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.