Hydrochemical baseline condition of groundwater at the Mizunami underground research laboratory (MIU)

Hydrochemical conditions up to depths of 1000 m below ground level around the Mizunami Underground Research Laboratory were investigated to construct a “baseline condition model” describing the undisturbed hydrochemical environment prior to excavation of the underground facilities at Mizunami, Gifu, Japan. Groundwater chemistry in this area was classified into a Na–Ca–HCO₃ type of groundwater in the upper part of sedimentary rock sequence and a Na–(Ca)–Cl type of groundwater in the deeper part of the sedimentary rock sequence and basement granite. The residence time of the groundwaters was estimated from their ¹⁴C contents to be approximately 9.3 ka in the middle part of the sedimentary rock and older than 50 ka in the deep part of the granite. The evolution processes of these groundwaters were inferred to be water–rock interactions such as weathering of plagioclase, dissolution of marine sulphate/sulphide minerals and carbonate minerals in the Na–Ca–HCO₃ type of groundwater, and mixing between “low-salinity water” in the shallow part and “higher-salinity water” in the deeper part of the granite in the Na–(Ca)–Cl type of groundwater. The source of salinity in the deeper part of the granite was possibly a palaeo-hydrothermal water or a fossil seawater that recharged in the Miocene, subsequently being modified by long-term water–rock interaction. The Cl-depth trend in granitic groundwater changes at a depth of −400 m below sea level. The hydrogeological properties controlling the groundwater flow and/or mixing processes such as advection and diffusion were inferred to be different at this depth in the granite. This hydrochemical conceptual model is indispensable not only when constructing the numerical model for evaluating the hydrochemical disturbance during construction and operation of the MIU facility, but also when confirming a hydrogeological model.     

Association of hydrogeological factors in temporal variations of fluoride concentration in a crystalline aquifer in India

The major part of groundwater in India is found in granitic aquifers. Fluoride in groundwater from a crystalline aquifer in a semi-arid region of granitic rocks in India, known as Maheshwaram watershed, was analyzed for spatial and temporal variability during 1999–2002 to assess the effect of hydrogeological factors on fluoride concentration. Samples were collected from 32 representative wells in the area for the pre- and post-monsoon seasons and analyzed for F content. The CHESS computer program was used to calculate ionic activities of aqueous species and the mineral saturation index (SI) for calcite and fluorite. The GARDENIA computer program was used to calculate the recharge values in the study area. The influences of dissolution kinetics of fluoride minerals and recharge from rainfall on fluoride concentration were of interest and results clearly indicate that fluoride content in groundwater depends on the interaction period of groundwater with host rock. Results could also be utilized for designing remedial measures particularly with dilution method in an optimal way.     

Estimating groundwater residence time using multiple regression model based on fluoride dissolution: an exploration of possibilities

High levels of fluoride concentration were observed in deep groundwater of the Mizunami area in Central Japan. Fluoride occurs mainly due to the reaction between granitic basement rock and groundwater. Granites were collected, crushed to powder, and then allowed to react with purified water for 80 days. Water–rock interaction results showed that the major factor affecting fluoride concentration is the residence time of the groundwater. Coexisting ions have also some contribution toward fluoride concentration. The groundwater residence time in the Mizunami area was estimated by applying results of water–rock interaction to correspond with field data. A regression model relating fluoride concentration, residence time, and coexisting ions was developed. The parameters of the regression model were determined using the genetic algorithms technique. Residence time was estimated by extrapolating experimental data to correspond with filed data. Near the recharge area, residence times in the potential fluoride source rock varied between 1 and 2,000 years, whereas near the discharge area residence times were in excess of tens of thousands of years. The groundwater residence time was also estimated by the groundwater particle-tracking-flow model. The estimates of groundwater residence time based on geochemical regression model were often larger than estimates of groundwater residence time developed by particle-tracking analysis using a groundwater flow model. There were large uncertainties—on the order of 10–10,000 years—in the estimates based on geochemical data.     

Geochemical characteristics of fluoride in groundwater of Gimcheon, Korea: lithogenic and agricultural origins

The occurrence of fluoride in groundwaters can be influenced by many factors. In Korea, the fluoride-rich groundwaters are normally associated with rock types, especially granite and gneiss. In Gimcheon, high-fluoride groundwaters (up to a maximum of 2.15 mg/L) were observed with bimodal distribution of concentrations. The groundwater in this area showed relatively high concentrations of anthropogenic chemicals such as nitrate, chloride, and sulfate. Statistical analysis showed that fluoride is positively correlated with pH, alkalinity, sodium, and lithium, indicating that the interaction with granite is the main cause enriching its concentration. In Gimcheon, δ¹⁸O data of groundwater showed a negative correlation with nitrate and can be used as an indicator of groundwater age. The four samples of fluoride-rich groundwater were plotted in the light δD and δ¹⁸O region, showing that they were the result of long water–rock reaction. However, other groundwater with a low-fluoride concentration was evenly distributed throughout all δD and δ¹⁸O ranges and did not show a statistically significant correlation with nitrate, indicating possible mixing with another source of fluoride. Considering the influence from the surface on the geochemical characteristics of groundwater in this area, anthropogenic sources including phosphate fertilizer containing fluoride and pesticides may also have partly contributed to the concentrations of fluoride in the low-fluoride groundwater. The scattered distribution of fluoride-rich groundwater and the significant correlation with lithium suggest that pegmatite is the main rock type increasing fluoride concentration in this area.     

Geochemical processes controlling the elevated fluoride concentrations in groundwaters of the Taiyuan Basin,Northern China

High fluoride groundwater with F⁻ concentration up to 6.20 mg/L occurs in Taiyuan basin, northern China. The high fluoride groundwater zones are mainly located in the discharge areas, especially in places where shallow groundwater occurs (the groundwater depth is less than 4 m). Regional hydrogeochemical investigation indicates that processes including hydrolysis of silicate minerals, cation exchange, and evaporation should be responsible for the increase in average contents of major ions in groundwater from the recharge areas to the discharge areas. The concentration of F⁻ in groundwater is positively correlated with that of HCO₃⁻ and Na⁺, indicating that groundwater with high HCO₃⁻ and Na⁺ contents help dissolve some fluoride-rich minerals. The water samples with high F⁻ concentration generally have relatively higher pH value, implying that alkaline environment favors the replacement of exchangeable F⁻ in fluoride-rich minerals by OH⁻ in groundwater. In addition, the mixing of karst water along the western mountain front and the evaporation may also be important factors for the occurrence of high fluoride groundwater. The inverse geochemical modeling using PHREEQC supports the results of hydrogeochemical analyses. The modeling results show that in the recharge and flow-through area of the northern Taiyuan basin, interactions between groundwater and fluoride-rich minerals are the major factor for the increase of F⁻ concentration, whereas in the discharge area of the northern basin, the evaporation as well as the mixing of karst water has greater contribution to the fluoride enrichment in groundwater.     

Geochemistry of fluoride rich groundwater in Kolar and Tumkur Districts of Karnataka

Groundwater is a significant water resource in India for domestic, irrigation, and industrial needs. By far the most serious natural groundwater-quality problem in India, in terms of public health, derives from high fluoride, arsenic, and iron concentrations. Hydrogeochemical investigation of fluoride contaminated groundwater samples from Kolar and Tumkur Districts in Karnataka are undertaken to understand the quality and potability of groundwater from the study area, the level of fluoride contamination, the origin and geochemical mechanisms driving the fluoride enrichment. Majority of the groundwater samples did not meet the potable water criteria as they contained excess (>1.5 mg/L) fluoride, dissolved salts (>500 mg/L) and total hardness (75–924 mg/L). Hydrogeochemical facies of the groundwater samples suggest that rock weathering and evaporation–crystallization control the groundwater composition in the study area with 50–67% of samples belonging to the Ca–HCO₃ type and the remaining falling into the mixed Ca–Na–HCO₃ or Ca–Mg–Cl type. The saturation index values indicated that the groundwater in the study area is oversaturated with respect to calcite and under-saturated with respect to fluorite. The deficiency of calcium ion concentration in the groundwater from calcite precipitation favors fluorite dissolution leading to excess fluoride concentration.     

Regional appraisal of the fluoride occurrence in groundwaters of Andhra Pradesh

Fluoride (F^?) is essential for normal bone growth, but higher concentration in the drinking water causes health problems which are reported in many states of India. Andhra Pradesh is one of the states which suffer from excess fluoride in groundwater particularly in the hard rock terrain. In this context, a study was conducted in Andhra Pradesh based on chemical analysis of water samples from hydrograph net work stations (dug wells) and exploratory bore wells. The concentration of fluoride in groundwaters ranges from traces to 9.75 mg/l. The occurrence of fluoride is mostly sporadic, uneven and varies with depth. The highly affected districts include Nalgonda and Warangal in Telangana region, Prakasam in coastal region, Anantapur and Kurnool in Rayalaseema region. In certain areas of Nalgonda district, 85% of wells have fluoride more than permissible limit (> 1.5 mg/l) for drinking water. High F^? is present in all the geological formations, predominantly in granitic aquifers, compared to the other formations. The average value of fluoride is high in the deeper zone (1.10 mg/L), compared to the shallow zone (0.69 mg/L). The fluoride-rich minerals present are the main sources for fluoride concentrations in groundwater. Residence time, evapotranspiration and weathering processes are some of the other supplementary factors for high fluoride concentrations in groundwater. Long-term data of hydrograph net work stations (dug wells) reveal that fluoride concentrations do not show any marked change of trend with respect to time. The concentration of fluoride is found to increase with increase of Na⁺and HCO ₃ ^? , and decrease with increase of Ca²⁺. Sodium bicarbonate waters are more effective in releasing fluoride from minerals into groundwater. High fluoride waters are of Na⁺ type. The paper presents a brief account of the study and its results.     

Fluoride occurrence and mobilization in geo-environment of semi-arid Granite watershed in southern peninsular India

Plausible forms of fluoride (F) responsible for the persistence of fluoride toxicity in ground water of a granitic terrain of semi-arid region, which is the main source of drinking water, have been studied. The study area in Anantapur District of Andhra Pradesh, India, is one of the chronic regions with excess fluoride in groundwater and the region is under transformation into aridity due to poor rainfall and over-exploitation of groundwater. Geochemical analysis of soil, groundwater, and rock samples of the study area revealed the presence of other toxic elements also in addition to fluoride which need to be addressed in drinking water sector in near future. Soil fluoride leaching experiments demonstrated the probable mode of mobilization of F into the groundwater through natural recharge process during monsoon. Analysis of saturation indices indicates that the fluorite solubility alone is not attributable to the high fluoride content in groundwater. The groundwater flow controls fluoride mobilization in the study area as it is evidenced through fluoride concentration and electrical conductivity increase from catchment to downstream region. Creation of lesser fluoride groundwater sources through rainwater harvesting and artificial recharge of groundwater in catchment areas is suggested as a long-term sustainable safe drinking water strategy.     

Geochemical processes controlling fluoride-bearing groundwater in the granitic aquifer of a semi-arid region

The aim of the present study is to identify the geochemical processes responsible for higher fluoride (F^–) content in the groundwater of the Yellareddigudem watershed located in Nalgonda district, Andhra Pradesh. The basement rocks in the study area comprise mainly of granites (pink and grey varieties), which contain F-bearing minerals (fluorite, biotite and hornblende). The results of the study area suggest that the groundwater is characterized by Na⁺: HCO facies. The F^– content varies from 0.42 to 7.50 mg/L. In about 68% of the collected groundwater samples, the concentration of F^– exceeds the national drinking water quality limit of 1.5 mg/L. The weathering of the granitic rocks causes the release of Na⁺ and HCO ions, which increase the solubility of ions. Ion exchange between Na+ and Ca²⁺, and precipitation of CaCO₃ reduce the activity of Ca²⁺. This favours dissolution of CaF₂ from the F-bearing minerals present in the host rocks, leading to a higher concentration of F^– in the groundwater. The study further suggests that the spatial variation in the F^– content appears to be caused by difference in the relative occurrence of F-bearing minerals, the degree of rockweathering and fracturing, the residence time of water in the aquifer materials and the associated geochemical processes. The study emphasizes the need for appropriate management measures to mitigate the effect of higher F groundwater on human health.     

Isotope hydrochemical approach to understand fluoride release into groundwaters of Ilkal area,Bagalkot District,Karnataka, India

Isotope and hydrochemical investigations have been carried out in the Ilkal area of Karnataka, India, in order to determine the source and mechanism of fluoride release into groundwaters and to understand groundwater hydrochemistry. Agriculture, granite quarrying and rock-polishing industries are the main occupations in this area. Closepet granite, Peninsular gneiss and Dharwar schists are the major geological formations. Results show that the fluoride concentration in groundwater is 0.3–6.5 mg/L and it is found to increase from recharge area to discharge area. Fluoride variability is found to be influenced by the geology of the area and depth wise correlation was not observed. Water samples are unsaturated with respect to fluorite, indicating the possibility of further increase in fluoride in groundwater. Positive correlations between fluoride with sodium and bicarbonate in groundwater show that high fluoride content and alkaline sodic characteristics are the result of dissolution of fluoride bearing minerals, possibly derived from weathered granite and gneiss. A positive correlation between fluoride and δ¹⁸O, and the presence of high tritium in fluoride-contaminated groundwater, point to contribution from surface waters, contaminated by anthropogenic activities. Dumping of rock wastes that are rich in fluoride into the streams by the rock-polishing industries plays a significant role in contaminating groundwater.     

Modeling of water–rock interactions in an aquitard of sandy clay in the coastal area near Beihai,China

Unconsolidated sand, gravel and clay deposits near Beihai and in the Leizhou Peninsula in southern China form an unconfined aquifer, aquitard and a confined aquifer. Water and soil samples were collected from the two aquifers in the coastal Beihai area for the determination of chemical compositions, minerals and soluble ions. Hydrogeochemical modeling of three flow paths through the aquitard are carried out using PHREEQC to determine water–rock interactions along the flow paths. The results indicate that the dissolution of anorthite, fluorite, halite, rhodochrosite and CO₂, and precipitation of potash feldspar and kaolinite may be occurring when groundwater leaks through the aquitard from the unconfined aquifer to the confined aquifer. Cation exchanges between Na and Ca can also happen along the flow paths.     

Geochemical processes regulating groundwater chemistry with special reference to nitrate and fluoride enrichment in Chhatarpur area, Madhya Pradesh, India

The present study focuses on the hydrogeochemical composition of groundwater in Chhatarpur area with special focus on nitrate and fluoride contamination, considering the fact that groundwater is the only major source of drinking water here. Carbonate and silicate mineral weathering followed by ground water–surface water interactions, ion exchange and anthropogenic activities are mainly responsible for high concentrations of cations and anions in the groundwater in the region. The average concentration of nitrate and fluoride found in 27 samples is 1.08 and 61.4 mg/L, respectively. Nitrate enrichment mainly occurs in areas occupied with intense fertilizer practice in agricultural fields. Since the area is not dominated by industrialization, the possibility of anthropogenic input of fluoride is almost negligible, thus the enrichment of fluoride in groundwater is only possible due to rock–water interaction. The highly alkaline conditions, which favor the fluorite dissolution, are the main process responsible for high concentration of fluoride.     

Grey model for prediction of pore pressure change

Prediction of pore pressure change is an effective tool to properly monitor changes of groundwater flow caused by any construction work in fractured rock mass. Due to the complexity of hydrogeologic conditions in fractured rock and the scale of interest of the study domain, prediction of pore pressure changes by numerical models has not been precise enough to meet monitoring requirements. Considering these problems, a Grey model that combines the finite element method (FEM) and the artificial neural network (ANN) was developed for more precise prediction of pore pressure changes. In this model, several patterns of pore pressure changes were calculated by FEM for a simplified hydrogeologic conceptual model at a scale smaller than a representative elementary volume. The ANN model was then constructed to predict the actual pore pressure change using these FEM results as inputs. This modeling approach was adopted to predict the pore pressure changes caused by the construction of shafts of Mizunami Underground Research Laboratory (MIU), Japan. From the results obtained for MIU, it can be concluded that the proposed Grey model is a powerful tool for monitoring of pore pressure changes.     

Petrogenesis and geological history of a uranium source rock: a case study in northeastern Washington,U.S.A.

A small (4 km²) drainage basin in northeastern Washington contains highly uraniferous groundwater and highly uraniferous peaty sediments of Holocene age. The U is derived from granitic bedrock that underlies the entire drainage basin and that contains 9–16 ppm U. This local bedrock was studied by petrographic, chemical and isotopic methods to determine conditions of its petrogenesis and post-emplacement history that may have contributed to its present high U content and source-rock capability. The original magma was derived by anatexis of Precambrian continental crust of probable mixed metaigneous and metasedimentary character. Mineral-melt partitioning controlled the enrichment of U in chemically evolved phases of the crystallizing melt. Following emplacement in the upper crust at ∼100Ma, the pluton interacted with meteoric-hydrothermal water at ambient temperatures 300°C. Locally intense fracturing promoted alteration, and fracturing and alteration probably continued during later regional uplift in the Eocene. Regional uplift was followed by low-temperature alteration and weathering in the middle to late Tertiary. The combined result of hydrothermal alteration and low-temperature alteration and weathering was the redistribution of U from primary mineral hosts such as allanite to new sites on fracture surfaces and in secondary minerals such as hematite. Zones of highly fractured and altered rock show the most obvious evidence of this process. A model is proposed in which high-angle fractures beneath the drainage basin were the sites of Tertiary supergene enrichments of U. Recent glacio-isostatic uplift has elevated these older enriched zones to shallow levels where they are now being leached by oxidizing groundwater. The chemistry, mineralogy, texture and geological history of this U source-rock suggest criteria for locating other granitic terrane that may contain uraniferous waters and associated young surficial U deposits. The details of U distribution and mobility at this site also apply to the general topic of U mobility in granitic rocks.     

Fluoride hydrogeochemistry and bioavailability in groundwater and soil of an endemic fluorosis belt,central Iran

Presence of fluoride in groundwater is a public health problem in the so-called endemic fluorosis belt of the central Iran, where the groundwater is the major source of drinking water in most urban and rural areas. Therefore, an attempt has been made to determine the hydrogeochemical factors controlling fluoride enrichment in the groundwater resources at this belt. Fluoride concentrations ranged from 0.20 to 1.99 mg/L (1.02 ± 0.47) in groundwater samples. The presence of different F-bearing minerals and also clay minerals in the soils and aquifer materials was confirmed using XRD analysis. To identify probable sources of dissolved F^? and investigate groundwater quality, multivariate statistical analyses were carried out. Geochemical modeling indicated that all samples were undersaturated with respect to fluorite, halite, gypsum and anhydrite and mostly oversaturated with respect to calcite and dolomite. Contrary to most high-fluoride regions in the World, the high F^? content was dominated by Na–Cl- and Ca–SO₄-type groundwater in the study area. Besides, fluoride showed negative relationship with pH and HCO₃ ^? in groundwater. In order to assess the bioavailability of fluoride in soils, a two-step chemical fractionation method was applied. The results showed that fluoride in soils mostly accompanied with the residual and water-soluble fractions and was poorly associated with soil’s bonding sites. Calculated aqueous migration coefficient demonstrated that fluoride in the studied soils was mobile to easily leachable to the groundwater. Finally, the results demonstrated that combination of water–rock interaction and influence of clay minerals is geochemical mechanism responsible for controlling fluoride enrichment in groundwater.     

Geochemical Modelling of Fluoride Concentration in Hard Rock Terrain of Madhya Pradesh, India

The aim of the present study is to locate and decipher the groundwater quality,types,and hydrogeochemical reactions,which are responsible for elevated concentration of fluoride in the Chhindwara district in Madhya Pradesh,India.Groundwater samples,quality data and other ancillary information were collected for 26 villages in the Chhindwara District,M.P.India during May 2006.The saturation index was computed for the selected samples in the region,which suggest that generally most of the minerals are saturated with respect to water.The concentration of fluoride in the region varies from 0.6 to 4.74 mg/l,which is much higher as per the national and international water quality standards.The study also reveals that the fluoride bearing rock formations are the main source of the higher concentration of fluoride in groundwater along with the conjuncture of land use change.Moreover,the area is a hard rock terrain and consists of fractured granites and amygdaloidal and highly jointed compact basalt acting as good aquifer,which is probably enriching the high content of fluoride in groundwater.High concentration of fluoride is found in deeper level of groundwater and it is possible due to rock-water interaction,which requires further detailed investigation.The highly alkaline conditions indicate fluorite dissolution,which works as a major process for higher concentration of fluoride in the study area.The results of this study will ultimately help in the identification of risk areas and taking measures to mitigate negative impacts related to fluoride pollution and toxicity.     

Mechanism of fluoride enrichment in groundwater of hard rock aquifers in Medak,Telangana State,South India

A total of 194 groundwater samples were collected from wells in hard rock aquifers of the Medak district, South India, to assess the distribution of fluoride in groundwater and to determine whether this chemical constituent was likely to be causing adverse health effects on groundwater user in the region. The study revealed that the fluoride concentration in groundwater ranged between 0.2 and 7.4 mg/L with an average concentration of 2.7 mg/L. About 57% of groundwater tested has fluoride concentrations more than the maximum permissible limit of 1.5 mg/L. The highest concentrations of fluoride were measured in groundwater in the north-eastern part of the Medak region especially in the Siddipeta, Chinnakodur, Nanganoor and Dubhaka regions. The areas are underlain by granites which contain fluoride-bearing minerals like apatite and biotite. Due to water–rock interactions, the fluoride has become enriched in groundwater due to the weathering and leaching of fluoride-bearing minerals. The pH and bicarbonate concentrations of the groundwater are varied from 6.6 to 8.8 and 18 to 527 mg/L, respectively. High fluoride concentration in the groundwater of the study area is observed when pH and the bicarbonate concentration are high. Data plotted in Gibbs diagram show that all groundwater samples fall under rock weathering dominance group with a trend towards the evaporation dominance category. An assessment of the chemical composition of groundwater reveals that most of the groundwater samples have compositions of Ca²⁺–Mg²⁺–Cl^? > Ca²⁺–Na⁺–HCO₃ ^? > Ca²⁺–HCO₃ ^? > Na⁺–HCO₃ ^?. This suggests that the characteristics of the groundwater flow regime, long residence time and the extent of groundwater interaction with rocks are the major factors that influence the concentration of fluoride. It is advised not to utilize the groundwater for drinking purpose in the areas delineated, and they should depend on alternate safe source.     

The origin of fluoride in the granitic aquifer of Porto Alegre, Southern Brazil

The Porto Alegre region, Southern Brazil, comprises a fractured aquifer system constituted by pre-Cambrian granitic and gneissic rocks, and a porous aquifer system formed by Cenozoic muddy–sandy to sandy sediments. A model is presented for the origin of the fluoride in the groundwater of the fractured aquifer system, based on ionic interrelations, a statistical analysis of physicochemical parameters and geochemical modeling. The fluoride is present at levels of up to 6.13 mg/L in groundwater and it arises due to the dissolution of secondary fluorite filling fractures in the granitic and gneissic rocks. The dissolution of fluorite occurs at the same time as calcite and dolomite solubilization. The statistical analysis identified three chemically distinct groups (named 1, 2 and 3) and two subgroups (1A and 1B) of groundwater in the fractured aquifer. The most significant differences between these groups are the different concentration ranges of fluoride, calcium, bicarbonate, magnesium, total dissolved solids and chloride and pH values, as well as the correlations between them. The compositional evolution of each groundwater group is governed mainly by how much high-salinity groundwater from the porous aquifer system is mixed with them and the different thermodynamic equilibrium conditions of calcite, dolomite and fluorite.     

Inferring the chemical parameters for the dissolution of fluoride in groundwater

Geochemical study of groundwater from 58 selected fluoride-rich areas in different parts of India that includes eight states indicates that: 1. These groundwaters are alkaline in pH (7.4-8.8) and their electrical conductivity varies from 530-2,680 µS/cm and fluoride concentration from 1.7-6.1 mg/l. Presence of fluoride-bearing minerals in the host rocks and their interaction with water is considered to be the main cause for fluoride in groundwater. 2. The decomposition, dissociation and dissolution are the main chemical processes for the occurrence of fluoride in groundwater. During rock-water interaction, concentration of fluoride in rock, aqueous ionic species and residence time of interaction, etc. are also important parameters. 3. This study indicates that 85% groundwater samples have EC: 1,000-2,000 µS/cm, pH: 7.5-8.5, and HCO₃/Ca (epm ratio): 0.8-2.3. 4. The Ca and HCO₃ contents of groundwater samples have shown good correlation with fluoride.     

Fluoride contamination in Gharbar Village of Dhanbad District,Jharkhand, India: source identification and management

This paper reports occurrence of high fluoride concentration in groundwater of Gharbar Village, Dhanbad District, Jharkhand, India. The concentration of fluoride varied from 0.3 to 14.9 mg/L in 27 groundwater samples. The correlation studies demonstrate that fluoride has strong positive correlation with pH and sodium and negative correlation with calcium. It indicates dominance of ion exchange activity and rock water interaction. Thermodynamic consideration shows that all the samples were oversaturated with calcite and most of the samples were under saturated with fluorite. The results indicate that occurrence of high concentration of fluoride is leading by geochemical composition of rocks, alkaline environmental condition, weathering of rocks and ion exchange processes.