Rutile Solubility in Supercritical Albite-H2O fluids: Implications for Element Mobility in Subduction Zones

Supercritical fluids with compositions intermediate between H2O and silicate are widely invoked as important transport agents in subduction zones. This proposal is in part motivated by the expectation that such fluids might have greater ability to dissolve and transport key trace elements at high P and T. As a test of this hypothesis, we measured the solubility of rutile (TiO2) in supercritical albite (ab, NaAlSi3O8)-H2O at 900°C, 1.5 GPa, from Xab = 0 to 0.3. At this P and T, rutile has very low solubility in H2O and there is full miscibility between H2O and ab melt. Experiments were conducted in a piston-cylinder apparatus with NaCl-graphite furnaces. In each, a 1.6 mm OD Pt inner capsule with a synthetic rutile crystal was lightly crimped and placed in a 3.5 OD Pt capsule with ultra pure H2O and powdered Amelia albite. Equilibrium was achieved after 4 hrs. Solubility was determined by the weight loss of the rutile grain. Quench textures consistent with supercritical behavior were observed in all runs. Residual corundum is present in the H2O-rich runs, but it decreases with increasing ab concentration. Results show that rutile solubility initially rises sharply with increasing ab concentration from 38 ppm in pure H2O to 739 ppm at Xab =0.05 (44 wt%). With further increase in ab, rutile solubility increases only slightly, to 922 ppm at Xab =0.25 (83 wt%). No significant solubility increase was noted near the critical compositon (~50 wt% ab). Our results show that intermediate fluids do not significantly enhance Ti solubility above dilute silicate-bearing solutions. The presence of residual Al2O3 and the sharp initial rise in rutile solubility at low Xab imply that, by analogy with silicate melts, Ti is present in solution as Na-Ti-O complexes (e.g., Dickenson and Hess, 1985, GCA, 49, 2289). However, the lack of residual corundum at high Xab suggests a transiton to different Ti species, perhaps aqueous NaAlSi3O8-like complexes. Our results give insight into rutile in high- P veins. Low Ti solubility requires that these features result from channelized flow and/or high fluid fluxes. For example, at our experimental conditions, growth of a 1 mm3 crystal from a fluid produced by 2 wt% dehydration from metabasalt and containing 5 wt% ab would require 61 m3 of rock, assuming the fluid precipitates all dissolved Ti. If the supercritical ab-H2O system adequately approximates the possible range of natural fluids, it is evident that supercritical fluids may not have the ability to dissolve and mobilize significant concentrations of nominally insoluble trace elements.