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Observations of high ferric iron content in diamond garnet inclusions and mantle plume melts suggest a highly heterogeneous distribution of ferric iron in the mantle. Recycling of oxidized materials such as carbonates from Earth’s surface by subduction could explain the observed variations. Here we present high-pressure high-temperature multi-anvil experiments to determine the redox reactions between calcium-, magnesium-, or iron-carbonate and ferrous iron-bearing silicate mineral (garnet or fayalite) at conditions representative of subduction zones with intermediate thermal structures. We show that both garnet and fayalite can be oxidized to ferric iron-rich garnets accompanied by reduction of calcium carbonate to form graphite. The ferric iron content in the synthetic garnets increases with increasing pressure, and is correlated with the Ca content in the garnets. We suggest that recycled sedimentary calcium carbonate could influence the evolution of the mantle oxidation state by efficiently increasing the ferric iron content in the deep upper mantle.

 

The essential data for interior and thermal evolution models of the Earth and super-Earths are the density and melting of mantle silicate under extreme conditions. Here, we report an unprecedently high melting temperature of MgSiO₃at 500 GPa by direct shockwave loading of pre-synthesized dense MgSiO₃(bridgmanite) using the Z Pulsed Power Facility. We also present the first high-precision density data of crystalline MgSiO₃to 422 GPa and 7200 K and of silicate melt to 1254 GPa. The experimental density measurements support our density functional theory based molecular dynamics calculations, providing benchmarks for theoretical calculations under extreme conditions. The excellent agreement between experiment and theory provides a reliable reference density profile for super-Earth mantles. Furthermore, the observed upper bound of melting temperature, 9430 K at 500 GPa, provides a critical constraint on the accretion energy required to melt the mantle and the prospect of driving a dynamo in massive rocky planets.

 

We conducted shock wave experiments on iron carbide Fe₃C up to a Hugoniot pressure of 245 GPa. The correlation between the particle velocity (u_p) and shock wave velocity (u_s) can be fitted into a linear relationship,u_s= 4.627(±0.073) + 1.614(±0.028)u_p. The density‐pressure relationship is consistent with a single‐phase compression without decomposition. The inference is further supported by the comparison of the observed Hugoniot density with the calculated Hugoniot curves of possible decomposition products. The new Hugoniot data combined with the reported 300‐K isothermal compression data yielded a Grüneisen parameter ofγ= 2.23(7.982/ρ)^0.29. The thermal equation of state of Fe₃C is further used to calculate the density profile of Fe₃C along the Earth's adiabatic geotherm. The density of Fe₃C was found to be too low (by ~5%) to match the observed density in the Earth's inner core, and Fe₃C is unlikely a dominant component of the inner core.

 

Understanding the effect of carbon on the density of hcp (hexagonal-close-packed) Fe-C alloys is essential for modeling the carbon content in the Earth’s inner core. Previous studies have focused on the equations of state of iron carbides that may not be applicable to the solid inner core that may incorporate carbon as dissolved carbon in metallic iron. Carbon substitution in hcp-Fe and its effect on the density have never been experimentally studied. We investigated the compression behavior of Fe-C alloys with 0.31 and 1.37 wt % carbon, along with pure iron as a reference, by in-situ X-ray diffraction measurements up to 135 GPa for pure Fe, and 87 GPa for Fe-0.31C and 109 GPa for Fe-1.37C. The results show that the incorporation of carbon in hcp-Fe leads to the expansion of the lattice, contrary to the known effect in body-centered cubic (bcc)-Fe, suggesting a change in the substitution mechanism or local environment. The data on axial compressibility suggest that increasing carbon content could enhance seismic anisotropy in the Earth’s inner core. The new thermoelastic parameters allow us to develop a thermoelastic model to estimate the carbon content in the inner core when carbon is incorporated as dissolved carbon hcp-Fe. The required carbon contents to explain the density deficit of Earth’s inner core are 1.30 and 0.43 wt % at inner core boundary temperatures of 5000 K and 7000 K, respectively.