Ryuichi Nomura

Spin crossover and iron-rich silicate melt in the Earth/'s deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earths lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core–mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO3 perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earths deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ∼76 GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg0.95Fe0.05)SiO3 glass indicate a spin collapse around 70 GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO3 liquid becomes more dense than coexisting solid at ∼1,800 km depth in the lower mantle. Soon after the Earths formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ∼1,000 km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO3 perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core–mantle boundary region.

Reconciling Magma-Ocean Crystallization Models with the present-day Structure of the Earth’s mantle

Terrestrial planets are thought to experience episode(s) of large-scale melting early in their history. Fractionation during magma-ocean freezing leads to unstable stratification within the related cumulate layers due to progressive iron enrichment upward, but the effects of incremental cumulate overturns during MO crystallization remain to be explored. Here, we use geodynamic models with a moving-boundary approach to study convection and mixing within the growing cumulate layer, and thereafter within the fully crystallized mantle. For fractional crystallization, cumulates are efficiently stirred due to subsequent incremental overturns, except for strongly iron-enriched late-stage cumulates, which persist as a stably stratified layer at the base of the mantle for billions of years. Less extreme crystallization scenarios can lead to somewhat more subtle stratification. In any case, the long-term preservation of at least a thin layer of extremely enriched cumulates with Fe# > 0.4, as predicted by all our models, is inconsistent with seismic constraints. Based on scaling relationships, however, we infer that final-stage Fe-rich magma-ocean cumulates originally formed near the surface should have overturned as small diapirs, and hence undergone melting and reaction with the host rock during sinking. The resulting moderately iron-enriched metasomatized/hybrid rock assemblages should have accumulated at the base of the mantle, potentially fed an intermittent basal magma ocean, and be preserved through the present-day. Such moderately iron-enriched rock assemblages can reconcile the physical properties of the large low shear-wave velocity provinces in the present-day lower mantle. Thus, we reveal Hadean melting and rock-reaction processes by integrating magma-ocean crystallization models with the seismic-tomography snapshot.

KINETIC CONDENSATION AND EVAPORATION OF METALLIC IRON AND IMPLICATIONS FOR METALLIC IRON DUST FORMATION

Metallic iron is one of the most abundant condensing materials in systems of solar abundance. Because metallic iron is responsible for the continuum opacity of dust particles, it has a large contribution to the thermal structure of circumstellar environments and hence to dust evolution itself. In order to understand the formation processes of metallic iron in circumstellar environments, condensation and evaporation kinetics of metallic iron were studied experimentally. Metallic iron condenses at the maximum rate with the condensation coefficient (a parameter ranging from 0 to 1 to represent kinetic hindrance for surface reaction) of unity under high supersaturation conditions, and evaporates nearly ideally (evaporation coefficient of unity) in vacuum. On the other hand, evaporation of metallic iron takes place with more kinetic hindrance in the presence of metallic iron vapor. It is also found that metallic iron atoms nucleate heterogeneously on Al2O3. Metallic iron does not necessarily condense homogeneously in circumstellar environments, but might condense through heterogeneous nucleation on pre-existing dust. Metallic iron formation proceeds with little kinetic hindrance for highly unequilibrated conditions, but the effects of kinetic hindrance may appear for evaporation and condensation occurring near equilibrium with a timescale of months to years in protoplanetary disks.