Core origin of seismic velocity anomalies at Earth's core-mantle boundary.

Seismic studies have found fine-scale anomalies at the core-mantle boundary (CMB), such as ultralow velocity zones (ULVZs)1,2 and the core rigidity zone3,4. ULVZs have been attributed to mantle-related processes5-10, but little is known about a possible core origin. The precipitation of light elements in the outer core has been proposed to explain the core rigidity zone3, but it remains unclear what processes can lead to such precipitation. Despite its importance for the outer core11, the melting behaviour of Fe-Si-H at relevant pressure-temperature conditions is not well understood. Here we report observations of the crystallization of B2 FeSi from Fe-9wt%Si melted in the presence of hydrogen up to 125 GPa and 3,700 K by using laser-heated diamond anvil cells. Hydrogen dramatically increases the Si concentration in the B2 crystals to a molar ratio of Si:Fe ≈ 1, whereas it mostly remains in the coexisting Fe liquid. The high Si content in the B2 phase makes it stable in a solid form at the outermost core temperatures and less dense than the surrounding liquids. Consequently, the Si-rich crystallites could form, float and be sedimented to the underside of the CMB interface, and that well explains the core side rigidity anomalies3,4. If a small amount of the FeSi crystals can be incorporated into the mantle, they would form dense low-velocity structures above the CMB, which may account for some ULVZs10. The B2 FeSi precipitation promoted by H in the outermost core provides a single core-driven origin for two types of anomalies at the CMB. Such a scenario could also explain the core-like tungsten isotope signatures in ocean island basalts12, after the materials equilibrated with the precipitates are entrained to the uppermost mantle by the mantle plumes connected to ULVZs.

Calcium dissolution in bridgmanite in the Earth's deep mantle.

Accurate knowledge of the mineralogy is essential for understanding the lower mantle, which represents more than half of Earth's volume. CaSiO3 perovskite is believed to be the third-most-abundant mineral throughout the lower mantle, following bridgmanite and ferropericlase1-3. Here we experimentally show that the calcium solubility in bridgmanite increases steeply at about 2,300 kelvin and above 40 gigapascals to a level sufficient for a complete dissolution of all CaSiO3 component in pyrolite into bridgmanite, resulting in the disappearance of CaSiO3 perovskite at depths greater than about 1,800 kilometres along the geotherm4,5. Hence we propose a change from a two-perovskite domain (TPD; bridgmanite plus CaSiO3 perovskite) at the shallower lower mantle to a single-perovskite domain (SPD; calcium-rich bridgmanite) at the deeper lower mantle. Iron seems to have a key role in increasing the calcium solubility in bridgmanite. The temperature-driven nature can cause large lateral variations in the depth of the TPD-to-SPD change in response to temperature variations (by more than 500 kilometres). Furthermore, the SPD should have been thicker in the past when the mantle was warmer. Our finding requires revision of the deep-mantle mineralogy models and will have an impact on our understanding of the composition, structure, dynamics and evolution of the region.

Stability of hydrides in sub-Neptune exoplanets with thick hydrogen-rich atmospheres.

Many sub-Neptune exoplanets have been believed to be composed of a thick hydrogen-dominated atmosphere and a high-temperature heavier-element-dominant core. From an assumption that there is no chemical reaction between hydrogen and silicates/metals at the atmosphere-interior boundary, the cores of sub-Neptunes have been modeled with molten silicates and metals (magma) in previous studies. In large sub-Neptunes, pressure at the atmosphere-magma boundary can reach tens of gigapascals where hydrogen is a dense liquid. A recent experiment showed that hydrogen can induce the reduction of Fe[Formula: see text] in (Mg,Fe)O to Fe[Formula: see text] metal at the pressure-temperature conditions relevant to the atmosphere-interior boundary. However, it is unclear whether Mg, one of the abundant heavy elements in the planetary interiors, remains oxidized or can be reduced by H. Our experiments in the laser-heated diamond-anvil cell found that heating of MgO + Fe to 3,500 to 4,900 K (close to or above their melting temperatures) in an H medium leads to the formation of Mg[Formula: see text]FeH[Formula: see text] and H[Formula: see text]O at 8 to 13 GPa. At 26 to 29 GPa, the behavior of the system changes, and Mg-H in an H fluid and H[Formula: see text]O were detected with separate FeH[Formula: see text]. The observations indicate the dissociation of the Mg-O bond by H and subsequent production of hydride and water. Therefore, the atmosphere-magma interaction can lead to a fundamentally different mineralogy for sub-Neptune exoplanets compared with rocky planets. The change in the chemical reaction at the higher pressures can also affect the size demographics (i.e., "radius cliff") and the atmosphere chemistry of sub-Neptune exoplanets.

Large H2O solubility in dense silica and its implications for the interiors of water-rich planets.

Sub-Neptunes are common among the discovered exoplanets. However, lack of knowledge on the state of matter in [Formula: see text]O-rich setting at high pressures and temperatures ([Formula: see text]) places important limitations on our understanding of this planet type. We have conducted experiments for reactions between [Formula: see text] and [Formula: see text]O as archetypal materials for rock and ice, respectively, at high [Formula: see text] We found anomalously expanded volumes of dense silica (up to 4%) recovered from hydrothermal synthesis above ∼24 GPa where the [Formula: see text]-type (Ct) structure appears at lower pressures than in the anhydrous system. Infrared spectroscopy identified strong OH modes from the dense silica samples. Both previous experiments and our density functional theory calculations support up to 0.48 hydrogen atoms per formula unit of ([Formula: see text])[Formula: see text] At pressures above 60 GPa, [Formula: see text]O further changes the structural behavior of silica, stabilizing a niccolite-type structure, which is unquenchable. From unit-cell volume and phase equilibrium considerations, we infer that the niccolite-type phase may contain H with an amount at least comparable with or higher than that of the Ct phase. Our results suggest that the phases containing both hydrogen and lithophile elements could be the dominant materials in the interiors of water-rich planets. Even for fully layered cases, the large mutual solubility could make the boundary between rock and ice layers fuzzy. Therefore, the physical properties of the new phases that we report here would be important for understanding dynamics, geochemical cycle, and dynamo generation in water-rich planets.

In situ X-ray diffraction of silicate liquids and glasses under dynamic and static compression to megabar pressures.

Properties of liquid silicates under high-pressure and high-temperature conditions are critical for modeling the dynamics and solidification mechanisms of the magma ocean in the early Earth, as well as for constraining entrainment of melts in the mantle and in the present-day core-mantle boundary. Here we present in situ structural measurements by X-ray diffraction of selected amorphous silicates compressed statically in diamond anvil cells (up to 157 GPa at room temperature) or dynamically by laser-generated shock compression (up to 130 GPa and 6,000 K along the MgSiO3 glass Hugoniot). The X-ray diffraction patterns of silicate glasses and liquids reveal similar characteristics over a wide pressure and temperature range. Beyond the increase in Si coordination observed at 20 GPa, we find no evidence for major structural changes occurring in the silicate melts studied up to pressures and temperatures exceeding Earth's core mantle boundary conditions. This result is supported by molecular dynamics calculations. Our findings reinforce the widely used assumption that the silicate glasses studies are appropriate structural analogs for understanding the atomic arrangement of silicate liquids at these high pressures.

Stability of ferrous-iron-rich bridgmanite under reducing midmantle conditions.

Our current understanding of the electronic state of iron in lower-mantle minerals leads to a considerable disagreement in bulk sound speed with seismic measurements if the lower mantle has the same composition as the upper mantle (pyrolite). In the modeling studies, the content and oxidation state of Fe in the minerals have been assumed to be constant throughout the lower mantle. Here, we report high-pressure experimental results in which Fe becomes dominantly Fe2+ in bridgmanite synthesized at 40-70 GPa and 2,000 K, while it is in mixed oxidation state (Fe3+/∑Fe = 60%) in the samples synthesized below and above the pressure range. Little Fe3+ in bridgmanite combined with the strong partitioning of Fe2+ into ferropericlase will alter the Fe content for these minerals at 1,100- to 1,700-km depths. Our calculations show that the change in iron content harmonizes the bulk sound speed of pyrolite with the seismic values in this region. Our experiments support no significant changes in bulk composition for most of the mantle, but possible changes in physical properties and processes (such as viscosity and mantle flow patterns) in the midmantle.

The O-O Bonding and Hydrogen Storage in the Pyrite-type PtO2.

We have synthesized pyrite-type PtO2 (py-PtO2) at 50-60 GPa and successfully recovered it at 1 bar. The observed O-O stretching vibration in Raman spectra provides direct evidence for inter-oxygen bonding in the structure. We also identified the O-H vibrations in py-PtO2 synthesized from the low-temperature areas, indicating hydrogenation, py-PtO2H x ( x ≤ 1). Diffraction patterns are consistent with a range of degrees of hydrogenation controlled by temperature. We found that py-PtO2 has a high bulk modulus, 314 ± 4 GPa. The chemical behaviors found in py-PtO2 have implications for the hydrogen storage in materials with anion-anion bonding, and the geochemistry of oxygen, hydrogen, and transition metals in the deep planetary interiors.

Spin and valence dependence of iron partitioning in Earth's deep mantle.

We performed laser-heated diamond anvil cell experiments combined with state-of-the-art electron microanalysis (focused ion beam and aberration-corrected transmission electron microscopy) to study the distribution and valence of iron in Earth's lower mantle as a function of depth and composition. Our data reconcile the apparently discrepant existing dataset, by clarifying the effects of spin (high/low) and valence (ferrous/ferric) states on iron partitioning in the deep mantle. In aluminum-bearing compositions relevant to Earth's mantle, iron concentration in silicates drops above 70 GPa before increasing up to 110 GPa with a minimum at 85 GPa; it then dramatically drops in the postperovskite stability field above 116 GPa. This compositional variation should strengthen the lowermost mantle between 1,800 km depth and 2,000 km depth, and weaken it between 2,000 km depth and the D" layer. The succession of layers could dynamically decouple the mantle above 2,000 km from the lowermost mantle, and provide a rheological basis for the stabilization and nonentrainment of large low-shear-velocity provinces below that depth.

Multiple seismic reflectors in Earth's lowermost mantle.

The modern view of Earth's lowermost mantle considers a D″ region of enhanced (seismologically inferred) heterogeneity bounded by the core-mantle boundary and an interface some 150-300 km above it, with the latter often attributed to the postperovskite phase transition (in MgSiO3). Seismic exploration of Earth's deep interior suggests, however, that this view needs modification. So-called ScS and SKKS waves, which probe the lowermost mantle from above and below, respectively, reveal multiple reflectors beneath Central America and East Asia, two areas known for subduction of oceanic plates deep into Earth's mantle. This observation is inconsistent with expectations from a thermal response of a single isochemical postperovskite transition, but some of the newly observed structures can be explained with postperovskite transitions in differentiated slab materials. Our results imply that the lowermost mantle is more complex than hitherto thought and that interfaces and compositional heterogeneity occur beyond the D″ region sensu stricto.

Thickness and Clapeyron slope of the post-perovskite boundary.

The thicknesses and Clapeyron slopes of mantle phase boundaries strongly influence the seismic detectability of the boundaries and convection in the mantle. The unusually large positive Clapeyron slope found for the boundary between perovskite (Pv) and post-perovskite (pPv) (the 'pPv boundary') would destabilize high-temperature anomalies in the lowermost mantle, in disagreement with the seismic observations. Here we report the thickness of the pPv boundary in (Mg(0.91)Fe(2+)(0.09))SiO(3) and (Mg(0.9)Fe(3+)(0.1))(Al(0.1)Si(0.9))O(3) as determined in a laser-heated diamond-anvil cell under in situ high-pressure (up to 145 GPa), high-temperature (up to 3,000 K) conditions. The measured Clapeyron slope is consistent with the D'' discontinuity. In both systems, however, the pPv boundary thickness increases to 400-600 +/- 100 km, which is substantially greater than the thickness of the D'' discontinuity (<30 km). Although the Fe(2+) buffering effect of ferropericlase could decrease the pPv boundary thickness, the boundary may remain thick in a pyrolitic composition because of the effects of Al and the rapid temperature increase in the D'' layer. The pPv boundary would be particularly thick in regions with an elevated Al content and/or a low Mg/Si ratio, reducing the effects of the large positive Clapeyron slope on the buoyancy of thermal anomalies and stabilizing compositional heterogeneities in the lowermost mantle. If the pPv transition is the source of the D'' discontinuity, regions with sharp discontinuities may require distinct compositions, such as a higher Mg/Si ratio or a lower Al content.

Mineralogical effects on the detectability of the postperovskite boundary.

The discovery of a phase transition in Mg-silicate perovskite (Pv) to postperovskite (pPv) at lowermost mantle pressure-temperature (P - T) conditions may provide an explanation for the discontinuous increase in shear wave velocity found in some regions at a depth range of 200 to 400 km above the core-mantle boundary, hereafter the D('') discontinuity. However, recent studies on binary and ternary systems showed that reasonable contents of Fe(2+) and Al for pyrolite increase the thickness (width of the mixed phase region) of the Pv - pPv boundary (400-600 km) to much larger than the D('') discontinuity (≤ 70 km). These results challenge the assignment of the D('') discontinuity to the Pv - pPv boundary in pyrolite (homogenized mantle composition). Furthermore, the mineralogy and composition of rocks that can host a detectable Pv → pPv boundary are still unknown. Here we report in situ measurements of the depths and thicknesses of the Pv → pPv transition in multiphase systems (San Carlos olivine, pyrolitic, and midocean ridge basaltic compositions) at the P - T conditions of the lowermost mantle, searching for candidate rocks with a sharp Pv - pPv discontinuity. Whereas the pyrolitic mantle may not have a seismologically detectable Pv → pPv transition due to the effect of Al, harzburgitic compositions have detectable transitions due to low Al content. In contrast, Al-rich basaltic compositions may have a detectable Pv - pPv boundary due to their distinct mineralogy. Therefore, the observation of the D('') discontinuity may be related to the Pv → pPv transition in the differentiated oceanic lithosphere materials transported to the lowermost mantle by subducting slabs.

Globally distributed subducted materials along the Earth's core-mantle boundary: Implications for ultralow velocity zones.

Ultralow velocity zones (ULVZs) are the most anomalous structures within the Earth's interior; however, given the wide range of associated characteristics (thickness and composition) reported by previous studies, the origins of ULVZs have been debated for decades. Using a recently developed seismic analysis approach, we find widespread, variable ULVZs along the core-mantle boundary (CMB) beneath a largely unsampled portion of the Southern Hemisphere. Our study region is not beneath current or recent subduction zones, but our mantle convection simulations demonstrate how heterogeneous accumulations of previously subducted materials could form on the CMB and explain our seismic observations. We further show that subducted materials can be globally distributed throughout the lowermost mantle with variable concentrations. These subducted materials, advected along the CMB, can provide an explanation for the distribution and range of reported ULVZ properties.

Ultrafast x-ray detection of low-spin iron in molten silicate under deep planetary interior conditions.

The spin state of Fe can alter the key physical properties of silicate melts, affecting the early differentiation and the dynamic stability of the melts in the deep rocky planets. The low-spin state of Fe can increase the affinity of Fe for the melt over the solid phases and the electrical conductivity of melt at high pressures. However, the spin state of Fe has never been measured in dense silicate melts due to experimental challenges. We report detection of dominantly low-spin Fe in dynamically compressed olivine melt at 150 to 256 gigapascals and 3000 to 6000 kelvin using laser-driven shock wave compression combined with femtosecond x-ray diffraction and x-ray emission spectroscopy using an x-ray free electron laser. The observation of dominantly low-spin Fe supports gravitationally stable melt in the deep mantle and generation of a dynamo from the silicate melt portion of rocky planets.

Electronic and magnetic structures of the postperovskite-type Fe2O3 and implications for planetary magnetic records and deep interiors.

Recent studies have shown that high pressure (P) induces the metallization of the Fe(2+)-O bonding, the destruction of magnetic ordering in Fe, and the high-spin (HS) to low-spin (LS) transition of Fe in silicate and oxide phases at the deep planetary interiors. Hematite (Fe(2)O(3)) is an important magnetic carrier mineral for deciphering planetary magnetism and a proxy for Fe in the planetary interiors. Here, we present synchrotron Mössbauer spectroscopy and X-ray diffraction combined with ab initio calculations for Fe(2)O(3) revealing the destruction of magnetic ordering at the hematite --> Rh(2)O(3)-II type (RhII) transition at 70 GPa and 300 K, and then the revival of magnetic ordering at the RhII --> postperovskite (PPv) transition after laser heating at 73 GPa. At the latter transition, at least half of Fe(3+) ions transform from LS to HS and Fe(2)O(3) changes from a semiconductor to a metal. This result demonstrates that some magnetic carrier minerals may experience a complex sequence of magnetic ordering changes during impact rather than a monotonic demagnetization. Also local Fe enrichment at Earth's core-mantle boundary will lead to changes in the electronic structure and spin state of Fe in silicate PPv. If the ultra-low-velocity zones are composed of Fe-enriched silicate PPv and/or the basaltic materials are accumulated at the lowermost mantle, high electrical conductivity of these regions will play an important role for the electromagnetic coupling between the mantle and the core.

Crystal structure and thermoelastic properties of (Mg0.91Fe0.09)SiO3 postperovskite up to 135 GPa and 2,700 K.

Intriguing seismic observations have been made for the bottom 400 km of Earth's mantle (the D'' region) over the past few decades, yet the origin of these seismic structures has not been well understood. Recent theoretical calculations have predicted many unusual changes in physical properties across the postperovskite transition, perovskite (Pv) --> postperovskite (PPv), that may provide explanations for the seismic observations. Here, we report measurements of the crystal structure of (Mg(0.91)Fe(0.09))SiO(3)-PPv under quasi-hydrostatic conditions up to the pressure (P)-temperature (T) conditions expected for the core-mantle boundary (CMB). The measured crystal structure is in excellent agreement with the first-principles calculations. We found that bulk sound speed (V(Phi)) decreases by 2.4 +/- 1.4% across the PPv transition. Combined with the predicted shear-wave velocity (V(S)) increase, our measurements indicate that lateral variations in mineralogy between Pv and PPv may result in the anticorrelation between the V(Phi) and V(S) anomalies at the D'' region. Also, density increases by 1.6 +/- 0.4% and Grüneisen parameter decreases by 21 +/- 15% across the PPv transition, which will dynamically stabilize the PPv lenses observed in recent seismic studies.

Evidence for the charge disproportionation of iron in extraterrestrial bridgmanite.

Bridgmanite, MgSiO3 with perovskite structure, is considered the most abundant mineral on Earth. On the lower mantle, it contains Fe and Al that strongly influence its behavior. Experimentalists have debated whether iron may exist in a mixed valence state, coexistence of Fe2+ and Fe3+ in bridgmanite, through charge disproportionation. Here, we report the discovery of Fe-rich aluminous bridgmanite coexisting with metallic iron in a shock vein of the Suizhou meteorite. This is the first direct evidence in nature of the Fe disproportionation reaction, which so far has only been observed in some high-pressure experiments. Furthermore, our discovery supports the idea that the disproportionation reaction would have played a key role in redox processes and the evolution of Earth.

Anomalous Behavior of 2D Janus Excitonic Layers under Extreme Pressures.

Newly discovered 2D Janus transition metal dichalcogenides layers have gained much attention from a theory perspective owing to their unique atomic structure and exotic materials properties, but little to no experimental data are available on these materials. Here, experimental and theoretical studies establish the vibrational and optical behavior of 2D Janus S-W-Se and S-Mo-Se monolayers under high pressures for the first time. Chemical vapor deposition (CVD)-grown classical transition metal dichalcogenides (TMD) monolayers are first transferred onto van der Waals (vdW) mica substrates and converted to 2D Janus sheets by surface plasma technique, and then integrated into a 500 µm size diamond anvil cell for high-pressure studies. The results show that 2D Janus layers do not undergo phase transition up to 15 GPa, and in this pressure regime, their vibrational modes exhibit a nonmonotonic response to the applied pressures (dω/dP). Interestingly, these 2D Janus monolayers exhibit unique blueshift in photoluminescence (PL) upon compression, which is in contrast to many other traditional semiconductor materials. Overall theoretical simulations offer in-depth insights and reveal that the overall optical response is a result of competition between the ab-plane (blueshift) and c-axis (redshift) compression. The overall findings shed the very first light on how 2D Janus monolayers respond under extreme pressures and expand the fundamental understanding of these materials.

Astrobiological stoichiometry.

Chemical composition affects virtually all aspects of astrobiology, from stellar astrophysics to molecular biology. We present a synopsis of the research results presented at the "Stellar Stoichiometry" Workshop Without Walls hosted at Arizona State University April 11-12, 2013, under the auspices of the NASA Astrobiology Institute. The results focus on the measurement of chemical abundances and the effects of composition on processes from stellar to planetary scales. Of particular interest were the scientific connections between processes in these normally disparate fields. Measuring the abundances of elements in stars and giant and terrestrial planets poses substantial difficulties in technique and interpretation. One of the motivations for this conference was the fact that determinations of the abundance of a given element in a single star by different groups can differ by more than their quoted errors. The problems affecting the reliability of abundance estimations and their inherent limitations are discussed. When these problems are taken into consideration, self-consistent surveys of stellar abundances show that there is still substantial variation (factors of ∼ 2) in the ratios of common elements (e.g., C, O, Na, Al, Mg, Si, Ca) important in rock-forming minerals, atmospheres, and biology. We consider how abundance variations arise through injection of supernova nucleosynthesis products into star-forming material and through photoevaporation of protoplanetary disks. The effects of composition on stellar evolution are substantial, and coupled with planetary atmosphere models can result in predicted habitable zone extents that vary by many tens of percent. Variations in the bulk composition of planets can affect rates of radiogenic heating and substantially change the mineralogy of planetary interiors, affecting properties such as convection and energy transport.