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.