Phase-equilibrium geobarometers for silicic rocks based on rhyolite-MELTS. Part 1: Principles, procedures, and evaluation of the method

Constraining the pressure of crystallization of magmas is an important but elusive task. In this work, we present a method to derive crystallization pressures for rocks that preserve glass compositions (either glass inclusions or matrix glass) representative of equilibration between melt, quartz, and 1 or 2 feldspars. The method relies on the well-known shift of the quartz-feldspar saturation surface toward higher normative quartz melt compositions with decreasing pressure. The critical realization for development of the method is the fact that melt, quartz and feldspars need to be in equilibrium at the liquidus for the melt composition. The method thus consists of calculating the saturation surfaces for quartz and feldspars using rhyolite-MELTS over a range of pressures, and searching for the pressure at which the expected assemblage (quartz+ 1 feldspar or quartz+ 2 feldspars) is found at the liquidus. We evaluate errors resulting from uncertainties in glass composition using a series of Monte Carlo simulations for a quartz-hosted glass inclusion composition from the Bishop Tuff, which reveal errors on the order of 20-45 MPa for the quartz+ 2 feldspars constraint and on the order of 25-100 MPa for the quartz+ 1 feldspar constraint; we suggest actual errors are closer to the lower bounds of these ranges. We investigate the effect of fluid saturation in two ways: (1) By applying our procedure over a range of water contents for three glass compositions; we show that the effect of fluid saturation is more important at higher pressures (similar to 300 MPa) than at lower pressures (similar to 100 MPa), but reasonable pressure estimates can be derived irrespective of fluid saturation for geologically relevant H2O concentrations[3 wt% and (2) by performing the same type of pressure determinations with a preliminary version of rhyolite-MELTS that includes a H2OCO2 mixed fluid phase; we use a range of H2O and CO2 concentrations for two compositions characteristic of early-erupted and late-erupted Bishop Tuff glass inclusions and demonstrate that calculated pressures are largely independent of CO2 concentration (for CO2\1,000 ppm), at least for relatively high H2O contents, as expected in most natural magmas, such that CO2 concentration can be effectively neglected for application of our method. Finally, we demonstrate that pressures calculated using the rhyolite-MELTS geobarometer compare well with those resulting from H2O-CO2 glass inclusion barometry and Al-in-hornblende barometry for an array of natural systems for which data have been compiled from the literature; the agreement is best for quartz-hosted glass inclusions, while matrix glass yields systematically lower rhyolite-MELTS pressures, suggestive of melt evolution during eruptive decompression.