It is well established that the fractionation of Li–F granitic magmas at depth leads to the accumulation of flux elements such as F and Li, and metal cations such as Ta and Nb in residual melts. However, it remains to be determined whether magmatic fractionation is sufficient to concentrate Nb and Ta into economically significant quantities, and what role hydrothermal–metasomatic processes play in the formation of such ore deposits. In the literature, reliable data about the solubility of Ta and Nb in hydrothermal solutions is missing or incomplete. This study provides a quantitative experimental estimation of the possible contribution from hydrothermal processes in Ta enrichment in cupolas of albitized and greisenized Li–F granite. Experimental studies of Ta2O5 and columbite–tantalite (Mn,Fe)(Nb,Ta)2O6 solubility were carried out in fluoride solutions consisting of HF, NaF, KF, and LiF. At low fluoride concentrations (0.01 and 0.1 m), Ta2O5 solubility at 550°C and 100 MPa under Co–CoO oxidizing conditions is low (near 10−5–10−4 m) in all fluoride solutions (HF, NaF, KF, LiF). At high fluoride concentrations (1 and 2 m) the highest Ta2O5 concentrations (10−1 m) were detected in HF solutions. In KF, NaF, and LiF solutions, the Ta2O5 solubility is also high (10−3–10−2 m). The dependence of columbite–tantalite (Nb2O5-59 wt. %, Ta2O5-18 wt. %) solubility as a function of solution composition, T, and P has also been investigated. Tantalum and Nb concentrations have the highest values in HF solutions at reduced conditions (up to 10−3 to 10−2 m Ta in 1 m HF). In 1 m NaF solutions, the concentrations of Nb and Ta are, respectively, 2.5 and 3 orders of magnitude less than those in the 1 m HF solutions. Solubility of Ta and Nb in KF solutions has intermediate values. It is established that in NaF and KF solutions the dependence of solubility on pressure is distinctly negative. The Nb and Ta contents increase with increasing concentrations of HF and KF in solution, however, they do not change with increasing NaF concentration. In NaHCO3, Na2CO3, and HCl solutions columbite–tantalite solubility is low. Even in 1 m chloride solutions the content is within the limits of 10−5 m for Nb and 10−6 to 10−8 m for Ta. We conclude that hydrothermal transport of Ta and Nb is possible only in concentrated fluoride solutions.
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