Cubic Fe-bearing majorite synthesized at 18-25 GPa and 1000 °C: implications for element transport, subducted slab rheology and diamond formation.

The chemistry and mineralogy of slabs subducted into lower mantle control slab rheology and impact the deep volatile cycle. It is known that the metamorphism of little-altered oceanic crust results in eclogite rocks with subequal proportions of garnet and clinopyroxene. With increasing pressure, these minerals react to stabilize pyrope-rich tetragonal majoritic garnet. However, some eclogites contain higher proportions of omphacitic clinopyroxene, caused by Na- and Si-rich metasomatism on the ocean floor or during subduction. The mineralogy of such eclogites is expected to evolve differently. Here, we discuss the results of the crystallization products of omphacitic glass at ~ 18 and ~ 25 GPa and 1000 °C to simulate P-T regimes of cold subduction. The full characterization of the recovered samples indicates evidence of crystallization of Na-, Si-rich cubic instead of tetragonal majorite. This cubic majorite can incorporate large amounts of ferric iron, promoting redox reactions with surrounding volatile-bearing fluids and, ultimately, diamond formation. In addition, the occurrence of cubic majorite in the slab would affect the local density, favoring the continued buoyancy of the slab as previously proposed by seismic observations. Attention must be paid to omphacitic inclusions in sublithospheric diamonds as these might have experienced back-transformation from the HP isochemical cubic phase.

Deep magma ocean formation set the oxidation state of Earth's mantle.

The composition of Earth's atmosphere depends on the redox state of the mantle, which became more oxidizing at some stage after Earth's core started to form. Through high-pressure experiments, we found that Fe2+ in a deep magma ocean would disproportionate to Fe3+ plus metallic iron at high pressures. The separation of this metallic iron to the core raised the oxidation state of the upper mantle, changing the chemistry of degassing volatiles that formed the atmosphere to more oxidized species. Additionally, the resulting gradient in redox state of the magma ocean allowed dissolved CO2 from the atmosphere to precipitate as diamond at depth. This explains Earth's carbon-rich interior and suggests that redox evolution during accretion was an important variable in determining the composition of the terrestrial atmosphere.

The oxidation state of the mantle and the extraction of carbon from Earth's interior.

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.

Lattice thermal conductivity of lower mantle minerals and heat flux from Earth's core.

The amount of heat flowing from Earth's core critically determines the thermo-chemical evolution of both the core and the lower mantle. Consisting primarily of a polycrystalline aggregate of silicate perovskite and ferropericlase, the thermal boundary layer at the very base of Earth's lower mantle regulates the heat flow from the core, so that the thermal conductivity (k) of these mineral phases controls the amount of heat entering the lowermost mantle. Here we report measurements of the lattice thermal conductivity of pure, Al-, and Fe-bearing MgSiO(3) perovskite at 26 GPa up to 1,073 K, and of ferropericlase containing 0, 5, and 20% Fe, at 8 and 14 GPa up to 1,273 K. We find the incorporation of these elements in silicate perovskite and ferropericlase to result in a ∼50% decrease of lattice thermal conductivity relative to the end member compositions. A model of thermal conductivity constrained from our results indicates that a peridotitic mantle would have k = 9.1 ± 1.2 W/m K at the top of the thermal boundary layer and k = 8.4 ± 1.2 W/m K at its base. These values translate into a heat flux of 11.0 ± 1.4 terawatts (TW) from Earth's core, a range of values consistent with a variety of geophysical estimates.

Iron partitioning and density changes of pyrolite in Earth's lower mantle.

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.

Pressure-induced magnetization in FeO: evidence from elasticity and Mössbauer spectroscopy.

The complete elastic tensor of Fe0.94O (wüstite) has been determined to 10 GPa using acoustic interferometry at GHz frequencies inside a diamond-anvil cell. The soft mode (C44) elastic constant of FeO is reduced by 20% over the experimental pressure range. An unusual discontinuity in the pressure derivatives of C11 and C12 at 4.7+/-0.2 GPa corresponds to the pressure at which the onset of a magnetic ordering transition is observed by high-pressure Mössbauer spectroscopy and neutron powder diffraction. Our new results combined with literature structural high P-T data suggest that there is a magnetic, although still cubic, phase of FeO between approximately 5 and approximately 17 GPa.

Iron isotope fractionation and the oxygen fugacity of the mantle.

The oxygen fugacity of the mantle exerts a fundamental influence on mantle melting, volatile speciation, and the development of the atmosphere. However, its evolution through time is poorly understood. Changes in mantle oxidation state should be reflected in the Fe3+/Fe2+ of mantle minerals, and hence in stable iron isotope fractionation. Here it is shown that there are substantial (1.7 per mil) systematic variations in the iron isotope compositions (delta57/54Fe) of mantle spinels. Spinel delta57/54Fe values correlate with relative oxygen fugacity, Fe3+/sigmaFe, and chromium number, and provide a proxy of changes in mantle oxidation state, melting, and volatile recycling.

Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle.

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.