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Abstract: Arc magmas erupted at the Earth’s surface are commonly more oxidized than those produced at mid-ocean ridges. Possible explanations for this high oxidation state are that the transfer of fluids during the subduction process results in direct oxidation of the sub-arc mantle wedge, or that oxidation is caused by the effect of later crustal processes, including protracted fractionation and degassing of volatile-rich magmas. This study sets out to investigate the effect of disequilibrium crustal processes that may involve coupled changes in H2O content and Fe oxidation state, by examining the degassing and hydration of sulphur-free rhyolites. We show that experimentally hydrated melts record strong increases in Fe3+/∑Fe with increasing H2O concentration as a result of changes in water activity. This is relevant for the passage of H2O-undersaturated melts from the deep crust towards shallow crustal storage regions, and raises the possibility that vertical variations in fO2 might develop within arc crust. Conversely, degassing experiments produce an increase in Fe3+/∑Fe with decreasing H2O concentration. In this case the oxidation is explained by loss of H2 as well as H2O into bubbles during decompression, consistent with thermodynamic modelling, and is relevant for magmas undergoing shallow degassing en route to the surface. We discuss these results in the context of the possible controls on fO2 during the generation, storage and ascent of magmas in arc settings, in particular considering the timescales of equilibration relative to observation as this affects the quality of the petrological record of magmatic fO2.

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Abstract: The evolution of basaltic magmas depends on their redox state, hence oxygen fugacity, but there is increasing evidence that this intensive thermodynamic variable may be less well understood in basalts than commonly supposed. The redox state of terrestrial basalts has to a large extent been inferred from the Fe3+/Fe2+ ratios of their quenched glasses. However, this quantity appears to be significantly affected during late and post-eruptive processes in magmatic systems (e.g. by degassing, charge-transfer reactions of redox-variable species, and alteration), so that the degree to which the Fe3+/Fe2+ ratios preserved in basaltic glasses reflect the oxidation state of the magma at high temperature is unclear. Because olivine is the first silicate mineral to crystallize from primitive basaltic liquids on cooling following decompression, the equilibrium partitioning relations preserved in olivine phenocrysts in basalts are, in principle, less disturbed by these late and post-eruptive processes and, therefore, may better reflect the high-temperature (pre-eruptive) conditions of the magma. Here we calibrate an oxybarometer based on the strong sensitivity of the partitioning of vanadium between olivine and silicate melt to oxygen fugacity. Our empirical parameterization, calibrated over a range of redox conditions between four log10 units above and below the quartz–fayalite–magnetite (QFM) oxygen buffer, takes into account the effects of temperature, olivine composition (i.e. Mg/Fe ratios) and melt composition (namely the activities of CaO, SiO2, AlO1·5, NaO0·5 and KO0·5), and allows oxygen fugacity determinations to within ∼0·25 log10 units. We also explore the sensitivity of the exchange partitioning of Sc and Y between olivine and melt to temperature as a geothermometer. Our calibration indicates that this geothermometer allows temperature to be estimated to within 15°C, but precision is strongly dependent on the Sc and Y measurements in olivine and melt.

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Abstract: Experiments at 20–97 GPa and 2000 K in the system CaO–MgO–TiO2–SiO2 constrain phase relations involving Mg-rich and Ca-rich perovskite solid solutions at conditions relevant to the Earth's deep Transition Zone and lower mantle. Bulk compositions were investigated with molar Ti/(Ti + Si) up to 0·5 within the quasi-ternary ‘perovskite plane’, which is defined by a reciprocal solution among the components MgSiO3, MgTiO3, CaSiO3, and CaTiO3. Multi-anvil experiments at 20 GPa and 2000 K on bulk compositions within the plane produce akimotoite coexisting with Ca-perovskites that lie close to the CaSiO3–CaTiO3 join. Higher-pressure experiments using a laser-heated diamond anvil cell constrain the position of a two-perovskite field that extends into the perovskite plane from the solvus along the MgSiO3–CaSiO3 binary join, WHERE limited mutual solubility exists between MgSiO3 and CaSiO3 perovskites. On the join MgSiO3–MgTiO3, MgTiO3 solubility in MgSiO3 perovskite increases with pressure, with MgSi0·8Ti0·2O3 perovskite stable at ∼50 GPa. Limited reciprocal solution at ∼25 GPa results in an expansive two-perovskite field that occupies much of the Si-rich portion of the perovskite plane. Solution of Ti into Mg-rich and Ca-rich perovskites enhances the solubility of reciprocal Ca and Mg components, respectively. Increase in pressure promotes reciprocal solution, and the two-phase field collapses rapidly with pressure toward the MgSiO3–CaSiO3 join. We find that a single-phase, orthorhombic perovskite with near equimolar Ca and Mg is stable in a composition with Ti/(Ti + Si) of only 0·05 at 97 GPa, requiring that by this pressure the two-phase field occupies a small area close to the MgSiO3–CaSiO3 join. On the basis of experiments at∼1500 K, temperature has only a mild effect on the position of the Ca-rich limb of the solvus. Ca(Ti,Si)O3 mineral inclusions in deep sublithospheric diamonds could not have formed in equilibrium with Mg-perovskite owing to their virtual lack of MgSiO3 component at pressures of Mg-perovskite stability, but may have equilibrated with Transition Zone MgSiO3-rich phases at lower pressures; this observation can be extended generally to near-endmember CaSiO3 inclusions. On an iron-free basis, the average bulk compositions of clinopyroxene–ilmenite and orthopyroxene–ilmenite megacrysts from kimberlites plot in single-perovskite fields at pressures greater than about 45 and 65 GPa, respectively, when projected onto the perovskite plane. We predict that the effect of iron will not be large, and estimate that single-phase perovskites may form at somewhat lower pressures than in the iron-free system. Thus, the origin of pyroxene–ilmenite megacrysts from single-phase perovskite solutions in the lower mantle is plausible on the basis of phase relations, although a lower pressure magmatic origin appears more likely. Deeply subducted Ti-rich lithologies such as ocean-island basalt will crystallize a single perovskite rather than a two-perovskite assemblage beginning at pressures of ∼80 GPa. Normal mid-ocean ridge basalt and primitive mantle peridotite are expected to remain within a two-phase perovskite field until Mg-perovskite transforms to post-perovskite.