Solubility of FeO in (Mg,Fe)SiO3 perovskite and the post-perovskite phase transition

Phase relations in Mg_0.5Fe_0.5SiO₃ and Mg_0.25Fe_0.75SiO₃ were investigated in a pressure range from 72 to 123 GPa on the basis of synchrotron X-ray diffraction measurements in situ at high-pressure and -temperature in a laser-heated diamond-anvil cell (LHDAC). Results demonstrate that Mg_0.5Fe_0.5SiO₃ perovskite is formed as a single phase at 85–108 GPa and 1800–2330 K, indicating a high solubility of FeO in (Mg,Fe)SiO₃ perovskite at high pressures. Post-perovskite appears coexisting with perovskite in Mg_0.5Fe_0.5SiO₃ above 106 GPa at 1410 K, the condition very close to the post-perovskite phase transition boundary in pure MgSiO₃. The coexistence of perovskite and post-perovskite was observed to 123 GPa. In addition, post-perovskite was formed coexisting with perovskite also in Mg_0.25Fe_0.75SiO₃ bulk composition at 106–123 GPa. In contrast to earlier experimental and theoretical studies, these results show that incorporation of FeO stabilizes perovskite at higher pressures. This could be due to a larger ionic radius of Fe²⁺ ion, which is incompatible with a small Mg²⁺ site in the post-perovskite phase.     

Superplume, supercontinent, and post-perovskite: Mantle dynamics and anti-plate tectonics on the Core–Mantle Boundary

The Western Pacific Triangular Zone (WPTZ) is the frontier of a future supercontinent to be formed at 250 Ma after present. The WPTZ is characterized by double-sided subduction zones to the east and south, and is a region dominated by extensive refrigeration and water supply into the mantle wedge since at least 200 Ma. Long stagnant slabs extending over 1200 km are present in the mid-Mantle Boundary Layer (MBL, 410–660 km) under the WPTZ, whereas on the Core–Mantle Boundary (CMB, 2700–2900 km depth), there is a thick high-V anomaly, presumably representing a slab graveyard. To explain the D″ layer cold anomaly, catastrophic collapse of once stagnant slabs in MBL is necessary, which could have occurred at 30–20 Ma, acting as a trigger to open a series of back-arc basins, hot regions, small ocean basins, and presumably formation of a series of microplates in both ocean and continent. These events were the result of replacement of upper mantle by hotter and more fertile materials from the lower mantle.The thermal structure of the solid Earth was estimated by the phase diagrams of Mid Oceanic Ridge Basalt (MORB) and pyrolite combined with seismic discontinuity planes at 410–660 km, thickness of the D″ layers, and distribution of the ultra-low velocity zone (ULVZ). The result clearly shows the presence of two major superplumes and one downwelling. Thermal structure of the Earth seems to be controlled by the subduction history back to 180 Ma, except in the D″ layer. The thermal structure of the D″ layer seems to be controlled by older slab-graveyards, as expected by paleogeographic reconstructions for Laurasia, Gondwana and Rodinia back to 700 Ma.Comparison of mantle tomography between the Pacific superplume and underneath the WPTZ suggests the transformation of a cold slab graveyard to a large-scale mantle upwelling with time. The Pacific superplume was born from the coldest CMB underneath the 1.0–0.75 Ga supercontinent Rodinia where huge amounts of cold slabs had accumulated through collision-amalgamation of more than 12 continents. A high velocity P-wave anomaly on a whole-mantle scale shows stagnant slabs restricted to the MBL of circum-Pacific and Tethyan regions. The high velocity zones can be clearly identified within the Pacific domain, suggesting the presence of slab graveyards formed at geological periods much older than the breakup of Rodinia. We speculate that the predominant subduction occurred through the formation period of Gondwana, presumably very active during 600 to 540 Ma period, and again from 400 to 300 Ma during the formation of the northern half of Pangea (Laurasia). We correlate the three dominant slab graveyards with three major orogenies in earth history, with the emerging picture suggesting that the present-day Pacific superplume is located at the center of the Rodinian slab graveyard.We speculate the mechanism of superplume formation through a comparison of the thermal structure of the mantle combined with seismic tomography under the Western Pacific Triangular Zone (WPTZ), Laurasia (Asia), Gondwana (Africa), and Rodinia (Pacific). The coldest mantle formed by extensive subduction to generate a supercontinent, changes with time of the order of several hundreds of million years to the hottest mantle underneath the supercontinent. The Pacific superplume is tightly defined by a steep velocity gradient on the margin, particularly well documented by S-wave velocity. The outermost region of the superplume is characterized by the Rodinia slab graveyard forming a donut-shape. We develop a petrologic model for the Pacific superplume and show how larger plumes are generated at shallower depths in the mantle. We link the mechanism of formation of the superplume to the presence of the mineral post-perovskite, the phase transformation of which to perovskite is exothermic, and thus aids in transporting core heat to mantle, and finally to planetary space by plumes.We summarize the characteristics of tectonic processes operating at the CMB to propose the existence of an “anti-crust” generated through “anti-plate tectonics” at the bottom of the mantle. The chemistry of the anti-crust markedly contrasts with that of the continental crust overlying the mantle. Both the crust and the anti-crust must have increased in volume through geologic time, in close relation with the geochemical reservoirs of the Earth. The process of formation of a new superplume closely accompanies the process of development of anti-crust at the bottom of mantle, through the production of dense melt from the partial melting of recycled MORB, observed now as the ULVZ. When CMB temperature is recovered to near 4000 K through phase transformation, the recycled MORB is partially melted imparting chemical buoyancy of the andesitic residual solid which rises up from CMB, leaving behind the dense melt to sink to CMB and thus increase the mass of anti-crust. These small-scale plumes develop to a large-scale superplume through collision and amalgamation with time. When all recycled MORBs are consumed, it is the time of demise of superplume. Immediately above the CMB, anti-plate tectonics operates to develop anti-crust through the horizontal movement of accumulated slab and their partial melting. Thus, we speculate that another continent, or even a supercontinent, has developed through geologic time at the bottom of the mantle.We also evaluate the heating vs. cooling models in relation to mantle dynamics. Rising plumes control not only the rifting of supercontinents and continents, but also the Atlantic stage as seen by anchored ridge by hotspots in the last 200 Ma in the Atlantic. Therefore, we propose that the major driving force for the mantle dynamics is the heat supplied from the high-T core, and not the slab pull force by cooling. The best analogy for this is the atmospheric circulation driven by the energy from Sun.     

Ab initio study of the high-pressure behavior of CaSiO3 perovskite

Using density functional simulations, within the generalized gradient approximation and projector-augmented wave method, we study structures and energetics of CaSiO₃ perovskite in the pressure range of the Earths lower mantle (0–150 GPa). At zero Kelvin temperature the cubic CaSiO₃ perovskite structure is unstable in the whole pressure range, at low pressures the orthorhombic (Pnam) structure is preferred. At 14.2 GPa there is a phase transition to the tetragonal (I4/mcm) phase. The CaIrO₃-type structure is not stable for CaSiO₃. Our results also rule out the possibility of decomposition into oxides.

High-pressure behavior of MnGeO3 and CdGeO3 perovskites and the post-perovskite phase transition

The stability and high-pressure behavior of perovskite structure in MnGeO₃ and CdGeO₃ were examined on the basis of in situ synchrotron X-ray diffraction measurements at high pressure and temperature in a laser-heated diamond-anvil cell. Results demonstrate that the structural distortion of orthorhombic MnGeO₃ perovskite is enhanced with increasing pressure and it undergoes phase transition to a CaIrO₃-type post-perovskite structure above 60 GPa at 1,800 K. A molar volume of the post-perovskite phase is smaller by 1.6% than that of perovskite at equivalent pressure. In contrast, the structure of CdGeO₃ perovskite becomes less distorted from the ideal cubic perovskite structure with increasing pressure, and it is stable even at 110 GPa and 2,000 K. These results suggest that the phase transition to post-perovskite is induced by a large distortion of perovskite structure with increasing pressure.     

Lower mantle dynamics with the post-perovskite phase change, radiative thermal conductivity, temperature- and depth-dependent viscosity

The new post-perovskite phase near the core-mantle boundary has important ramifications on lower mantle dynamics. We have investigated the dynamical impact arising from the interaction of temperature- and depth-dependent viscosity with radiative thermal conductivity, up to a lateral viscosity contrast of 10⁴, on both the ascending and descending flows in the presence of both the endothermic phase change at 670 km depth and an exothermic post-perovskite transition at 2650 km depth. The phase boundaries are approximated as localized zones. We have employed a two-dimensional Cartesian model, using a box with an aspect-ratio of 10, within the framework of the extended Boussinesq approximation. Our results for temperature- and depth-dependent viscosity corroborate the previous results for depth-dependent viscosity in that a sufficiently strong radiative thermal conductivity plays an important role for sustaining superplumes in the lower mantle, once the post-perovskite phase change is brought into play. This aspect is especially emphasized, when the radiative thermal conductivity is restricted only to the post-perovskite phase. These results revealed a greater degree of asymmetry is produced in the vertical flow structures of the mantle by the phase transitions. Mass and heat transfer between the upper and lower mantle will deviate substantially from the traditional whole-mantle convection model. Streamlines revealed that an overall complete communication between the top and lower mantle is difficult to be achieved.     

Lattice preferred orientation in CaIrO<Subscript>3</Subscript> perovskite and post-perovskite formed by plastic deformation under pressure

Lattice preferred orientations (LPO) developed in perovskite and post-perovskite structured CaIrO₃ were studied using the radial X-ray diffraction technique combined with a diamond anvil cell. Starting materials of each phase were deformed from 0.1 MPa to 6 GPa at room temperature. Only weak LPO was formed in the perovskite phase, whereas strong LPO was formed in the post-perovskite phase with an alignment of the (010) plane perpendicular to the compression axis. The present result suggests that the (010) is a dominant slip plane in the post-perovskite phase and it is in good agreement with the crystallographic prediction, dislocation observations via transmission electron microscopy, and a recent result of simple shear deformation experiment at 1 GPa–1,173 K. However, the present result contrasts markedly from the results on MgGeO₃ and (Mg,Fe)SiO₃, which suggested that the (100) or (110) is a dominant slip plane with respect to the post-perovskite structure. Therefore it is difficult to discuss the behavior of the post-perovskite phase in the Earth’s deep interior based on existing data of MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃. The possible sources of the differences between MgGeO₃, (Mg,Fe)SiO₃ and CaIrO₃ are discussed.     

Ferrous iron in post-perovskite from first-principles calculations

We investigate by first-principles calculations the effect of ferrous iron, Fe²⁺, on the structure and the equation of state of MgSiO₃ post-perovskite. We find that ferrous iron is high-spin over the pressure range of the mantle assuming a ferromagnetic structure. The bulk modulus and the specific volume increase with the addition of ferrous iron to MgSiO₃. We find that Fe partitions preferentially to post-perovskite and broadens the two-phase pressure range.     

High-pressure phase transitions of CaRhO<Subscript>3</Subscript> perovskite

High-pressure phase transitions of CaRhO₃ perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO₃ perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO₃-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V _m  = 33.43(1) cm³/mol. The Rietveld analysis also indicated that CaRhO₃ perovskite has the GdFeO₃-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V _m  = 34.04(1) cm³/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V _m  = 33.66(1) cm³/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO₃ intermediate phase suggest that the phase has edge-sharing RhO₆ octahedra and may have an intermediate structure between perovskite and post-perovskite.     

CaPtO3 as a novel post-perovskite oxide

Structural, morphological, magnetic, and thermal properties have been investigated for a novel post-perovskite oxide CaPtO₃ synthesized under high pressure. By comparing obtained structural parameters with those for known post-perovskite compounds, we argue that the chemical bond has a strong covalent character. Precise measurements of the Langevin susceptibility χ ₀ = −9.6 × 10⁻⁵ emu/mol and Debye temperature θ ∼ 470 K provide a good opportunity to confirm the reliability of first-principle calculations on predicting physical properties of the Earth’s D” layer.     

High-pressure generation in the Kawai-type multianvil apparatus equipped with tungsten-carbide anvils and sintered-diamond anvils,and X-ray observation on CaSnO3 and (Mg,Fe)SiO3

We extended the attainable pressure of the Kawai-type multianvil apparatus to 71.3 GPa and 120.3 GPa at room temperature by equipping it with tungsten carbide (WC) and sintered diamond (SD) cubic anvils, respectively. In the experiments with WC anvils, pressure decreased largely, ΔP ∼−20 GPa, on heating from room temperature to 1500 K. In the experiments with SD anvils, pressure also dropped to 105 GPa from 120 GPa at 1673 K. In order to generate higher pressure and temperatures, therefore, innovation of SD material in both quality and size are essential, together with improvements of cell assembly. Besides pressure generation, we conducted in situ energy-dispersive X-ray diffraction observations on CaSnO₃ and (Mg,Fe)SiO₃ in the experiments with WC and SD anvils, respectively. We observed the growth of new peaks, which can be assigned to the post-perovskite phase, transformed from a starting material of CaSnO₃ perovskite at 48.4 GPa and 1500 K, although they are not clearly identified. In contrast, we could not observe the post-perovskite phase of (Mg,Fe)SiO₃ in the present P–T conditions generated by experiments with SD anvils.