The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.