Because of dissolution of lighter elements such as sulfur, carbon, hydrogen, and oxygen, Earth's outer core is about 10 percent less dense than molten iron at the relevant pressure and temperature conditions. To determine whether hydrogen can account for a major part of the density deficit and is therefore an important constituent in the molten iron outer core, the hydrogen concentration in molten iron was measured at 7.5 gigapascals. From these measurements, the metal-silicate melt partitioning coefficient of hydrogen was determined as a function of temperature. If the magma ocean of primordial Earth was hydrous, more than 95 mole percent of H2O in this ocean should have reacted with iron to form FeHx, and about 60 percent of the density deficit is reconciled by adding hydrogen to the core.

Iron may critically influence the physical properties and thermochemical structures of Earth's lower mantle. Its effects on thermal conductivity, with possible consequences on heat transfer and mantle dynamics, however, remain largely unknown. We measured the lattice thermal conductivity of lower-mantle ferropericlase to 120 GPa using the ultrafast optical pump-probe technique in a diamond anvil cell. The thermal conductivity of ferropericlase with 56% iron significantly drops by a factor of 1.8 across the spin transition around 53 GPa, while that with 8-10% iron increases monotonically with pressure, causing an enhanced iron substitution effect in the low-spin state. Combined with bridgmanite data, modeling of our results provides a self-consistent radial profile of lower-mantle thermal conductivity, which is dominated by pressure, temperature, and iron effects, and shows a twofold increase from top to bottom of the lower mantle. Such increase in thermal conductivity may delay the cooling of the core, while its decrease with iron content may enhance the dynamics of large low shear-wave velocity provinces. Our findings further show that, if hot and strongly enriched in iron, the seismic ultralow velocity zones have exceptionally low conductivity, thus delaying their cooling.

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO 3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO 3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; [3] O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO 3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO 3 melt toward deeper part of the Earth's lower mantle.silicate melts at high pressure ͉ tricluster oxygen T he nature of silicate melts at high pressure and temperature governs magmatic processes in the Earth's interior and it probably dominated the differentiation of Earth in the Hadean magma ocean where significant fractions of the Earth were melts (1-3). It has been suggested that the potential presence of silicate melts, primarily in MgSiO 3 composition, at the top of the transition zone (4-6) and in the core-mantle boundary (7,8) significantly contributes to the seismic heterogeneity of the regions. Pressure-induced structural changes in the silicate melts play an important role in the macroscopic thermodynamic, transport, and electronic properties at high pressure (e.g., refs. 9-13). Despite their importance and implications for global geophysical processes in the Earth's interior as precursors to crystalline MgSiO 3 phases, including perovskite and postperovskite (14, 15), the high-pressure structures of MgSiO 3 glass and melt remain enigmatic because of their inherent structural disorder and the lack of suitable experimental probes at high pressures. In other binary alkali and ternary aluminosilicate glasses, the densification mechanism is mostly associated with an increase, either gradual or abrupt, in the coordination number of the framework cations, such as Si and Al from 4 to 5 and 6 at the expense of the nonbridging oxygen (NBO) (11,12,(16)(17)(18)(19)(20). However, pressure dependence of the coord...

Knowledge of the electronic structure of amorphous and liquid silica at high pressures is essential to understanding their complex properties ranging from silica melt in magma to silica glass in optics, electronics, and material science. Here we present oxygen near K-edge spectra of SiO 2 glass to 51 GPa obtained using x-ray Raman scattering in a diamond-anvil cell. The x-ray Raman spectra below ϳ10 GPa are consistent with those of quartz and coesite, whereas the spectra above ϳ22 GPa are similar to that of stishovite. This pressureinduced spectral change indicates an electronic bonding transition occurring from a fourfold quartzlike to a sixfold stishovitelike configuration in SiO 2 glass between 10 GPa and 22 GPa. In contrast to the irreversible densification, the electronic bonding transition is reversible upon decompression. The observed reversible bonding transition and irreversible densification call for a coherent understanding of the transformation mechanism in compressed SiO 2 glass.

High‐quality single‐crystals of (Al,Fe)‐bearing bridgmanite, Mg0.88 Fe3+0.065Fe2+0.035Al0.14Si0.90O3, of hundreds of micrometer size were synthesized at 24 GPa and 1800 °C in a Kawai‐type apparatus from the starting hydrous melt containing ~6.7 wt% water. Analyses of synthesized bridgmanite using petrographic microscopy, scanning electron microscopy, and transmission electron microscopy show that the crystals are chemically homogeneous and inclusion free in micrometer‐ to nanometer‐spatial resolutions. Nanosecondary ion mass spectrometry (NanoSIMS) analyses on selected platelets show ~1,020(±70) ppm wt water (hydrogen). The high water concentration in the structure of bridgmanite was further confirmed using polarized and unpolarized Fourier‐transform infrared spectroscopy (FTIR) analyses with two pronounced OH‐stretching bands at ~3,230 and ~3,460 cm−1. Our results indicate that lower‐mantle bridgmanite can accommodate relatively high amount of water. Therefore, dehydration melting at the topmost lower mantle by downward flow of transition zone materials would require water content exceeding ~0.1 wt%.

Knowing the elasticity of ferropericlase across the spin transition can help explain seismic and mineralogical models of the lower-mantle including the origin of seismic heterogeneities in the middle to lowermost parts of the lower mantle1234. However, the effects of spin transition on full elastic constants of ferropericlase remain experimentally controversial due to technical challenges in directly measuring sound velocities under lower-mantle conditions12345. Here we have reliably measured both VP and VS of a single-crystal ferropericlase ((Mg0.92,Fe0.08)O) using complementary Brillouin Light Scattering and Impulsive Stimulated Light Scattering coupled with a diamond anvil cell up to 96 GPa. The derived elastic constants show drastically softened C11 and C12 within the spin transition at 40–60 GPa while C44 is not affected. The spin transition is associated with a significant reduction of the aggregate VP/VS via the aggregate VP softening because VS softening does not visibly occur within the transition. Based on thermoelastic modelling along an expected geotherm, the spin crossover in ferropericlase can contribute to 2% reduction in VP/VS in a pyrolite mineralogical model in mid lower-mantle. Our results imply that the middle to lowermost parts of the lower-mantle would exhibit enhanced seismic heterogeneities due to the occurrence of the mixed-spin and low-spin ferropericlase.

We demonstrate an alternative principle to efficiently store molecular hydrogen fuel into clathrate hydrate medium. Hydrogen-free hydrate powders quickly absorb the hydrogen gas at moderate pressure appropriate for industrial applications. The absorption kinetics was observed in situ by nuclear magnetic resonance (NMR) spectroscopy in a pressurized tube. The diffusion of hydrogen through the solid hydrate medium was directly measured by pulsed field gradient NMR. At temperatures down to 250K, the stored hydrogen is still mobile so that the hydrate storage should work well even in cold environments.

Density of the Earth's core is lower than that of pure iron and the light element(s) in the core is a long-standing problem. Hydrogen is the most abundant element in the solar system and thus one of the important candidates. However, the dissolution process of hydrogen into iron remained unclear. Here we carry out high-pressure and high-temperature in situ neutron diffraction experiments and clarify that when the mixture of iron and hydrous minerals are heated, iron is hydrogenized soon after the hydrous mineral is dehydrated. This implies that early in the Earth's evolution, as the accumulated primordial material became hotter, the dissolution of hydrogen into iron occurred before any other materials melted. This suggests that hydrogen is likely the first light element dissolved into iron during the Earth's evolution and it may affect the behaviour of the other light elements in the later processes.