| The progressive enrichment in volatiles and light incompatible elements observed during upper-crustal differentiation of granitic and rhyolitic magmas leads to significant changes in melt physical-chemical properties and has important implications for ore deposition and volcanic devolatization. Thermodynamic calculations and experimental studies of melting equilibria in the Na 2O-K2O-Al2O3-SiO2-F 2O-1-H2O system are used to evaluate mineral stabilities, fluid compositions, the extent of fluoride-silicate liquid-liquid immiscibility, fluorine and water solubility limits and differentiation paths of natural fluorine-bearing silicic magmas. The interaction of fluorine with rock-forming aluminosilicates corresponds to progressive fluorination by the thermodynamic component F2O-1. Formation of fluorine-bearing minerals first occurs in peralkaline and silica-undersaturated systems that buffer fluorine concentrations at very low levels (villiaumite, fluorite). The highest concentrations of fluorine are achieved in peraluminous silica-oversaturated systems, saturated with fluorite or topaz. Thermodynamic models of fluorosilicate melts indicate clustering of silicate tetrahedra in the Na2O-SiO 2-F2O-1 system, whereas initial NaAl-F short-range order evolves into partial O-F disorder in the albite-cryolite system. Experiments performed at 520-1100°C and 0.1-100 MPa completely describe liquidus relations and differentiation paths of fluorine-bearing felsic magmas. Coordination differences and short-range order effects between [NaAl]-F, Na-F vs. Si-O lead to the fluoride-silicate liquid immiscibility, which extends from the silica-cryolite binary through the peralkaline albite-silica-cryolite ternary and closes in multicomponent, topaz-bearing systems owing to the destabilizing effect of increasing peraluminosity. Liquidus relations indicate that fluoride-silicate liquid-liquid immiscibility is inaccessible to quartz-feldspar-saturated granitic melts. Differentiation paths of Ca-poor granitic melts with fluorine reach the cryolite or topaz saturation surface, respectively, and, depending on aluminosity buffering by rock-forming silicates, may evolve to the high fluorine concentrations of the haplogranite-topaz-cryolite-H2O eutectic at max. 5.9 wt. % F, 540°C, 100 MPa and H2O saturation. In contrast, the potential of Ca-rich silicic magmas for fluorine enrichment is severely limited by fluorite crystallization. Fluorite solubility is determined by individual concentrations of CaO and F2O-1 in the melt and exhibits a minimum at subaluminous compositions due to the short-range ordering of Ca-Al and alkali-F. These results provide a framework for differentiation of natural fluorine-bearing magmas and have applications in electrolytic and flux metallurgy. |
