Experimental determination of quartz solubility and melting in the system SiO2–H2O–NaCl at 15–20 kbar and 900–1100 °C: implications for silica polymerization and the formation of supercritical fluids

Abstract

We investigated quartz solubility and melting in the system SiO2–NaCl–H2O at 15–20 kbar and 900–1100 °C using hydrothermal piston–cylinder methods. The solubility of natural, high-purity quartz was determined by weight loss. Quartz solubility decreases with increasing NaCl mole fraction (X NaCl) at fixed pressure and temperature. The decline is greatest at low X NaCl. The solubility patterns can be explained by changes in the concentration and identity of silica oligomers. Modeling of results at 1000 °C, 15 kbar, reveals that silica monomers and dimers predominate at low Si concentration (high X NaCl), that higher oligomers assumed to be trimers become detectable at X NaCl = 0.23, and that the trimers contain >50 % of dissolved Si at X NaCl = 0. The modeling further implies a hydration number for the silica monomer of 1.6, significantly lower than is observed in previous studies. Results at 15 kbar and 1100 °C provide evidence of two coexisting fluid phases. Although solubility could not be determined directly in these cases, the presence or absence of phases over a range of bulk compositions permitted mapping of the topology of the phase diagram. At 1100 °C, 15 kbar, addition of only a small amount of NaCl (X NaCl = 0.05) leads to separation of two fluid phases, one rich in H2O and SiO2, the other rich in NaCl with lower SiO2. Textural identification of two fluids is supported by very low quench pH due to preferential partitioning of Na into the fluid that is rich in SiO2 and H2O, confirmed by electron microprobe analyses. The addition of NaCl causes the upper critical end point on the SiO2–H2O melting curve to migrate to significantly higher pressure. Correspondence between depolymerization and phase separation of SiO2–H2O–NaCl fluids indicates that polymerization plays a fundamental role in producing critical mixing behavior in silicate–fluid systems.