Fluid and rock interactions in silicate and aluminosilicate systems at elevated pressure and temperature.

Abstract

Understanding fluid chemistry in the subduction zone environment is key to unraveling the details of element transport from the slab to the surface. Solubilities of cations, such as silicon, in water strongly affect both the physical and chemical properties of supercritical metamorphic fluids. Modeling the thermodynamics of fluid-rock interactions requires therefore a profound understanding of cation dissolution and aqueous speciation. In situ Raman experiments of the silica-water, alumina-water, and alumina water systems were performed in an externally heated Bassett-type diamond-anvil cell at the Department of Geological Sciences, University of Michigan. Natural quartz samples and synthetic ruby samples were used in the experiments. Samples were loaded in the sample chamber with a water pressure medium. All experiments used rhenium gaskets of uniform thickness with a 500 mum drill hole for the sample chamber. Temperature was measured using K-type thermocouples encompassing both the upper and lower diamond anvils. Pressures are obtained on the basis of the Raman shift of the 464 cm<super>-1</super> quartz mode where possible or the Raman shift of the tips of the diamond anvils according to a method developed in this work. This work characterizes the state of stress in the diamond anvil cell, which is used as the basis for the pressure calibration using only the diamond anvils. Raman measurements of silicate fluid confirm the presence of H₄SiO₄ and H₆Si₂O₇ in solution and expand the pressure range for in-situ structural observations in the silica-water system. Additionally, we identify the presence of another silica species present at mantle conditions, which occurs at long time scales in the diamond cell. This study provides the first in situ data in the alumina-water and alumina-silica-water systems at pressures and temperatures relevant to the slab environment. Al(OH)₃ appears to be the dominant form of alumina present under these conditions and in the alumina-silica-water system exists simultaneously with a silica monomer species. Raman peaks also suggest the presence of an aqueous alumina-silica dimer specie.