Solubility of niobium in the system CaCO3–CaF2–NaNbO3 at 0.1 GPa pressure: implications for the crystallization of pyrochlore from carbonatite magma

Experimental data are presented for the solubility of NaNbO3 in the ternary system CaCO3–CaF2–NaNbO3 (or calcite–fluorite–lueshite) over the temperature range 500–1,000°C at 0.1 GPa pressure. Liquidus to solidus phase relationships are given for the pseudo-binary join ([CaCO3]60[CaF2]40)100-x–(NaNbO3)x (0<x<60 wt%). These data show that the maximum solubility of NaNbO3 in these liquids is about 17 wt% (or 13.8 wt% Nb2O5) at approximately 930°C, and is represented by the appearance of pyrochlore as the primary liquidus phase. The sub-liquidus assemblages with decreasing temperature for NaNbO3 contents of 20–50 wt% are: pyrochlore + liquid; pyrochlore + CaF2 + liquid; pyrochlore + CaF2 + CaCO3 + liquid. The solidus assemblage is pyrochlore + CaF2 + CaCO3 at temperatures of approximately 700°C (20 wt% NaNbO3) and 600°C (40 wt% NaNbO3). NaNbO3 is present only in sub-solidus assemblages. These data show that in this fluorine-bearing anhydrous system pyrochlore is the principal Nb-hosting supra-solidus phase, in contrast to fluorine-free hydrous melts from which perovskite-structured compounds crystallize. The crystallization of pyrochlore and/or perovskite-structured compounds from haplocarbonatite liquids is thus considered to be dependent upon the F/OH ratio of the melt.