Fluoride removal by calcite: evidence for fluorite precipitation and surface adsorption

Fluoride contamination of groundwater, both anthropogenic and natural, is a major problem worldwide. In this study, fluoride removal by crushed limestone (99% pure calcite) was investigated by batch studies and surface-sensitive techniques from solutions with fluoride concentrations from 150 μmol/L (3 mg/L) to 110 mM (~2100 mg/L). Surface-sensitive techniques, including atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) as well as ζ potential measurements, confirm that, in addition to precipitation reactions, adsorption of fluoride also occurs. Results indicate that fluoride adsorption occurs immediately over the entire calcite surface with fluorite precipitating at step edges and kinks, where dissolved Ca²⁺ concentration is highest. The PHREEQ geochemical model was applied to the observed data and indicates that existing models, especially at low fluoride concentrations and high pH (>7.5) are not equipped to describe this complex system, largely because the PHREEQ model includes only precipitation reactions, whereas a combination of adsorption and precipitation parameters are required