 78 30.3 63.3 151.6 90.6 206.1 116.6 260.6

39.8 9.7 4.8 39.3 4.2 10.5 9.4 2 2.4 7.5

68.1 68.1 156.3 56.1 10 60.1 16 100.2 140 30

165.3 78.3 366 157.9 12 163.4 26.3 211.8 396 108

Na-Mg-HCO3-Cl Na-Mg-HCO3-Cl Mg-HCO3- Cl Mg-HCO3-Cl Na-Ca-Mg-HCO3-Cl Mg-Na-Cl-HCO3 Na-Mg-Cl Mg-Ca- HCO3 Mg-HCO3 Na-Mg-HCO3

Fig. 5. Piper Trilinear plot depicting the hydrochemical facies of groundwater samples during pre-monsoon season (2016).

where, all ions are in meq/L.

VH2SO4 = Volume of H2SO4 solution

2.5.2. Sodium percentage Sodium percentage (SP) is an important factor for determining the quality of groundwater for irrigation. Sodium in irrigational water reduces infiltration rate to the root zones. The Na% (Wilcox, 1955) was estimated by using Eq. (4):

2.4. Chemical data analyses The chemical data was first checked for ion balance. Only those data where the ion balance error was less than 20% was retained for this study, while the others were discarded. This data was further analyzed with the help of suitable graphical plots like: Piper's Trilinear plot, bivariate plot and box and whisker diagram. As the objective was focused around F-, thus in the bivariate plot with F-, the two data where F- was not detected was not considered. Further for assessment of irrigation water quality various plots were used which is discussed below.

Na% = ((Na + K )/(Ca2 + + Mg2 + + Na+ + K+)) × 100

(4)

where, all ions are in meq/L. 2.5.3. Magnesium hazard Magnesium in irrigation water increases alkalinity in soil and it reduces crop yield. The magnesium hazard (MH) is estimated with the help of Eq. (5) (Szabolcs and Darab, 1964):

2.5. Assessment of irrigation water quality The quality of groundwater for irrigation was evaluated with the help of various plots such as: Sodium Adsorption Ratio (SAR), Sodium percentage (SP), Magnesium Hazard (MH), Kelly's Ratio (KR) and Residual Sodium Carbonate (RSC).

MH = (Mg2 +/(Ca2 + + Mg2 +)) × 100

(5)

where, all concentrations are in meq/L.

2.5.1. Sodium adsorption ratio SAR defines the rate of infiltration of water to the crops (Ayers and Westcot, 1985) and thus affects the permeability. The SAR was estimated using Eq. (3):

2.5.4. Kelly's ratio Kelly's Ratio (KR) is the ratio of concentration of sodium to magnesium and calcium (Kelly, 1963). Low calcium concentration in irrigation water reduces rate of infiltration. The KR is calculated by the Eq. (6):

SAR = Na+/√ (Ca2 + + Mg2 +)/2

KR = Na+/(Ca2 + + Mg2 +)

(3) 5

(6)


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Fig. 6. Bivariate plots showing the relationships between fluoride concentration with EC, Ca2+ and pH during pre-monsoon season.

Fig. 7. Depth wise variations of EC, fluoride and Ca in Siwani block during pre-monsoon season.

RSC = (CO32 − + HCO−3 ) − (Ca2 + + Mg2 +)

where all values are in meq/L.

(7)

where all values are in meq/L. 2.5.5. Residual sodium carbonate RSC estimates alkalinity hazard of soil. Balaji et al. (2017) states that high RSC value drastically reduces infiltration capacity. The RSC is calculated using Eq. (7):

3. Geological characteristics of the study area On a regional scale, the geology of the region is covered by the 6


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Fig. 8. Major ion compositions in groundwater samples Note the concentration units are in meq/L.

Fig. 9. XRD of bulk sediments from Siwani block.

7


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and Sainiwas village of Siwani block in Haryana. Further Meenakshi. et al. (2004) reported 6.7 mg/L of fluoride from village Malar in Jind district. Similarly 16.6 mg/L of fluoride was also reported from Hissar district (Ravindra and Garg, 2006). 4. Results and discussion 4.1. Groundwater chemistry 4.1.1. Major ion chemistry Among the major anions (Table 3), HCO3 was dominant during premonsoon and its concentration varies from 130 to 1500 mg/L and concentration of the SO4 varies from 16.9 to 136 mg/L. While the concentration of Cl varies from 20 to 678 mg/L. Similarly among the cations, Mg was dominant with concentration in the range of 12–396 mg/L and concentration of Na varies from 30.3 to 410 mg/L. While the concentration of Ca varies from 10 to 156 mg/L and the concentration of K varies from 2 to 40 mg/L. The pH of the groundwater is usually high and range between 7.3 and 9.3 with an average of 8.3. This indicates alkaline nature of the groundwater.

Fig. 10. A schematic drawing elucidating fluoride enrichment in the groundwater of the study area (After Jacks et al., 2005).

argillaceous rocks of Alwar Group and the Alwar quartzite of Delhi Supergroup, Malani volcanics suite of lower Vindhyan Supergroup, older Quaternary alluvial deposits and Holocene to recent aeolian sands (CGWB, 2012; Fig. 2). The Siwani block is mostly covered by older Quaternary alluvium and Holocene to recent aeolian sands (Fig. 2). The subsurface geology consists of inter bedded deposits of gravel, sand, silt, and clay mixed with kankars (Fig. 3) in various proportions (GSI, 2012).

4.2. Fluoride concentration in groundwater This study reports very high value of fluoride concentration beyond the maximum permissible limit set by WHO (2011) and BIS (2012) i.e 1.5 mg/L in the study area. The fluoride concentration varies between 0.3 and 18.5 mg/L while fluoride is not detected in two samples. Groundwater samples from localities such as Sainiwas, Barwa, Siwani, Motipura and Gaindawas have high fluoride concentrations (Table 3).

3.1. Groundwater level In the study area, the alluvium, sands, silt, kankars and gravel form the water bearing zones (CGWB, 2012). In general the shallow aquifers are unconfined. A further insight into the hydrogeology of the area is attempted by studying variation of water level (Fig. 4). The variation in groundwater level for May 2014 and the water table contours for the same season (Fig. 4) was studied. In general, groundwater level in the area varies in the range of 2–10 m below ground level (mbgl). The shallower water level in the range of 2–5 mbgl is found in northern parts of the study area around Siwani and Tosham (Fig. 4). The groundwater level increases towards the eastern and western fringes of the district where the groundwater level is at the range of 20 m bgl and upto 30–40 m bgl respectively. The groundwater table elevation varies in the range of 200–222 m above mean sea level. Prima facie it appears shallower water level in the region such as Siwani, Bawani Khera and Tosham region has higher hydraulic head.

4.3. Hydrochemical facies The Piper's (1944) trilinear diagram is most efficient for comparing and representing Hydrochemical facies. The groundwater samples were plotted in the diagram for understanding the Hydrochemical facies of the groundwater system of the Siwani block (Fig. 5). The groundwater in general is dominated by Mg-Na- HCO3-Cl type waters (Table 3). Samples such as Motipura and Siwani1 have chloride dominance, while all other samples are bicarbonate dominant (Fig. 5). 4.4. Interrelationship between fluoride with other hydrochemical parameters The bivariate plot of F- with EC, Ca and pH shows interesting results (Fig. 6). Though, the overall EC of groundwater samples are high (> 2000 µS/cm), interestingly F- concentration in the groundwater shows significant negative correlation with EC. Similarly, fluoride concentration in the groundwater shows reasonably good negative correlation with Ca. It indicates that higher F- concentration in

3.2. Fluoride in groundwater of the state of Haryana A number of earlier studies have explored the fluoride concentrations in groundwater of Haryana state (Table 2 and Fig. 2). Garg et al. (2009) observed a maximum value of 86 and 76 mg/L from Motipura Table 4 Statistical analyses of the groundwater samples from Siwani block.

Depth pH EC CO3 HCO3 Cl¯ SO4 NO3 F¯ Na K Ca Mg

Depth

pH

EC

CO3

HCO3

Cl¯

SO4

NO3

F¯

Na

K

Ca

Mg

1.00 0.47 0.42 0.73 − 0.27 − 0.25 0.01 − 0.09 − 0.27 0.24 − 0.54 − 0.17 − 0.01

1.00 0.07 0.89 − 0.06 − 0.26 0.47 − 0.32 0.44 0.32 − 0.19 − 0.36 − 0.30

1.00 0.14 0.56 0.11 − 0.17 − 0.12 − 0.55 0.55 − 0.50 0.64 0.62

1.00 − 0.21 − 0.34 0.25 − 0.08 0.22 0.27 − 0.19 − 0.41 − 0.28

1.00 0.02 0.11 0.13 − 0.26 0.40 − 0.20 0.67 0.54

1.00 − 0.10 − 0.24 − 0.27 0.23 − 0.04 − 0.06 − 0.12

1.00 − 0.10 0.58 0.07 − 0.37 − 0.34 − 0.38

1.00 0.07 − 0.40 0.46 0.01 0.15

1.00 − 0.25 0.45 − 0.50 − 0.47

1.00 − 0.37 − 0.03 − 0.19

1.00 − 0.19 − 0.14

1.00 0.95

1.00

8


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Table 5 Irrigation parameters for groundwater and their classification. PARAMETERS

Permissible Range

Classification

Sample name

Sodium Adsorption Ratio (SAR)

< 10

Excellent

Sodium Percentage (SP)

10–18 18–26 > 26 0–20

Good Fair Poor Excellent

20–40 40–60 60–80 > 80 2 < 1.25 1.25–2.5 > 2.5

Good Permissible Doubtful Unsuitable Suitable Marginal Unsuitable Suitable Marginal Unsuitable

< 50 > 50

Suitable Unsuitable

Motipura, Jhumpa,Kallan, Siwani 1, Siwani 2, Barwa 2 Jhumpa Kallan1, Gaindawas, Sainiwas1, Sainiwas2 Barwa 1 Nil Nil Motipura, Jhumpa,Kallan, Sainiwas1, Siwani 1, Siwani 2, Barwa 2, Gaindawas, Jhumpa Kallan1, Sainiwas2, Gaindawas. Nil Nil Nil Nil Motipura, Jhumpa Kallan, Sainiwas1, Siwani 2, Barwa 2, Jhumpa Kallan1, Siwani 1, Barwa 1 Sainiwas2, Gaindawas, Sainiwas1, Motipura, Jhumpa Kallan, Sainiwas1, Jhumpa Kallan1. Nil Nil Barwa 1, Sainiwas2, Gaindawas, Sainiwas2, Barwa2 Nil Motipura, Jhumpa Kallan, Sainiwas1, Siwani 1, Siwani 2, Barwa 1, Barwa 2, Jhumpa Kallan1, Sainiwas 2, Gaindawas

Kelly's Ratio (KR)

Residual Sodium Carbonate (RSC)

Magnesium Hazard (MH)

groundwater is linked to depletion of Ca. The bivariate plot of F- with pH indicates that the fluoride polluted groundwater is alkaline in nature. Further, though not very significant, yet there is a positive correlation of F- with pH, indicating possible F- enrichment with increase in alkalinity (Fig. 6). The depth wise plot of EC (Fig. 7) suggests that the deeper aquifers are more saline than shallower one. This is due to the fact that the groundwater in deeper aquifers has longer residence time. It is also observed that fluoride concentration in some shallow aquifers is higher than the deeper aquifers, which might be indicating evapotranspiration linkage to the fluoride enrichment in groundwater (Fig. 7). In contrast to this the concentration of Ca does not show a distinct variation with depth (Fig. 7). The box and whisker diagram was used for comparison of major ions (Fig. 8). The diagram suggests that one data in parameters such as Cl, SO4 and NO3 from Siwani block is highly variable than the other data (Fig. 8a). It also reveals dominance of HCO3-, Mg and Na ions over and above the others. Further Fig. 8b reveals that the concentration of Ca2+ is much lower than the Mg2+. As discussed earlier, it is quite possible that the evapotranspiration in the semiarid climate triggers precipitation of Ca2+. Further, this enriches groundwater in Na and Mg ions. All these chemical processes leads to an increase in F- level. Jacks et al. (2005) had a similar observation for fluoride enrichment in groundwater.

dominance of Mg2+ and Na+ ions in the groundwater. The high pH of the groundwater triggers release of fluoride from hydroxyl groups of minerals such as biotite and sepiolite leading to fluoride enrichment beyond permissible limits in the groundwater. Similar observations for release of F- in the groundwater system were also made by Jacks et al. (2005). 4.6. Statistical analyses with correlation matrix The correlation matrix helps us in appreciating association of the ions. The correlation matrix (Table 4) reveals that the F- has reasonably good positive correlation with pH, cations like K+ and anions like SO42-. While F- has negative correlation with EC, Ca2+ and Mg2+. This indicates that in future, with due course of time, the increase in Fconcentration may lead to further precipitation of Mg2+ with Ca2+ leading to enrichment of Na+ in groundwater. This is in confirmation with hypothesis for fluoride enrichment in groundwater of the discharge areas with passage of time (Jacks et al., 2005). The EC has good positive correlation with HCO3- and Na+, while it has negative correlation with F-. Thus it also emerges out that EC of the groundwater is controlled by HCO3- ions. 5. Irrigation water quality The irrigation water quality is assessed in detail and the results are given as Table 5. The SAR and SP values suggest that majority of the groundwater samples have excellent irrigation water quality. In perspective of the Kelly's Ratio (KR), two samples are marginal and two samples are found to be unsuitable for irrigation. Similarly with respect to the Residual Sodium Carbonate (RSC) values, almost five samples are unsuitable for irrigation. While the MH values suggest that all the groundwater samples of the pre-monsoon seasons are unsuitable for irrigation.

4.5. Bulk sediment chemistry The X-ray diffraction pattern (XRD) of the sediment collected from 1.5 m below the ground indicates the presence of fluoride bearing miner i.e. Biotite (K(Mg,Fe)3(AlS10)(F,OH)2. Further, the presence of secondary mineral like sepiolite, which is weathering product of biotite (Yalcin and Bozkaya, 1995) authenticates geogenic enrichment of F- in groundwater by weathering of the biotites (Fig. 9). Fig. 10 is the general geochemical observation seen in the Siwani block. A schematic drawing elucidating fluoride enrichment in the groundwater (after Jacks et. al, 2005) is given as Fig. 10. It is proposed that initially F- from atmosphere and fertilizer is mobilized in to the groundwater system by recharge from rainfall runoff and irrigation return flow. Also limited weathering of biotite contributes F- in to the groundwater system. Further, the chemistry of groundwater evolves by evapotranspiration induced Ca2+ precipitation leading to the

6. Conclusions The study reveals that fluoride pollution in groundwater of Siwani block of Haryana has reached alarming levels. The evapotranspiration process in the area induces Ca2+ precipitation leading to the dominance of Mg2+ and Na+ ions in the groundwater. The high pH of the groundwater triggers release of F- from hydroxyl groups of minerals such as biotite and sepiolite leading to fluoride enrichment beyond 9


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permissible limits in the groundwater. The occurrence of F- and NO32together beyond desirable limit in a few samples also indicate possibility anthropogenic enrichment of F- in groundwater. With respect to suitability of water for irrigation, in a few localities groundwater is not suitable for irrigation and in the context of Magnesium Hazard (MH) almost all samples are unsuitable for irrigation. A time has come to have a deeper insight in to the issue in a holistic water management framework.

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