Accepted Manuscript

FIMAR: A new Fluoride Index for identification of sites to mitigate geogenic

contamination by managed aquifer recharge

L. Kalpana, K. Brindha, L. Elango

PII: S0045-6535(18)32406-8
DOI: https://doi.org/10.1016/j.chemosphere.2018.12.084
Reference: CHEM 22783

To appear in: ECSN

Received Date: 4 September 2018

Revised Date: 29 October 2018
Accepted Date: 10 December 2018

Please cite this article as: 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.

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 ACCEPTED MANUSCRIPT
Manuscript number CHEM56639

FIMAR: A new Fluoride Index for identification of sites to mitigate geogenic

contamination by Managed Aquifer Recharge

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L. Kalpana1, K. Brindha2§, and L. Elango1*

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Department of Geology, Anna University, Chennai 600 025, India

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Hydrogeology Group, Institute of Geological Sciences, Freie Universität Berlin, 12249

Berlin, Germany

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*Corresponding author: elango34@hotmail.com; elango@annauniv.edu
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Email: brindhakarthikeyan@gmail.com; brindha.karthikeyan@fu-berlin.de
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1 Manuscript number CHEM56639

2 FIMAR: A new Fluoride Index for identification of sites to mitigate geogenic

3 contamination by Managed Aquifer Recharge

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5 L. Kalpana1, K. Brindha2, and L. Elango1*

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7 Department of Geology, Anna University, Chennai 600 025, India

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8 Hydrogeology Group, Institute of Geological Sciences, Freie Universität Berlin, 12249

9 Berlin, Germany

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11 *Corresponding author: elango34@hotmail.com; elango@annauniv.edu

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13 Abstract
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14 The objective of this study is to develop a Fluoride Index for mitigation of geogenic
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15 contamination through Managed Aquifer Recharge (FIMAR). This was tested by applying to

16 the Pambar river basin in southern India. About 40% of the study area had fluoride >1.5
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17 mg/L, contributed from the dissolution of fluorite, fluorapatite, biotite and hornblende.

18 Relationship between groundwater level and fluoride concentration exhibited two types of
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19 relationship. In shallow wells, groundwater recharge during monsoon increases the

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20 groundwater level and dilutes the fluoride concentration. During summer, evaporation

21 decreases the groundwater levels and increases the fluoride content. In deep wells, the

22 groundwater recharge flushes the fluoride-rich salts deposited in the unsaturated zone, due to

23 evaporation, in the pre-monsoon season and thus, increases the fluoride concentration with

24 increase in groundwater level. This relationship was used as a key layer in FIMAR. Overlay

25 analysis including the well type derived from the groundwater level and fluoride fluctuation,
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26 average fluoride concentration, geology, geomorphology, soil, drainage density, land use,

27 lineament density and thickness of the weathered zone indicated 30% of the area was suitable

28 for MAR to mitigate fluoride contamination. Since the construction of new MAR structures is

29 cost-intensive, it is proposed to rejuvenate the existing ponds in the areas identified by

30 FIMAR to induce recharge and dilute fluoride concentration. The positive impact was

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31 confirmed using numerical and geochemical modelling. This proves that FIMAR can be used

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32 as a planning tool in fluoride endemic areas and that the future MAR methods will be

33 beneficial to mitigate fluoride contamination.

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34

35 Keywords: Fluoride index; FIMAR; geogenic contamination; managed aquifer recharge;

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FEFLOW; PHREEQC; Pambar River basin; sub-surface dams
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1. Introduction
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39 Major health concern due to high fluoride in groundwater (>1.5 mg/L) is well known and
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40 drinking this groundwater has affected millions of people in different parts of the world. An
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41 estimated 260 million people consume water with fluoride concentration above 1 mg/L

42 (WHO, 1994). Prolonged intake of fluoride above 4 mg/L is known to cause skeletal fluorosis
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43 (Ayoob and Gupta, 2006; Mohammadi et al., 2017). Children are the most affected by high

44 fluoride in drinking water leading to bone deformities and learning disabilities (Raju, 2017;
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Yu et al., 2018).
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45

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47 Of the total 85 million tons of fluoride deposits on the earth’s crust, 12 million tons are found

48 in the rocks and sediments of India (Teotia and Teotia, 1994). Hence, fluoride problem in

49 groundwater is intensive and alarming in the country (Brindha and Elango, 2011).

50 Nineteen administrative states in India contain groundwater with high fluoride concentration

51 (>1.5 mg/L) (CGWB, 2010). Understanding the pathways and mechanisms that drive the
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52 fluoride enrichment in groundwater is vital to formulate scientific methods to overcome this

53 geogenic contamination. Ex-situ methods to remove excess fluoride are more practical in

54 areas where pre-treatment of water is carried out prior to water supply. But, these ex-situ

55 treatment methods are seldom used due to the lack of skills in operation and maintenance and

56 due to the problem associated with the disposal of fluoride rich sludge, which is of

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57 environmental concern. Hence, in rural areas with insufficient or limited water supply, people

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58 have to depend on the untreated high fluoride containing groundwater for drinking and

59 domestic use.

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61 In recent decades, managed aquifer recharge (MAR) through percolation ponds, check dams,

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riverbank filtration etc. are more and more used towards increasing groundwater storage, but
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63 not focused towards improving the groundwater quality. Very few studies exist on the impact
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64 of MAR on lowering fluoride in groundwater, but with mixed results (Bhagavan and Raghu,

65 2005; Andrade, 2012; Gowrisankar et al., 2017). Few studies have also shown increase in
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66 fluoride after implementing MAR (Bhagavan and Raghu, 2005; Pettenati et al., 2014).
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67 Brindha et al. (2016) indicated that an understanding of the temporal variation in groundwater

68 level and fluoride concentration, measured at least on bi-monthly basis is necessary to identify
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69 suitable locations for MAR to mitigate this problem. Such studies carried out in fluoride

endemic areas helped in identifying locations for recharge and in successfully reducing the
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71 fluoride concentration in groundwater below 1.5 mg/L (Brindha et al., 2016).

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73 In order to cope up with wide-scale depletion in groundwater resources, various steps is taken

74 by the Indian Government as well as other agencies. Huge investment is made for sustainable

75 groundwater resources development and management (Ministry of Water Resources, 2016).

76 Nevertheless, such MAR measures have to be taken carefully and judiciously in regions with
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77 fluoride rich groundwater. Hence, in this study a new tool is proposed which can be used by

78 different agencies and the society to identify appropriate locations for improving groundwater

79 storage and overcome the fluoride problem. This index is applied to a fluoride endemic area

80 in the Pambar River basin and the results are evaluated. The three key objectives of this study

81 are: (1) to identify the spatial and temporal evolution of high fluoride groundwater from the

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82 geogenic sources and the mechanisms of fluoride enrichment in groundwater in a part of the

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83 Pambar River basin, (2) to develop a new index to map areas where MAR can be adopted to

84 mitigate high fluoride groundwater and (3) to determine the feasibility of MAR to reduce high

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85 fluoride in the identified locations through numerical and geochemical models.

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87 2. Description of the study area

88 The study area (about 600 km2) is located at about 180 km SW of Chennai, the capital of the
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89 southern state of Tamil Nadu and forms a part of the Pambar River basin (Figure 1a). It is drained

90 by the Pambar River and the streams form dendritic to sub-dendritic drainage pattern (Figure
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91 S1a). The altitude varies from 340 m msl to 1021 m msl and the slope varies from 0o to 41.3o
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92 (Figure S1b). Highest elevation (1021 m msl) is at the summit of the Yelagiri hill, in the north.

Except the hills and hillocks, the area is gently sloping from north (420 m msl) to south (340 m
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94 msl) (Figure S1c). This area experiences arid to semi-arid climate. Average annual rainfall ranges
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95 from 750 to 900 mm.

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97 The study area comprises of metamorphosed Archean basement with gneisses, charnockite and

98 igneous intrusions of Proterozoic age (Figure 1a). The types of gneisses occurring in this area are

99 primarily epidote hornblende biotite gneiss, hornblende biotite gneiss, fissile hornblende biotite

100 gneiss and granitoid gneiss. Charnockites, formed by prograde metamorphism of the gneisses is

101 felsic in nature (Rao and Narayana, 1988). In the late Proterozoic age, igneous intrusions had

102 taken place through deep crustal fractures (Rao and Narayana, 1988). Among the igneous
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103 intrusions, pyroxenite, an ultramafic rock is younger. It is rich in calcium and magnesium bearing

104 pyroxene minerals. The intruded syenite is peralkaline in nature. Carbonatite intrusion in the area

105 is geologically significant in India. These carbonatite rocks contain calcite, fluorite and

106 fluorapatite minerals. Subsequently dolerites are intruded as dykes (Rao and Narayana, 1988).

107 The igneous intrusions are mostly trending in NNE-SSW direction. Geomorphologic features of

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108 the area include pediments, hills and plateaus (Figure S1d).

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110 This area generally comprises of massive rocks as the basement that are highly weathered and

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111 turned to regolith occurring up to a depth of 2.5 m from the ground surface. Basement rocks are

112 exposed at the surface at several locations. The maximum thickness of soil layer is 2.5 m, highly

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weathered zone is 4 m and that of moderately weathered zone is 16.5 m which was identified
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114 during the field visits in the large diameter open wells. Groundwater occurs in unconfined
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115 condition in the weathered and fractured part of the hard rocks. It is tapped by both open wells

116 (shallow, <20 m deep) and tube wells (deep, up to 150 m). Figure 1b shows a hydrogeological
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117 cross section of the sub-surface along the line AA’ . Clayey loam covers major part of the area
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118 followed by red loam, sandy loam and silty clay loam (Figure S1e). Black cotton soil is also

119 found in a few parts. Agriculture is the main activity in this area (Figure S1f) and about 91% of
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120 the area is used for this purpose. Water required for agriculture could not be met from the meagre

surface water storage and therefore, groundwater serves as a vital source.

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123 3. Materials and Methods

124 A field survey was carried out in January 2011 and preliminary observations were made in more

125 than 100 wells located in this area. Lithology, thickness of the weathered rock, depth of the well,

126 groundwater level, electrical conductivity (EC) and pH were recorded. EC and pH was measured

127 using digital portable meters (YSI 556MPS). Elevation of the points from where depth to

128 groundwater level was observed was determined using TRIMBLE explorer 3 Global Positioning
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129 System. After this primary survey, thirty-five representative wells were chosen for regular

130 monitoring (Figure 1a). These monitoring wells include 7 deep bore wells with depth up to 90 m

131 and 28 large diameter open wells. Systematic monitoring was carried out once in two months

132 from January 2011 to June 2012. During every sampling campaign, the groundwater level was

133 measured and a water sample was collected. Pre-cleaned polyethylene bottles (500 ml) were used

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134 to collect the groundwater samples. Alkalinity was measured in the field by titration according to

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135 standard methods (APHA 1998). Major ions and fluoride were analysed in the laboratory by ion

136 chromatography (Metrohm 861 Advanced Compact Ion Chromatograph). Precision of the

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137 analytical methods was ensured by running appropriate standards and blanks. Ion balance error

138 was calculated and was within ±5%.

139
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140 3.1 Data used for spatial maps
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141 Toposheets from Survey of India (SoI) (scale 1:50,000) covering the study area were used to

142 delineate the topography and drainage. Land use/land cover information was derived from
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143 Bhuvan (2008) maintained by the National Remote Sensing Centre (NRSC). Geological map was
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144 prepared initially from the geological map obtained from the Geological Survey of India (scale 1:

145 50,000). This was updated using the Indian Remote Sensing (IRS) satellite 1D –Linear Imaging
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146 Self Scanning sensor (LISS) imagery (dated 18th January 2011) obtained from NRSC and

validated through ground- truth verification. The geomorphological and lineament maps were
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148 prepared using IRS LISS III image and by field observations. Soil map of the area was prepared

149 from the district soil map obtained from SoI. All maps were prepared using ArcMap 10.2.

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151 3.2 Groundwater model conceptualization, calibration and validation

152 Numerical modelling of groundwater flow was carried out using FEFLOW 6. The model was

153 conceptualised as a four-layered system until the fractured zone. For the model development,

154 rainfall data from three rain gauge stations (from 1996 to 2011), groundwater level data of three
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155 monitoring wells (from 1996 to 2011) and information on aquifer characteristics (transmissivity

156 and storativity) were obtained from the Public Works Department (PWD). Part of the groundwater

157 level data between the year 2001 and 2004 were missing and hence, this time-period could not be

158 included in most of the analysis. Apart from this, groundwater level recorded in the monitoring

159 wells as a part of this study was also used.

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160

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161 The model was first calibrated for the steady state condition and then the unsteady state condition.

162 As the groundwater level data of April 1996 was more realistic, this was considered as the initial

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163 water level. Initially, the aquifer parameters derived from pump test data of PWD were assigned

164 spatially. After several trials the best possible match between observed and computed groundwater

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level was obtained (R2= 0.99) (Figure S2a). Standard value of aquifer parameters collected from
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166 literature, the values obtained from pump tests, along with the initial and final ranges used for
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167 steady state calibration are given in Table S1.

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169 In the unsteady state, the groundwater model was calibrated with the recharge of the aquifer by
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170 rainfall and discharge of the groundwater for various purposes. Groundwater level and rainfall

171 data from 1996 to 2004 and the corresponding discharge rates were used for calibration. Rainfall
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172 recharge was estimated as suggested by the Groundwater Estimation Committee (GEC, 1997) and

it varied from 1 to 12%. Groundwater is mainly pumped for agricultural purposes and the
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174 pumping is based on the cropping pattern and rainfall. Therefore, the model period was divided

175 into normal years (+19% to -19% of average annual rainfall), moderate drought years (-19% to -

176 59% of average annual rainfall) and severe drought years (-59% to -99% of average annual

177 rainfall). Expected pumping rates to meet the requirement of various crops were estimated for the

178 different years and used in the model input. Similarly, water requirement for domestic purposes in

179 the settlements was calculated by considering 100 liters of water requirement per person per day,

180 as suggested by the World Health Organisation (WHO) and multiplied with the population of the
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181 settlement. Location of the settlements was delineated from the land use maps. The model was

182 calibrated from April 1996 to December 2004. A good fit was observed between the computed

183 and observed water levels (R2=0.89) (Figure S2b). For the validation, the groundwater model was

184 run for a further period from 2005 to 2011. Simulated groundwater head was compared with the

185 observed groundwater levels in the PWD monitoring wells (Figure S3) which showed reasonable

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186 match. The validated model was used to predict the effect of increase in groundwater level by

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187 MAR.

188

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189 3.3 Geochemical model

190 Geochemical processes and chemical reactions control the occurrence, distribution and

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behavior of chemical ions in groundwater. The saturation index (SI) helps to indicate if a
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192 solution is in equilibrium, over-saturated or in under-saturated state. This was calculated using
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193 PHREEQC 3.1. Apart from this, the mixing of surface water from MAR structures and

194 groundwater with high fluoride concentration was also predicted using this geochemical
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195 model.
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197 4 Results and discussion

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198 Totally 280 groundwater samples were collected and analysed during this study. Detailed
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199 chemical parameters and composition of groundwater samples are summarized in Table S2.
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200 Groundwater chemistry indicates 85% of the area with alkaline pH (up to 9.5) conditions.

201 Most of the analysed groundwater samples indicate fresh to brackish conditions. Geochemical

202 evolution of groundwater show Ca-Na-HCO3, Na-Cl, Ca-Mg-Cl and Ca-HCO3 types (Figure

203 S4). General dominance of cations was in the order of Ca>Mg>Na>K and anions was

204 HCO3>Cl>SO4>F.

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206 4.1 Fluoride occurrence and sources

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207 The maximum concentration of fluoride in groundwater recorded during this study was 4.3

208 mg/L. Based on the Bureau of Indian Standards for drinking water quality (BIS, 1993),

209 fluoride <0.6 mg/L and >1.5 mg/L are unsuitable. Nearly 17% of the area had <0.6 mg/L

210 fluoride and 43% of the area had fluoride between 0.6 to 1.5 mg/L (Figure 2a). But, 40% had

211 fluoride concentration above 1.5 mg/L. Dental fluorosis is prevalent in the study area which

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212 was observed during the field visits (Figure 2b).

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214 Evaporation and rock-water interaction were the major processes controlling the groundwater

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215 chemistry (Brindha et al., 2016). The key fluoride bearing minerals in the rocks of the study

216 area that release fluoride in groundwater are: (1) fluorite (CaF2) and fluorapatite (Ca5(PO4)3F)

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in the carbonatite intrusions, (2) hornblende (Ca2(Mg, Fe, Al)5 (Al,Si)8O22(OH,F)2) and biotite
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218 (K(Mg, Fe)3(AlSi3O10)(F,OH)2) in gneisses. Fluoride content in fluorite is 48.7%, in
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219 fluorapatite is 3.8%, hornblende is 2.9% and biotite is 1.1% (Jagadeshan et al., 2015a).

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221 Alkaline pH of groundwater is more favourable for fluoride dissolution which has been
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222 reported in many fluoride endemic areas (Saxena and Ahmed, 2003; Jagadeshan et al., 2015a;

223 Olaka et al., 2016). Higher the alkalinity, higher is the leaching of fluoride. The alkalinity is
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224 controlled by the leaching of organic matters from the soil layer and also by weathering of

silicate minerals. Silicate minerals like feldspars increase the alkalinity of groundwater by
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226 releasing HCO3 and sodium (equation 1). The positive correlation between pH and fluoride

227 concentration indicates the fluoride release from the inherent rocks in an alkaline environment

228 (Figure 2c-e).

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230 2NaAlSi3O8 + 2H2CO3 + 9H2O → Al2Si2O5(OH)4 + 2Na + 4H4SiO4 + 2HCO3 (2)

231 (Feldspar) (Silicate weathering) (Clay) (1)

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233 4.2 Release of fluoride from different minerals

234 Fluorite is a common mineral in granite and other igneous rocks and a minor constituent in

235 gneisses. In the study area, fluorite occurs in the carbonatite intrusions and the release of

236 fluoride is facilitated by the bicarbonate in groundwater as given in equation 2.

237 CaF2 + 2HCO3 → CaCO3 + H2O + 2F + CO2 (2)

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238

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239 Fluorapatite, a variety of apatite mineral is also abundant in the carbonatite intrusions of

240 this area. The governing reaction (equation 3) for the release of fluoride from fluorapatite

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241 is given by,

242 Ca5(PO4)3F + OH → Ca5(PO4)3OH + F (3)

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244 Fluoride contribution from the silicate minerals like biotite and hornblende, which are the
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245 major minerals in the gneisses of the area are given in equations 4 and 5.

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247 K(Mg, Fe) AlSi3O10(OH, F)2 + 5H2O + 4CO2 → K + Mg + Fe(OH)3 + 4HCO3 + H + 2F

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248 + Al2Si2O5(OH)4 + 2SiO2 (4)

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250 CaNa(Mg, Fe, Al) (Si7Al)O22 (OH, F)2 + H2O + CO2 → Ca + Mg + Na + Fe(OH)3+ HCO3

+ 2F + Al2Si2O5(OH)4 + SiO2
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252 (5)

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254 These reactions not only increase the alkalinity, but also release calcium and magnesium

255 along with fluoride. Released calcium and magnesium tend to exchange with the sodium in

256 the regolith. This reverse ion exchange process increases the sodium content in

257 groundwater (equation 6).

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259 Ca(Mg) + Na-Clay ↔ 2Na + Ca(Mg)Clay (6)

260 Reverse ion exchange was also confirmed by the plot of Na-Cl versus (Ca+Mg)-

261 (HCO3+SO4) (Figure 2f) as the points form a line with slope close to -1. Similar process

262 was also witnessed in the fluoride rich groundwater in other parts India (Saxena and

263 Ahmed, 2003; Jagadeshan et al., 2015a; Panneer et al., 2017). Figure 2g shows the

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264 oversaturation of calcite with increasing pH. This indicates that in alkaline environment,

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265 calcium will precipitate as calcite. This will decrease the calcium content and will favor the

266 fluoride release into groundwater. Presence of kankar deposits noticed during field visits in

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267 several parts of the area confirms the calcite precipitation. Oversaturation of calcite and

268 undersaturation of fluorite also confirms the availability of favourable conditions for the

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fluoride release (Figure 2h). Calcite precipitation is also eased by the evaporation process,
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270 which is commonly experienced in arid and semi-arid areas.
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272 4.3 Index to identify suitable locations for MAR

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273 Fluoride Index for mitigation of the geogenic contamination through Managed Aquifer
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274 Recharge (FIMAR) was developed by integration of different important controlling factors.

275 The most important factors that contribute to the MAR structures are geology,
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276 geomorphology, soil, drainage density, land use, lineament density and the thickness of

weathered zone. However, traditionally in a study like this, the present levels of fluoride in
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278 groundwater or the relation between temporal variation in groundwater level and

279 corresponding fluoride concentration are not considered. It was argued that it is imperative to

280 determine the relationship between temporal groundwater level variation and fluoride

281 concentration in groundwater prior to deciding the location for MAR structures to dilute the

282 fluoride concentration (Brindha et al., 2016). If the MAR structures are not identified based

283 on the long-term relationship in temporal variation between groundwater level and fluoride,
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284 there is a possibility of adverse impact (Bhagavan and Raghu, 2005; Pettenati et al., 2014).

285 Hence, in this study this relationship is also considered.

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287 FIMAR map was developed through index and overlay analysis, a widely used method for

288 mapping wherein ranks are assigned to components within a layer and weights are assigned to

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289 different layers used in the study. FIMAR is calculated using the equation 7,

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291 FIMAR = (WTr x WTw) + (MFr x MFw) + (Gr x Gw) + (GMr x GMw) + (Sr x Sw) + (DDr x

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292 DDw) + (LUr x LUw) + (LDr x LDw) + (TWr x TWw) (7)

293

294 where,
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295 ‘FIMAR’ = Fluoride Index for mitigation of the geogenic contamination through Managed
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296 Aquifer Recharge,

297 ‘WT’ = well type,

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298 ‘MF’ = mean fluoride concentration in the sampling wells,

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299 ‘G’ = geology,

300 ‘GM’ = geomorphology,

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301 ‘S’ = soil type,

‘DD’ = drainage density,

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303 ‘LU’ = land use,

304 ‘LD’ = lineament density,

305 ‘TW’ = thickness of the weathered zone,

306 ‘r’ = rank for the different components within a layer and

307 ‘w’ = weight of the layer.

308
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309 Recharge and discharge (evaporation and dilution) play a significant role in determining the

310 temporal variation of the fluoride concentration in groundwater. Groundwater level in the

311 study area varies from 1.8 to 19.2 m bgl. Brindha et al. (2011) reported two types of well

312 classification based on the groundwater level fluctuation and fluoride concentration in

313 groundwater. According to this classification, in Type I wells (1) groundwater fluctuates at

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314 shallow depth from the ground surface, (2) rise in groundwater level occurs with decrease in

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315 fluoride concentration and vice versa. Recharge of groundwater during monsoon, dilutes the

316 fluoride concentration and high evaporation in these arid/semi-arid zones results in decrease

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317 in groundwater levels and increase in fluoride concentration (Brindha et al., 2011). In Type II

318 wells, (1) groundwater fluctuates at greater depths from the ground surface, (2) rise in

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groundwater level increases the fluoride concentration and vice versa. This is associated with
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320 the evaporation and settling of fluoride rich salts in the unsaturated zone during summer and
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321 the flushing of these salts along with the infiltrating rainwater during monsoon (Brindha et al.,

322 2011; Jagadeshan et al., 2015a, b; Brindha et al., 2016).

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323
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324 Variation in the concentration of fluoride and groundwater level was plotted and based on the

325 relationship, they were classified as Type I (inversely related) and Type II (directly related)
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326 wells (Figures S5a, b). Spatially Type II wells were more distributed in the central part and

the Type I wells were in the northern and southern areas (Figure 3a). It was observed that in
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328 certain Type I cases, the groundwater rises after rainfall with a time lag of one month.

329 Groundwater table was fluctuating within 10 m bgl in Type I and greater than 10 m in Type II

330 (Figure 3b). Also, more number of Type II wells had fluoride above 1.5 mg/L (Figure 3c) due

331 to continuous interaction of groundwater with rock matrix in deeper groundwater

332 environment. Fluctuation in fluoride concentration with groundwater level is governed by

333 several factors like occurrence of fluoride bearing rocks, weathering intensity, soil type, well

334 depth and recharge-discharge. Hence, it is evident that depth to groundwater play a key role in
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335 distinguishing the well type. If MAR is adopted, it would work in Type I wells, whereas in

336 Type II wells, it will increase the fluoride concentration, thus making the situation worse.

337 Only after prolonged period of rainfall, the fluoride level is expected to decrease even in Type

338 II wells. However, such as situation is unlikely due to monsoonal rains which usually occur in

339 spells of two or three days. Hence, rank 1 was assigned to Type I wells as they are more

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340 favourable for MAR and Type II wells are given rank 2 (Figure S6a).

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341

342 Average fluoride concentration in groundwater during the study period was used to delineate

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343 the areas with high fluoride (Figure 3d). Spatial variation in fluoride concentration during the

344 different sampling period based on the average fluoride indicates that the southern part of the

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study area is most affected. Regions with average fluoride concentration above the
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346 permissible limit of 1.5 mg/L were given a rank 1 because these places are important to be
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347 diluted by MAR (Figure S6b).

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349 Similarly, all the components of other layers were assigned ranks (Table S3, Figure S6c-f).
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350 Well type and fluoride content that have a comparatively greater impact than the other

351 parameters were assigned higher weights (Table S3). The newly developed FIMAR applied to
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352 the present study site classifies 30% of the area as suitable for MAR (Figure 4). In order to

validate the outcome of the proposed FIMAR for this study site, both numerical and
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354 geochemical modelling was carried out.

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356 4.4 Numerical and geochemical modelling

357 Brindha et al. (2016) reported the impact of a check dam on diluting the fluoride

358 concentration in groundwater of this area. This study compared the groundwater level and the

359 fluoride concentration over time in an open well located near the check dam. In this well, the

360 concentration of fluoride was continuously decreasing after the implementation of MAR
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361 irrespective of the possible presence of fluoride rich minerals in the rocks. The concentration

362 of fluoride did not exceed the maximum permissible limit of 1.5 mg/L throughout the study

363 period. This confirmed the positive effect of MAR in fluoride mitigation. But, the impact of

364 the method on the entire study area was unknown.

365

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366 These check dams are specially constructed structures along the rivers to facilitate recharge.

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367 Such infrastructure is expensive and may not be feasible in all areas. Alternative choice for

368 MAR could be the surface water bodies that increase recharge and help to maintain the

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369 shallow groundwater level. This area though has an abundant of surface water bodies such as

370 ponds, due to lack of maintenance many of these water bodies have disappeared. This is

371
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evident from the water bodies mapped in the year 1973 and 2008 (Figure S7). Increase in
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372 groundwater levels after rainfall is not effective due to the disappearance of water bodies
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373 which has reduced the rainfall recharge and increased the runoff. An analysis of long term

374 variation in groundwater level and rainfall shows the maximum increase in groundwater
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375 column up to 10 m for 130 mm increase in rainfall and minimum increase of groundwater
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376 column (1 m) for 10 mm rainfall. This is an effect of natural recharge without MAR. By

377 rejuvenating of the unused ponds that are not maintained in recent days and using them as
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378 percolation ponds may increase groundwater recharge. This may in turn dilute the

groundwater with high fluoride concentration. During the study period, though the fluoride
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380 concentration in groundwater was relatively less in the rainy season due to dilution by

381 groundwater recharge in Type I wells, the concentration of fluoride was still above 1.5 mg/L

382 in many wells. Hence, increasing groundwater recharge at these locations may decrease the

383 fluoride below 1.5 mg/L. To understand this effect, the groundwater flow model and the

384 geochemical model were used.

385
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386 A well showing Type I relation (well no. 6) was chosen for the numerical model (Figure 5a).

387 Groundwater level fluctuation between the two sampling period is up to 2.5 m and the

388 average concentration of fluoride in the well is 3 mg/L. Comparison of groundwater level and

389 fluoride indicated that a rise of about 2.5 m in groundwater level results in a reduction in

390 about 1 mg/L of fluoride (Figure 5b). Still, the natural rainfall recharge is not sufficient to

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391 reduce the fluoride concentration below 1.5 mg/L. Two surface water bodies existed near well

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392 no 6 (Figure 5a), but were completely silted up due to poor maintenance and were abandoned.

393 If the two water bodies are rejuvenated and water is stored, the groundwater level in well no.

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394 6 will increase. Through many trail runs of the groundwater model, it was found that if these

395 two ponds have at least 1 m water depth, maximum benefit may be obtained due to recharge.

396
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Prediction of groundwater head was carried out from December 2011 with 1 m of water depth
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397 throughout the year except between March and May. About 5 m increase in groundwater level
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398 is observed (Figure 5c). With this predicted increase in groundwater level, fluoride

399 concentration in the well will be reduced by 2 mg/L. Hence the effect of increased
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400 groundwater recharge will make groundwater in the well suitable for drinking purposes with
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401 respect to fluoride.

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403 Geochemical variation of groundwater in the two well types with respect to calcite was

analysed. Type I wells were more oversaturated with calcite which is responsible for increase
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405 in the leaching of fluoride to groundwater (Figure 6a). Variation in calcite oversaturation,

406 though not significantly different in Type II during and after monsoon, it was comparatively

407 higher in the monsoon period (Figure 6b). Predicting the mixing of surface water and

408 groundwater from a Type I well by geochemical modelling showed the reduction in fluoride

409 concentration and other ions by MAR and evidences that the recharge of groundwater by the

410 ponds will improve the groundwater quality. The ponds during the study were dry and hence,

411 surface water sample from a pond in the upstream of the two MAR ponds (Figure 5a) was
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412 collected and analysed (January 2012). The chemistry of this water is assumed to be the

413 chemical composition of the water that would be stored in the MAR ponds because both the

414 MAR ponds and the sampled pond are located on same rock (epidote hornblende biotite

415 gneiss) and soil (clay and clayey loam) type. Fluoride in the surface water was 0.1 mg/L and

416 in well no. 6 in January 2012 was 2.3 mg/L. The Ministry of Water Resources, Government

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417 of India considers 50% of water stored in water conservation structures is recharged into the

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418 ground. But in this model, even with 40% of recharge, the fluoride in well no. 6 was reduced

419 to 1.45 mg/L (Figure 6c). The pH of groundwater becomes acidic with the increase in mixing

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420 of surface water (Figure 6d) and with the decrease in fluoride concentration in the water, the

421 SI of fluorite mineral also reduces (Figure 6e). The overall groundwater quality also improved

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with the MAR ponds located near Type I wells and the trend of reduction of calcium,
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423 magnesium and sodium are shown in Figures 6f-h. Thus both the field observation, numerical
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424 and geochemical modelling confirms that the suitability of the regions for MAR by the

425 proposed FIMAR.

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427 5. Conclusion

428 An index (FIMAR) is developed based on a geospatial analysis to identify suitable locations
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429 for MAR structures to mitigate high fluoride in groundwater. This was applied to a fluoride

endemic region forming a part of the Pambar River basin, southern India. The dissolution of
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431 fluoride from fluoride bearing minerals like fluorite, fluorapatite, biotite and hornblende and

432 the ion exchange process in the weathered and highly fractured aquifer system is responsible

433 for the elevated amount of fluoride. The analysis of long term rainfall and groundwater level

434 revealed that the natural rainfall recharge vary between 1 to 12% which was not sufficient to

435 dilute fluoride. Fluctuation between groundwater level and fluoride concentration monitored

436 over a two-year period is used as a key layer in the geospatial analysis. The favourable

437 locations where additional recharge will result in mitigating fluoride were identified using
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438 FIMAR. This analysis indicates that considering places with deep groundwater levels for

439 locating recharge options to improve the groundwater may not be effective in regions with

440 high fluoride. Possibility of using the existing non-functional ponds as MAR structures to

441 improve the groundwater quality near the locations identified by FIMAR was tested using the

442 numerical and geochemical methods. Groundwater level simulation and geochemical

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443 modelling of the effect of additional recharge from the MAR indicate that the fluoride

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444 concentration in groundwater can be reduced to desirable levels if the ponds are rejuvenated

445 and 40% of recharge is achieved. This study confirms that the regions with shallow

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446 groundwater are suitable for MAR. Thus, this study for the first time develops an index for

447 location of MAR structures to mitigate fluoride. This FIMAR will serve as a planning tool to

448 mitigate fluoride in endemic regions.

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449
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450 Acknowledgements

451 The present work is part of the Doctoral work of the first author. Funding by the Centre with
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452 Potential for Excellence in Environmental Science scheme of the University Grants
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453 Commission (Grant no. F.No.1-9/2004(NS/PE)) is gratefully acknowledged.

454
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455 References
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456 Andrade, R., 2012. Integrated use of geophysical, hydrological and geographic information
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457 system (GIS) methods in enhancing the groundwater quality in a fluoride-endemic

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461 Bhagavan, S.V.B.K., Raghu, V., 2005. Utility of check dams in dilution of fluoride

462 concentration in ground water and the resultant analysis of blood serum and urine of
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463 villagers, Anantapur District, Andhra Pradesh, India. Environmental Geochemistry

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468 BIS, 1993. Indian standard specififcations for drinking water. IS: 10500, 1992 (Reaffirmed

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487 Jagadeshan, G., Kalpana, L., Elango, L., 2015b. Hydrogeochemistry of high fluoride

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520 Teotia, S.P., Teotia, M., 1994. Endemic fluorosis in India: A challenging national health

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523 Health Status and Fluoride Use [meeting held in Geneva from 22 to 28 November
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524 1993], World Health Organization, Geneva.

525 Yu, X., Chen, J., Li, Y., Liu, H., Hou, C., Zeng, Q., Cui, Y., Zhao, L., Li, P., Zhou, Z., Pang,
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526 S., Tang, S., Tian, K., Zhao, Q., Dong, L., Xu, C., Zhang, X., Zhang, S., Liu, L.,
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527 Wang, A., 2018. Threshold effects of moderately excessive fluoride exposure on

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1 List of figures

2 Figure 1 (a) Location of the study area with geology and sampling locations, (b) cross section

3 along A-A’

4 Figure 2 (a) Fluoride concentration in different range in groundwater samples and associated risk,

5 (b) photograph of a person with dental fluorosis, (c, d, e) bivariate plot of pH and fluoride in few

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6 sampling locations, (f) plot of Na-Cl versus (Ca+Mg)-(HCO3-SO4) showing ion exchange

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7 process, (g) plot of pH versus SI of calcite indicating calcite precipitation, (h) plot of SI of calcite

8 and SI of fluorite showing calcite oversaturation and fluorite undersaturation.

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9 Figure 3 Spatial variation of (a) well type based on the groundwater level and fluoride

10 fluctuation, (b) number of observations with different groundwater level range in Type I and II

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wells, (c) number of samples in different ranges of fluoride concentration in Type I and II wells,
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12 (d) spatial concentration of fluoride in different range.
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13 Figure 4 Demarcation of the area as suitable and unsuitable for MAR based on the FIMAR

14 Figure 5 (a) Location of the percolation ponds near the modelled well (well no. 6) in the model
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15 domain, (b) temporal variations in groundwater level and fluoride concentration in the modelled
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16 well, (c) Temporal variation in predicted groundwater level with increased recharge in the

17 modelled well.
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18 Figure 6 Calcite saturation in different seasons in (a) Type I wells, (b) Type II wells. Different

percentages of surface water mixing with groundwater and respective change in (c) fluoride
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20 concentration in groundwater, (d) pH of groundwater, (e) SI of fluorite, (f) calcium concentration

21 in groundwater, (g) magnesium concentration in groundwater and (h) sodium concentration in

22 groundwater.

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Highlights

• About 40% of the groundwater samples have fluoride above 1.5 mg/L.

• New Fluoride Index applied to identify sites for mitigating geogenic contamination

through Managed Aquifer Recharge (FIMAR).

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• FIMAR indicates 30% of the study area is suitable for managed aquifer recharge.

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• Results from FIMAR is validated through numerical and geochemical models.

• Rejuvenating the existing water bodies will increase recharge by 40% and reduce

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fluoride below 1.5 mg/L.

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