[1] Experiments to investigate the partitioning of oxygen between liquid iron and (Mg,Fe)O magnesiowüstite were conducted at 30-70 GPa and 2800-3500 K using a laser-heated diamond anvil cell. A thin foil was prepared from the reacted regions in the recovered samples using a focused ion beam. The compositions of coexisting quenched iron and magnesiowüstite were measured using a transmission electron microscope equipped with energy dispersive X-ray spectroscopy and electron energy-loss spectroscopy. In order to understand and model the results, additional experiments were performed to determine the activity of oxygen, or rather FeO, in liquid Fe metal. Multianvil experiments to measure the oxygen contents of coexisting immiscible metallic and ionic liquids in the Fe-FeO system were performed up to 25 GPa. The results were used to extract excess mixing properties for Fe-FeO liquids at high pressure and temperature. These properties were used to derive a model that describes oxygen partitioning in the Fe-Mg-O system that is independent of the actual experimental partitioning data. The model indicates that the oxygen content of liquid Fe becomes a strong nonlinear function of the FeO content of magnesiowüstite at pressures greater than 25 GPa. This prediction is in excellent agreement with the experimental partitioning data, which is faithfully reproduced in most instances. The new results confirm that the Earth's core is undersaturated in oxygen with respect to the FeO content of the bulk mantle, which will result either in FeO being depleted from the very base of the mantle or lead to the development of an FeO-enriched outer layer of the core. These possibilities are not mutually exclusive.
Siderophile elements are depleted in the Earth's mantle, relative to chondritic meteorites, as a result of equilibration with core-forming Fe-rich metal. Measurements of metal-silicate partition coefficients show that mantle depletions of slightly siderophile elements (e.g. Cr, V ) must have occurred at more reducing conditions than those inferred from the current mantle FeO content. This implies that the oxidation state (i.e. FeO content) of the mantle increased with time as accretion proceeded. The oxygen fugacity of the present-day upper mantle is several orders of magnitude higher than the level imposed by equilibrium with core-forming Fe metal. This results from an increase in the Fe 2 O 3 content of the mantle that probably occurred in the first 1 Ga of the Earth's history. Here we explore fractionation mechanisms that could have caused mantle FeO and Fe 2 O 3 contents to increase while the oxidation state of accreting material remained constant (homogeneous accretion). Using measured metal-silicate partition coefficients for O and Si, we have modelled core-mantle equilibration in a magma ocean that became progressively deeper as accretion proceeded. The model indicates that the mantle would have become gradually oxidized as a result of Si entering the core. However, the increase in mantle FeO content and oxygen fugacity is limited by the fact that O also partitions into the core at high temperatures, which lowers the FeO content of the mantle. (Mg,Fe)(Al,Si)O 3 perovskite, the dominant lower mantle mineral, has a strong affinity for Fe 2 O 3 even in the presence of metallic Fe. As the upper mantle would have been poor in Fe 2 O 3 during core formation, FeO would have disproportionated to produce Fe 2 O 3 (in perovskite) and Fe metal. Loss of some disproportionated Fe metal to the core would have enriched the remaining mantle in Fe 2 O 3 and, if the entire mantle was then homogenized, the oxygen fugacity of the upper mantle would have been raised to its present-day level.
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