Oxygen thermobarometry measurements on spinel peridotite rocks indicate that the oxygen fugacity at the top of the upper mantle falls within ±2 log units of the fayalite-magnetite-quartz (FMQ) oxygen buffer. Measurements on garnet peridotites from cratonic lithosphere reveal a general decrease in fo2 with depth, which appears to result principally from the effect of pressure on the controlling Fe3+/Fe2+ equilibria. Modeling of experimental data indicates that at approximately 8 GPa, mantle fo2 will be 5 log units below FMQ and at a level where Ni-Fe metal becomes stable. Fe-Ni alloy and an Fe2O3-garnet component will be formed as a result of the disproportionation of FeO, which is experimentally demonstrated through observations of high Fe3+/ΣFe ratios in minerals in equilibrium with metallic Fe. In the lower mantle, the favorable coupled substitution of Al and Fe3+ into (Fe,Mg)SiO3 perovskite results in very high perovskite Fe3+/ΣFe ratios in equilibrium with metallic Fe. As a result, the lower mantle should contain approximately 1 weight% metallic Fe formed through FeO disproportionation, if the bulk oxygen content is the same as the upper mantle. Loss of disproportionated metallic Fe from the lower mantle during core formation could explain the higher Fe3+/ΣFe ratio of the present-day upper mantle when compared to that expected during core formation. The influence of pressure on mantle fo2 has important implications for the speciation of C-O-H-S volatile phases in Earth today and during its early evolution.

The oxidation state recorded by rocks from the Earth's upper mantle can be calculated from measurements of the distribution of Fe3+ and Fe2+ between the constituent minerals. The capacity for minerals to incorporate Fe3+ may also be a significant factor controlling the oxidation state of the mantle, and high-pressure experimental measurements of this property might provide important insights into the redox state of the more inaccessible deeper mantle. Here we show experimentally that the Fe3+ content of aluminous silicate perovskite, the dominant lower-mantle mineral, is independent of oxygen fugacity. High levels of Fe3+ are present in perovskite even when it is in chemical equilibrium with metallic iron. Silicate perovskite in the lower mantle will, therefore, have an Fe3+/total Fe ratio of at least 0.6, resulting in a whole-rock ratio of over ten times that of the upper mantle. Consequently, the lower mantle must either be enriched in Fe3+ or Fe3+ must form by the disproportionation of Fe2+ to produce Fe3+ plus iron metal. We argue that the lower mantle contains approximately 1 wt% of a metallic iron-rich alloy. The mantle's oxidation state and siderophile element budget have probably been influenced by the presence of this alloy.

Determining the oxygen fugacity of Earth's silicate mantle is of prime importance because it affects the speciation and mobility of volatile elements in the interior and has controlled the character of degassing species from the Earth since the planet's formation. Oxygen fugacities recorded by garnet-bearing peridotite xenoliths from Archaean lithosphere are of particular interest, because they provide constraints on the nature of volatile-bearing metasomatic fluids and melts active in the oldest mantle samples, including those in which diamonds are found. Here we report the results of experiments to test garnet oxythermobarometry equilibria under high-pressure conditions relevant to the deepest mantle xenoliths. We present a formulation for the most successful equilibrium and use it to determine an accurate picture of the oxygen fugacity through cratonic lithosphere. The oxygen fugacity of the deepest rocks is found to be at least one order of magnitude more oxidized than previously estimated. At depths where diamonds can form, the oxygen fugacity is not compatible with the stability of either carbonate- or methane-rich liquid but is instead compatible with a metasomatic liquid poor in carbonate and dominated by either water or silicate melt. The equilibrium also indicates that the relative oxygen fugacity of garnet-bearing rocks will increase with decreasing depth during adiabatic decompression. This implies that carbon in the asthenospheric mantle will be hosted as graphite or diamond but will be oxidized to produce carbonate melt through the reduction of Fe(3+) in silicate minerals during upwelling. The depth of carbonate melt formation will depend on the ratio of Fe(3+) to total iron in the bulk rock. This 'redox melting' relationship has important implications for the onset of geophysically detectable incipient melting and for the extraction of carbon dioxide from the mantle through decompressive melting.

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Phase transitions and the chemical composition of minerals in Earth's interior influence geophysical interpretations of its deep structure and dynamics. A pressure-induced spin transition in olivine has been suggested to influence iron partitioning and depletion, resulting in a distinct layered structure in Earth's lower mantle. For a more realistic mantle composition (pyrolite), we observed a considerable change in the iron-magnesium partition coefficient at about 40 gigapascals that is explained by a spin transition at much lower pressures. However, only a small depletion of iron is observed in the major high-pressure phase (magnesium silicate perovskite), which may be explained by preferential retention of the iron ion Fe3+. Changes in mineral proportions or density are not associated with the change in partition coefficient. The observed density profile agrees well with seismological models, which suggests that pyrolite is a good model composition for the upper to middle parts of the lower mantle.

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Chemical data from the MESSENGER spacecraft revealed that surface rocks on Mercury are unusually enriched in sulfur compared to samples from other terrestrial planets. In order to understand the speciation and distribution of sulfur on Mercury, we performed high temperature (1200-1750 • C), lowto high-pressure (1 bar to 4 GPa) experiments on compositions representative of Mercurian lavas and on the silicate composition of an enstatite chondrite. We equilibrated silicate melts with sulfide and metallic melts under highly reducing conditions (IW-1.5 to IW-9.4; IW = iron-wüstite oxygen fugacity buffer). Under these oxygen fugacity conditions, sulfur dissolves in the silicate melt as S 2− and forms complexes with Fe 2+ , Mg 2+ and Ca 2+ . The sulfur concentration in silicate melts at sulfide saturation (SCSS) increases with increasing reducing conditions (from <1 wt.% S at IW-2 to >10 wt.% S at IW-8) and with increasing temperature. Metallic melts have a low sulfur content which decreases from 3 wt.% at IW-2 to 0 wt.% at IW-9. We developed an empirical parameterization to predict SCSS in Mercurian magmas as a function of oxygen fugacity ( f O 2 ), temperature, pressure and silicate melt composition. SCSS being not strictly a redox reaction, our expression is fully valid for magmatic systems containing a metal phase. Using physical constraints of the Mercurian mantle and magmas as well as our experimental results, we suggest that basalts on Mercury were free of sulfide globules when they erupted. The high sulfur contents revealed by MESSENGER result from the high sulfur solubility in silicate melt at reducing conditions. We make the realistic assumption that the oxygen fugacity of mantle rocks was set during equilibration of the magma ocean with the core and/or that the mantle contains a minor metal phase and combine our parameterization of SCSS with chemical data from MESSENGER to constrain the oxygen fugacity of Mercury's interior to IW-5.4 ± 0.4. We also calculate that the mantle of Mercury contains 7-11 wt.% S and that the metallic core of the planet has little sulfur (<1.5 wt.% S). The external part of the Mercurian core is likely to be made up of a thin (<90 km) FeS layer.

International audienceThe lower mantle is dominated by a magnesium- and iron-bearing mineral with the perovskite structure. Iron has the ability to adopt different electronic configurations, and transitions in its spin state in the lower mantle can significantly influence mantle properties and dynamics. However, previous studies aimed at understanding these transitions have provided conflicting results1–4. Here we report the results of high-pressure (up to 110 GPa) and high-temperature (up to 1,000 K) experiments aimed at understanding spin transitions of iron in perovskite at lower-mantle conditions . Our M¨ossbauer and nuclear forward scattering data for two lower-mantle perovskite compositions demonstrate that the transition of ferrous iron from the high-spin to the intermediate-spin state occurs at approximately 30 GPa, and that high temperatures favour the stability of the intermediate-spin state. We therefore infer that ferrous iron adopts the intermediate-spin state throughout the bulk of the lower mantle. Our X-ray data show significant anisotropic compression of lower-mantle perovskite containing intermediate-spin ferrous iron, which correlates strongly with the spin transition. We predict spin-state heterogeneities in the uppermost part of the lower mantle associated with sinking slabs and regions of upwelling. These may affect local properties, including thermal and electrical conductivity, deformation (viscosity) and chemical behaviour, and thereby affect mantle dynamics