The influence of δ-(Al,Fe)OOH on seismic heterogeneities in Earth's lower mantle.

The high-pressure phases of oxyhydroxides (δ-AlOOH, ε-FeOOH, and their solid solution), candidate components of subducted slabs, have wide stability fields, thus potentially influencing volatile circulation and dynamics in the Earth's lower mantle. Here, we report the elastic wave velocities of δ-(Al,Fe)OOH (Fe/(Al + Fe) = 0.13, δ-Fe13) to 79 GPa, determined by nuclear resonant inelastic X-ray scattering. At pressures below 20 GPa, a softening of the phonon spectra is observed. With increasing pressure up to the Fe3+ spin crossover (~ 45 GPa), the Debye sound velocity (vD) increases. At higher pressures, the low spin δ-Fe13 is characterized by a pressure-invariant vD. Using the equation of state for the same sample, the shear-, compressional-, and bulk-velocities (vS, vP, and vΦ) are calculated and extrapolated to deep mantle conditions. The obtained velocity data show that δ-(Al,Fe)OOH may cause low-vΦ and low-vP anomalies in the shallow lower mantle. At deeper depths, we find that this hydrous phase reproduces the anti-correlation between vS and vΦ reported for the large low seismic velocity provinces, thus serving as a potential seismic signature of hydrous circulation in the lower mantle.

Structural Changes in Liquid Lithium under High Pressure.

We have experimentally studied the effect of compression on the structure of liquid lithium (Li) by multiangle energy dispersive X-ray diffraction in a large-volume cupped-Drickamer-Toroidal cell. The structure factors, s(q), of liquid Li have been successfully determined under an isothermal compression at 600 ± 30 K and at pressures up to 11.5 GPa. The first peak position in s(q) is found to increase with increasing pressure and is showing an obvious slope change starting at ∼7.5 GPa. The slope change is interpreted as a structural change from bcc-like to fcc-like local ordering in liquid Li. At pressures above 8.7 GPa, the liquid Li becomes predominantly fcc-like up to the highest pressure of 11.5 GPa in this study. The observed structural changes in liquid Li are consistent with the recently determined melting curve of Li.

Observation of 9-Fold Coordinated Amorphous TiO2 at High Pressure.

Knowledge of the structure in amorphous dioxides is important in many fields of science and engineering. Here we report new experimental results of high-pressure polyamorphism in amorphous TiO2 (a-TiO2). Our data show that the Ti coordination number (CN) increases from 7.2 ± 0.3 at ∼16 GPa to 8.8 ± 0.3 at ∼70 GPa and finally reaches a plateau at 8.9 ± 0.3 at ≲86 GPa. The evolution of the structural changes under pressure is rationalized by the ratio (γ) of the ionic radius of Ti to that of O. It appears that the CN ≈ 9 plateau correlates with the two 9-fold coordinated polymorphs (cotunnite, Fe2P) with different γ values. This CN-γ relationship is compared with those of a-SiO2 and a-GeO2, displaying remarkably consistent behavior between CN and γ. The unified CN-γ relationship may be generally used to predict the compression behavior of amorphous AO2 compounds under extreme conditions.