Structural and Electronic Transitions in Liquid FeO Under High Pressure.

FeO represents an important end-member for planetary interiors mineralogy. However, its properties in the liquid state under high pressure are poorly constrained. Here, in situ high-pressure and high-temperature X-ray diffraction experiments, ab initio simulations, and thermodynamic calculations are combined to study the local structure and density evolution of liquid FeO under extreme conditions. Our results highlight a strong shortening of the Fe-Fe distance, particularly pronounced between ambient pressure and ∼40 GPa, possibly related with the insulator to metal transition occurring in solid FeO over a similar pressure range. Liquid density is smoothly evolving between 60 and 150 GPa from values calculated for magnetic liquid to those calculated for non-magnetic liquid, compatibly with a continuous spin crossover in liquid FeO. The present findings support the potential decorrelation between insulator/metal transition and the high-spin to low-spin continuous transition, and relate the changes in the microscopic structure with macroscopic properties, such as the closure of the Fe-FeO miscibility gap. Finally, these results are used to construct a parameterized thermal equation of state for liquid FeO providing densities up to pressure and temperature conditions expected at the Earth's core-mantle boundary.

Quantitative 4D X-ray microtomography under extreme conditions: a case study on magma migration.

X-ray computed tomography (XCT) is a well known method for three-dimensional characterization of materials that is established as a powerful tool in high-pressure/high-temperature research. The optimization of synchrotron beamlines and the development of fast high-efficiency detectors now allow the addition of a temporal dimension to tomography studies under extreme conditions. Presented here is the experimental setup developed on the PSICHE beamline at SOLEIL to perform high-speed XCT in the Ultra-fast Tomography Paris-Edinburgh cell (UToPEc). The UToPEc is a compact panoramic (165° angular aperture) press optimized for fast tomography that can access 10 GPa and 1700°C. It is installed on a high-speed rotation stage (up to 360°â€…s-1) and allows the acquisition of a full computed tomography (CT) image with micrometre spatial resolution within a second. This marks a major technical breakthrough for time-lapse XCT and the real-time visualization of evolving dynamic systems. In this paper, a practical step-by-step guide to the use of the technique is provided, from the collection of CT images and their reconstruction to performing quantitative analysis, while accounting for the constraints imposed by high-pressure and high-temperature experimentation. The tomographic series allows the tracking of key topological parameters such as phase fractions from 3D volumetric data, and also the evolution of morphological properties (e.g. volume, flatness, dip) of each selected entity. The potential of this 4D tomography is illustrated by percolation experiments of carbonate melts within solid silicates, relevant for magma transfers in the Earth's mantle.

Melting properties by X-ray absorption spectroscopy: common signatures in binary Fe-C, Fe-O, Fe-S and Fe-Si systems.

X-ray absorption spectroscopy (XAS) is a widely used technique to probe the local environment around specific atomic species. Applied to samples under extreme pressure and temperature conditions, XAS is sensitive to phase transitions, including melting, and allows gathering insights on compositional variations and electronic changes occurring during such transitions. These characteristics can be exploited for studies of prime interest in geophysics and fundamental high-pressure physics. Here, we investigated the melting curve and the eutectic composition of four geophysically relevant iron binary systems: Fe-C, Fe-O, Fe-S and Fe-Si. Our results show that all these systems present the same spectroscopic signatures upon melting, common to those observed for other pure late 3d transition metals. The presented melting criterion seems to be general for late 3d metals bearing systems. Additionally, we demonstrate the suitability of XAS to extract melt compositional information in situ, such as the evolution of the concentration of light elements with increasing temperature. Diagnostics presented in this work can be applied to studies over an even larger pressure range exploiting the upgraded synchrotron machines, and directly transferred to time-resolved extreme condition studies using dynamic compression (ns) or fast laser heating (ms).

Tetrahedrally coordinated carbonates in Earth's lower mantle.

Carbonates are the main species that bring carbon deep into our planet through subduction. They are an important rock-forming mineral group, fundamentally distinct from silicates in the Earth's crust in that carbon binds to three oxygen atoms, while silicon is bonded to four oxygens. Here we present experimental evidence that under the sufficiently high pressures and high temperatures existing in the lower mantle, ferromagnesian carbonates transform to a phase with tetrahedrally coordinated carbons. Above 80 GPa, in situ synchrotron infrared experiments show the unequivocal spectroscopic signature of the high-pressure phase of (Mg,Fe)CO3. Using ab-initio calculations, we assign the new infrared signature to C-O bands associated with tetrahedrally coordinated carbon with asymmetric C-O bonds. Tetrahedrally coordinated carbonates are expected to exhibit substantially different reactivity than low-pressure threefold coordinated carbonates, as well as different chemical properties in the liquid state. Hence, this may have significant implications for carbon reservoirs and fluxes, and the global geodynamic carbon cycle.

New host for carbon in the deep Earth.

The global geochemical carbon cycle involves exchanges between the Earth's interior and the surface. Carbon is recycled into the mantle via subduction mainly as carbonates and is released to the atmosphere via volcanism mostly as CO(2). The stability of carbonates versus decarbonation and melting is therefore of great interest for understanding the global carbon cycle. For all these reasons, the thermodynamic properties and phase diagrams of these minerals are needed up to core mantle boundary conditions. However, the nature of C-bearing minerals at these conditions remains unclear. Here we show the existence of a new Mg-Fe carbon-bearing compound at depths greater than 1,800 km. Its structure, based on three-membered rings of corner-sharing (CO(4))(4-) tetrahedra, is in close agreement with predictions by first principles quantum calculations [Oganov AR, et al. (2008) Novel high-pressure structures of MgCO(3), CaCO(3) and CO(2) and their role in Earth's lower mantle. Earth Planet Sci Lett 273:38-47]. This high-pressure polymorph of carbonates concentrates a large amount of Fe((III)) as a result of intracrystalline reaction between Fe((II)) and (CO(3))(2-) groups schematically written as 4FeO + CO(2) → 2Fe(2)O(3) + C. This results in an assemblage of the new high-pressure phase, magnetite and nanodiamonds.