Sapphirine and spinel phase relationships in the system FeO-MgO-Al₂O₃-SiO₂-TiO₂-O₂ in the presence of quartz and hypersthene

Abstract

Sapphirine and spinel can accommodate significant ferric iron and therefore the mineral equilibria involving these phases must be sensitive to a(O₂). In this paper we examine the theoretical phase relationships involving sapphirine and spinel in addition to sillimanite, garnet, cordierite, rutile, hematite-ilmenite solid solution (henceforth ilmenite), and magnetite-ulvospinel solid solution (henceforth magnetite), in the presence of quartz and hypersthene in the system FeO-MgO-Al₂O₃-SiO₂-TiO₂-O₂ (FMASTO), with particular reference to the topological inversion in P-T postulated by Hensen (Hensen 1986). Documented natural associations suggest that the appropriate topology for assemblages involving magnetite and ilmenite is Hensen's higher a(O₂) one, while, in contrast, the topology for assemblages involving ilmenite and rutile is the lower a(O₂) one. The exact configuration of the inversion between these two topologies remains uncertain because of uncertainties in the ferric/ferrous iron partitioning between sapphirine and spinel-cordierite at high temperatures. By comparison with experimental data and natural occurences, the sillimanite-sapphirine-cordierite-garnet-hypersthene-quartz assemblage is in equilibrium at about 1000°–1020° C and 7–8 kbars, while sapphirine-cordierite-spinel-garnet-hypersthene-quartz occurs at temperatures in excess of those attainable during crustal metamorphism, for ilmenite-rutile buffered assemblages. This implies that sapphirine-rutil-ehypersthene-quartz assemblages, as found in the Napier Complex, Antarctica, can only occur at > 1000° C. Also, spinel-rutile-hypersthene-quartz assemblages should not be found in rocks because temperatures in excess of 1100° C are expected to be involved in their formation. The temperatures of formation of spinel-sillimanite-sapphirine-garnethypersthene-quartz, sapphirine-spinel-cordierite-sillimanite-hypersthene-quartz, and sillimanite-spinel-cordieritegarnet-hypersthene-quartz in assemblages buffered by magnetite and ilmenite are less well constrained, but are likely to be in the range 900°–1000° C. These conclusions apply to rocks with compositions close to FMASTO; the perturbing effects of substantial concentrations of additional components, in particular Ca, mainly in garnet, and Zn and Cr, mainly in spinel, may invalidate these conclusions.