Thermodynamic modeling of post-entrapment crystallization in igneous phases

Inclusions of quenched silicate liquid in igneous phenocryst phases represent important windows into the pre-eruption chemistry of volcanic rocks. Melt inclusions are subject to a variety of potential modifications after entrapment, which obscure the connection between final inclusion composition, and entrapment conditions. We concentrate on the effects of postentrapment crystallization (PEC) in the cooling inclusion. PEC is neither an isobaric nor an isochoric process. Pressure decreases between 2 and 27 bars per degree of cooling, depending on the chemistry of melt and host and on the degree of PEC. In the equilibrium case, between about 50% and 65% of this pressure effect is due to thermal expansivity of the liquid, 10-35% from thermal expansivity of the host, and 5-40% from mass transfer between the inclusion and host. This complicates the application of simple element-partitioning schemes for back-calculating the effects of post-entrapment crystallization except in the simplest cases. We present a thermodynamic algorithm for PEC correction. This method is based on the self-consistent thermodynamic model set used in the MELTS software package. The algorithm moves backward through the PEC process, incrementally adding equilibrium crystal composition to the liquid while accounting for consequent variations in pressure and oxygen fugacity. Entrapment conditions are assumed to have been reached when the instantaneous liquidus solid composition most closely matches that of the bulk host crystal. Besides giving information on the degree of PEC and initial inclusion composition, the proposed algorithm can provide constraints on the pressure, temperature and oxygen fugacity at the time of entrapment. Olivine- and orthopyroxene-hosted inclusions from Popocatepetl, Mexico help constrain pre-eruption conditions for mixed magmas from recent eruptive products. Feldspar-hosted inclusions from Satsuma-Iwojima, Japan suggest that these magmas were substantially undersaturated with respect to supercritical vapor phase at the time of entrapment and underwent on the order of 29% post-entrapment crystallization. Quartz-hosted inclusions can potentially be employed in more silicic compositions, but this will require refinement of existing thermodynamic models. (C) 2004 Elsevier B.V. All rights reserved.