Leucocratic magmatic melts with the maximum fluorine concentrations: Experiment and relations in nature

Experimental data indicate that high F concentrations in leucocratic aluminosilicate melts (of granite and nepheline syenite composition) bring about the crystallization of F-rich minerals (topaz, villiaumite, and cryolite) on the liquidus. The crystallization of the minerals is controlled by the silicity, agpaitic coefficient, and proportions of alkalis in the system SiO₂-Al₂O₃-Na₂O-K₂O-F-H₂O. Our earlier experimental data on this system are compared with petrographic and petrochemical data on granites and nepheline syenites containing accessory topaz, cryolite, and villiaumite. The composition of topaz- and cryolite-bearing rocks is proved to correspond to the experimentally established equilibrium fields of F-rich aluminosilicate melt with these minerals. It is proved that the high-F minerals can crystallize from melt. The partial substitution of K and Na for Li modifies phase relations in the system, first of all, significantly expands the equilibrium field of aluminosilicate melt and alkaline aluminofluoride melts. The two melts are proved to be immiscible within broad compositional ranges in the SiO₂-Al₂O₃-Na₂O-Li₂O-F-H₂O system at 800–650°C and 1 kbar. Experimental data indicate that fluoride brine can coexist with aluminosilicate melts in nature. This finds support data on melt inclusions in granites and alkaline rocks whose contents of major components, water and fluorine are close to those in the experimental glasses. Our data lend support to the hypothesis that large cryolite bodies at the Ivigtut, Pitinga, Ulog-Tanzek, and other deposits were formed by fluoride salt melts that separated from F-rich aluminosilicate magmas late in the course of their differentiation. It is experimentally established that fluoride salt melts are able to concentrate valuable trace elements, such as Li, W, Nb, Hf, Sc, U, Th, and REE, which suggests that such melts can play an important role in the origin of rare-metal deposits genetically related to rocks that crystallize from magmas rich in F.