Fluoride occurrence in geothermal water of fault zone area, Southeast China

Fluoride (F^-) is a common trace component in groundwater, and long-term exposure to high-F^- groundwater is harmful to human health. Fluoride concentrations that exceed the World Health Organization guideline for drinking water (1.5 mg/L) have been detected in thermal and non-thermal groundwater from Southeast China, where the causes of the high fluoride occurrence are lack of study. To study the formation and migration mechanism of high fluoride groundwater from Southeast China, we carried out a systemic sampling of water samples in the surrounding area of Heyuan deep fault zone and Zijin-Boluo fault zone, then a comprehensive discussion including water hydrogeochemical, stable isotope composition, as well as hydrogeology analysis was conducted. Fluoride concentrations in geothermal and non-thermal water samples range from 1.11 to 22.76 mg/L and 0.04-8.3 mg/L, respectively. High temperature, alkaline conditions, and the depleted Ca²⁺ by reverse cation exchange and calcite precipitation would promote the release of fluoride from host rock to geothermal water. The availability of Ca-bearing and F-bearing minerals in host rock causes significant differences in fluoride concentrations between carbonate reservoir and granite reservoir. Hydrochemical diagrams reveal that the composition of groundwater is affected by mixing and that fractures act as the mixing channels in our study area. The addition of cold groundwater limits the fluoride concentrations by lowing temperature and increasing Ca²⁺ levels of geothermal water. Additionally, the relationship between F^- and SiO₂ indicates that geothermal water promotes the fluoride enrichment in cold groundwater, especially in confined aquifers which are more susceptible to geothermal water. The direct input of geothermal fluoride and secondary enrichment caused by alkaline condition contribute to the formation of high F^- concentrations (7.2-8.3 mg/L) in confined groundwater. Our findings highlight that the natural evolution of geothermal systems in fault zone can result in the formation of geogenic contaminated groundwater.