Effects of fluorine on the solubilities of Nb, Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

Abstract

The effect of fluorine on the solubilities of Mn-columbite (MnNb2O6), Mn-tantalite (MnTa2O6), zircon (ZrSiO4) and hafnon (HfSiO4) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2000 bars. The melt corresponds to the intersection of the granite minimum with the albite-orthoclase tieline (Ab72Or28) in the quartz-albite-orthoclase system (Q-Ab-Or) due to the addition of P2O5 to the melt. The melt content of P2O5 is 1.7 wt. %, and also contains 1.1 and 2.02 wt. % of Li2O and B2O3, respectively. The composition of the starting glass represents the composition of melts from which rare-elements pegmatites crystallized. Up to 6 wt. % fluorine was added as AgF in order to keep the aluminum saturation index (ASI) of the melt constant. In an additional experiment F was added as AlF3 to make the glass peraluminous. The nominal ASI (molar Al/[Na+K]) of the melts is close to 1 and approximately 1.32 in peraluminous glasses, but if Li considered as an alkali, the ASI of the melts are alkaline (0.85) and subaluminous (1.04), respectively. The solubility products [MnO]*[Nb2O5] and [MnO]*[Ta2O5] are nearly independent of the F content of the melt, approximately 18.19 ± 1.2 and 43.65 ± 2.5 x10-4 KSP (mol2/kg2), respectively. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content, which increases from 2.03 ± 0.03 x10-4 (mol/kg) ZrO2 and 4.04 ± 0.2 x10-4 (mol/kg) HfO2 for melts with 0 wt. % F to 3.81 ± 0.3 x10-4 (mol/kg) ZrO2 and 6.18 ± 0.04 x10-4 (mol/kg) HfO2 for melts with 8 wt. % F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb-Ta and Zr-Hf are complexed differently.