An in situ experimental study of Zr<SUP>4+</SUP> transport capacity of water-rich fluids in the temperature and pressure range of the deep crust and upper mantle

Throughout the Earth's history, mass transport involved fluids. In order to address the circumstances under which Zr4+ may have been transported in this manner, its solubility behavior in aqueous fluid with and without NaOH and SiO2 in equilibrium with crystalline ZrO2 was determined from 550 to 950 degrees C and 60 to 1200 MPa. The measurements were carried out in situ while the samples were at the temperatures and pressures of interest. In ZrO2-H2O and ZrO2-SiO2-H2O fluids, the Zr4+ concentration ranges from <= 10 to similar to 70 ppm with increasing temperature and pressure. Addition of SiO2 to the ZrO2-H2O system does not affect these values appreciably. In these two environments, Zr4+ forms simple oxide complexes in the H2O fluid with Delta H similar to 40 kJ/mol for the solution equilibrium, ZrO2(solid) = ZrO2(fluid). The Zr4+ concentration in aqueous fluid increases about an order of magnitude upon addition of 1 M NaOH, which reflects the formation of zirconate complexes. The principal solution mechanism is ZrO2 + 4NaOH = Na4ZrO4 + 2H(2)O with Delta H similar to 200 kJ/mol. Addition of both SiO2 and NaOH to ZrO2-H2O enhances the Zr4+ by an additional factor of about 5 with the formation of partially protonated alkali zircon silicate complexes in the fluid. The principal solution mechanism is 2ZrO(2) + 2NaOH + 2SiO(2) = Na2Zr2Si2O9+ H2O with Delta H similar to 40 kJ/mol. These results, in combination with other published experimental data, imply that fluid released during high-temperature/high-pressure dehydration of hydrous mineral assemblages in the Earth's interior under some circumstances may carry significant concentrations of Zr and probably other high field strength elements (HFSEs). This suggestion is consistent with the occurrence of Zr-rich veins in high-grade metamorphic eclogite and granulite terranes. Moreover, aqueous fluids transported from dehydrating oceanic crust into overlying mantle source rocks of partial melting also may carry high-abundance HFSE of fluids released from dehydrating slabs and transported to the source rock of partial melting in the overlying mantle wedge. These processes may have been operational in the Earth's history within which subduction resembling that observed today was operational.