Density deficit of Earth's core revealed by a multimegabar primary pressure scale.

An accurate pressure scale is a fundamental requirement to understand planetary interiors. Here, we establish a primary pressure scale extending to the multimegabar pressures of Earth's core, by combined measurement of the acoustic velocities and the density from a rhenium sample in a diamond anvil cell using inelastic x-ray scattering and x-ray diffraction. Our scale agrees well with previous primary scales and shock Hugoniots in each experimental pressure range and reveals that previous scales have overestimated laboratory pressures by at least 20% at 230 gigapascals. It suggests that the light element content in Earth's inner core (the density deficit relative to iron) is likely to be double what was previously estimated, or Earth's inner core temperature is much higher than expected, or some combination thereof.

Sound velocity of hexagonal close-packed iron to the Earth's inner core pressure.

Here we determine the compressional and shear wave velocities (vp and vs) of hexagonal close-packed iron, a candidate for the main constituent of the Earth's inner core, to pressures above 300 gigapascals using a newly designed diamond anvil cell and inelastic X-ray scattering combined with X-ray diffraction. The present results reveal that the vp and vs of the Preliminary reference Earth model (PREM) inner core are 4(±2)% and 36(±17)% slower than those of the pure iron, respectively at the centre of the core. The density and sound velocity of the PREM inner core can be explained by addition of 3(±1) wt% silicon and 3(±2) wt% sulphur to iron‒5 wt% nickel alloy. Our suggested inner core composition is consistent with the existing outer core model with oxygen, as the growth of the inner core may have created a secular enrichment of the element in the outer core.

Superhydrous aluminous silica phases as major water hosts in high-temperature lower mantle.

Water transported by subducted oceanic plates changes mineral and rock properties at high pressures and temperatures, affecting the dynamics and evolution of the Earth's interior. Although geochemical observations imply that water should be stored in the lower mantle, the limited amounts of water incorporation in pyrolitic lower-mantle minerals suggest that water in the lower mantle may be stored in the basaltic fragments of subducted slabs. Here, we performed multianvil experiments to investigate the stability and water solubility of aluminous stishovite and CaCl2-structured silica, referred to as poststishovite, in the SiO2-Al2O3-H2O systems at 24 to 28 GPa and 1,000 to 2,000 °C, representing the pressure-temperature conditions of cold subducting slabs to hot upwelling plumes in the top lower mantle. The results indicate that both alumina and water contents in these silica minerals increase with increasing temperature under hydrous conditions due to the strong Al3+-H+ charge coupling substitution, resulting in the storage of water up to 1.1 wt %. The increase of water solubility in these hydrous aluminous silica phases at high temperatures is opposite of that of other nominally anhydrous minerals and of the stability of the hydrous minerals. This feature prevents the releasing of water from the subducting slabs and enhances the transport water into the deep lower mantle, allowing significant amounts of water storage in the high-temperature lower mantle and circulating water between the upper mantle and the lower mantle through subduction and plume upwelling. The shallower depths of midmantle seismic scatterers than expected from the pure SiO2 stishovite-poststishovite transition pressure support this scenario.

Natural Fe-bearing aluminous bridgmanite in the Katol L6 chondrite.

Bridgmanite, the most abundant mineral of the Earth's lower mantle, has been reported in only a few shocked chondritic meteorites; however, the compositions of these instances differ from that expected in the terrestrial bridgmanite. Here, we report the first natural occurrence of Fe-bearing aluminous bridgmanite in shock-induced melt veins within the Katol L6 chondrite with a composition that closely matches those synthesized in high-pressure and temperature experiments over the last three decades. The Katol bridgmanite coexists with majorite and metal-sulfide intergrowths. We found that the natural Fe-bearing aluminous bridgmanite in the Katol L6 chondrite has a significantly higher Fe3+/ΣFe ratio (0.69 ± 0.08) than coexisting majorite (0.37 ± 0.10), which agrees with experimental studies. The Katol bridgmanite is arguably the closest natural analog for the bridgmanite composition expected to be present in the Earth's lower mantle. Textural observations and comparison with laboratory experiments suggest that the Katol bridgmanite formed at pressures of ∼23 to 25 gigapascals directly from the chondritic melt generated by the shock event. Thus, the Katol L6 sample may also serve as a unique analog for crystallization of bridgmanite during the final stages of magma ocean crystallization during Earth's formation.

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.

The role of water in Earth's mantle.

Geophysical observations suggest that the transition zone is wet locally. Continental and oceanic sediment components together with the basaltic and peridotitic components might be transported and accumulated in the transition zone. Low-velocity anomalies at the upper mantle-transition zone boundary might be caused by the existence of dense hydrous magmas. Water can be carried farther into the lower mantle by the slabs. The anomalous Q and shear wave regions locating at the uppermost part of the lower mantle could be caused by the existence of fluid or wet magmas in this region because of the water-solubility contrast between the minerals in the transition zone and those in the lower mantle. δ-H solid solution AlO2H-MgSiO4H2 carries water into the lower mantle. Hydrogen-bond symmetrization exists in high-pressure hydrous phases and thus they are stable at the high pressures of the lower mantle. Thus, the δ-H solid solution in subducting slabs carries water farther into the bottom of the lower mantle. Pyrite FeO2H x is formed due to a reaction between the core and hydrated slabs. This phase could be a candidate for the anomalous regions at the core-mantle boundary.

Interstitial hydrogen atoms in face-centered cubic iron in the Earth's core.

Hydrogen is likely one of the light elements in the Earth's core. Despite its importance, no direct observation has been made of hydrogen in an iron lattice at high pressure. We made the first direct determination of site occupancy and volume of interstitial hydrogen in a face-centered cubic (fcc) iron lattice up to 12 GPa and 1200 K using the in situ neutron diffraction method. The transition temperatures from the body-centered cubic and the double-hexagonal close-packed phases to the fcc phase were higher than reported previously. At pressures <5 GPa, the hydrogen content in the fcc iron hydride lattice (x) was small at x < 0.3, but increased to x > 0.8 with increasing pressure. Hydrogen atoms occupy both octahedral (O) and tetrahedral (T) sites; typically 0.870(±0.047) in O-sites and 0.057(±0.035) in T-sites at 12 GPa and 1200 K. The fcc lattice expanded approximately linearly at a rate of 2.22(±0.36) Å3 per hydrogen atom, which is higher than previously estimated (1.9 Å3/H). The lattice expansion by hydrogen dissolution was negligibly dependent on pressure. The large lattice expansion by interstitial hydrogen reduced the estimated hydrogen content in the Earth's core that accounted for the density deficit of the core. The revised analyses indicate that whole core may contain hydrogen of 80(±31) times of the ocean mass with 79(±30) and 0.8(±0.3) ocean mass for the outer and inner cores, respectively.

Discovery of moganite in a lunar meteorite as a trace of H2O ice in the Moon's regolith.

Moganite, a monoclinic SiO2 phase, has been discovered in a lunar meteorite. Silica micrograins occur as nanocrystalline aggregates of mostly moganite and occasionally coesite and stishovite in the KREEP (high potassium, rare-earth element, and phosphorus)-like gabbroic-basaltic breccia NWA 2727, although these grains are seemingly absent in other lunar meteorites. We interpret the origin of these grains as follows: alkaline water delivery to the Moon via carbonaceous chondrite collisions, fluid capture during impact-induced brecciation, moganite precipitation from the captured H2O at pH 9.5 to 10.5 and 363 to 399 K on the sunlit surface, and meteorite launch from the Moon caused by an impact at 8 to 22 GPa and >673 K. On the subsurface, this captured H2O may still remain as ice at estimated bulk content of >0.6 weight %. This indicates the possibility of the presence of abundant available water resources underneath local sites of the host bodies within the Procellarum KREEP and South Pole Aitken terranes.

Diamond formation in the deep lower mantle: a high-pressure reaction of MgCO3 and SiO2.

Diamond is an evidence for carbon existing in the deep Earth. Some diamonds are considered to have originated at various depth ranges from the mantle transition zone to the lower mantle. These diamonds are expected to carry significant information about the deep Earth. Here, we determined the phase relations in the MgCO3-SiO2 system up to 152 GPa and 3,100 K using a double sided laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction. MgCO3 transforms from magnesite to the high-pressure polymorph of MgCO3, phase II, above 80 GPa. A reaction between MgCO3 phase II and SiO2 (CaCl2-type SiO2 or seifertite) to form diamond and MgSiO3 (bridgmanite or post-perovsktite) was identified in the deep lower mantle conditions. These observations suggested that the reaction of the MgCO3 phase II with SiO2 causes formation of super-deep diamond in cold slabs descending into the deep lower mantle.

Effect of cation substitution on bridgmanite elasticity: A key to interpret seismic anomalies in the lower mantle.

Seismological observations show that, in some regions of the lower mantle, an increase in bulk sound velocity, interestingly, occurs in the same volume where there is a decrease in shear velocity. We show that this anti-correlated behavior occurs on cation substitution in bridgmanite by making single crystal elasticity measurements of MgSiO3 and (Mg,Fe,Al)(Si,Al)O3 using inelastic x-ray scattering in the ambient conditions. Cation substitution of ferrous iron and aluminum may explain large low shear velocity provinces in the lower mantle.

Constraints on Earth's inner core composition inferred from measurements of the sound velocity of hcp-iron in extreme conditions.

Hexagonal close-packed iron (hcp-Fe) is a main component of Earth's inner core. The difference in density between hcp-Fe and the inner core in the Preliminary Reference Earth Model (PREM) shows a density deficit, which implies an existence of light elements in the core. Sound velocities then provide an important constraint on the amount and kind of light elements in the core. Although seismological observations provide density-sound velocity data of Earth's core, there are few measurements in controlled laboratory conditions for comparison. We report the compressional sound velocity (V P) of hcp-Fe up to 163 GPa and 3000 K using inelastic x-ray scattering from a laser-heated sample in a diamond anvil cell. We propose a new high-temperature Birch's law for hcp-Fe, which gives us the V P of pure hcp-Fe up to core conditions. We find that Earth's inner core has a 4 to 5% smaller density and a 4 to 10% smaller V P than hcp-Fe. Our results demonstrate that components other than Fe in Earth's core are required to explain Earth's core density and velocity deficits compared to hcp-Fe. Assuming that the temperature effects on iron alloys are the same as those on hcp-Fe, we narrow down light elements in the inner core in terms of the velocity deficit. Hydrogen is a good candidate; thus, Earth's core may be a hidden hydrogen reservoir. Silicon and sulfur are also possible candidates and could show good agreement with PREM if we consider the presence of some melt in the inner core, anelasticity, and/or a premelting effect.

Discovery of coesite and stishovite in eucrite.

Howardite-eucrite-diogenite meteorites (HEDs) probably originated from the asteroid 4 Vesta. We investigated one eucrite, Béréba, to clarify a dynamic event that occurred on 4 Vesta using a shock-induced high-pressure polymorph. We discovered high-pressure polymorphs of silica, coesite, and stishovite originating from quartz and/or cristobalite in and around the shock-melt veins of Béréba. Lamellar stishovite formed in silica grains through a solid-state phase transition. A network-like rupture was formed and melting took place along the rupture in the silica grains. Nanosized granular coesite grains crystallized from the silica melt. Based on shock-induced high-pressure polymorphs, the estimated shock-pressure condition ranged from ∼8 to ∼13 GPa. Considering radiometric ages and shock features, the dynamic event that led to the formation of coesite and stishovite occurred ca. 4.1 Ga ago, which corresponds to the late heavy bombardment period (ca. 3.8-4.1 Ga), deduced from the lunar cataclysm. There are two giant impact basins around the south pole of 4 Vesta. Although the origin of HEDs is thought to be related to dynamic events that formed the basins ca. 1.0 Ga ago, our findings are at variance with that idea.

Jadeite in Chelyabinsk meteorite and the nature of an impact event on its parent body.

The Chelyabinsk asteroid impact is the second largest asteroid airburst in our recorded history. To prepare for a potential threat from asteroid impacts, it is important to understand the nature and formational history of Near-Earth Objects (NEOs) like Chelyabinsk asteroid. In orbital evolution of an asteroid, collision with other asteroids is a key process. Here, we show the existence of a high-pressure mineral jadeite in shock-melt veins of Chelyabinsk meteorite. Based on the mineral assemblage and calculated solidification time of the shock-melt veins, the equilibrium shock pressure and its duration were estimated to be at least 3-12 GPa and longer than 70 ms, respectively. This suggests that an impactor larger than 0.15-0.19 km in diameter collided with the Chelyabinsk parent body at a speed of at least 0.4-1.5 km/s. This impact might have separated the Chelyabinsk asteroid from its parent body and delivered it to the Earth.

A compact system for generating extreme pressures and temperatures: an application of laser-heated diamond anvil cell to inelastic X-ray scattering.

A compact system for generating extreme pressures and temperatures was developed for versatile experiments based on laser-heated diamond anvil cell technique. This system has been used for inelastic X-ray scattering measurements for iron.

Discovery of seifertite in a shocked lunar meteorite.

Many craters and thick regoliths of the moon imply that it has experienced heavy meteorite bombardments. Although the existence of a high-pressure polymorph is a stark evidence for a dynamic event, few high-pressure polymorphs are found in a lunar sample. α-PbO2-type silica (seifertite) is an ultrahigh-pressure polymorph of silica, and is found only in a heavily shocked Martian meteorite. Here we show evidence for seifertite in a shocked lunar meteorite, Northwest Africa 4734. Cristobalite transforms to seifertite by high-pressure and -temperature condition induced by a dynamic event. Considering radio-isotopic ages determined previously, the dynamic event formed seifertite on the moon, accompanying the complete resetting of radio-isotopic ages, is ~2.7 Ga ago. Our finding allows us to infer that such intense planetary collisions occurred on the moon until at least ~2.7 Ga ago.

Natural dissociation of olivine to (Mg,Fe)SiO3 perovskite and magnesiowustite in a shocked Martian meteorite.

We report evidence for the natural dissociation of olivine in a shergottite at high-pressure and high-temperature conditions induced by a dynamic event on Mars. Olivine (Fa(34-41)) adjacent to or entrained in the shock melt vein and melt pockets of Martian meteorite olivine-phyric shergottite Dar al Gani 735 dissociated into (Mg,Fe)SiO(3) perovskite (Pv)+magnesiowüstite (Mw), whereby perovskite partially vitrified during decompression. Transmission electron microscopy observations reveal that microtexture of olivine dissociation products evolves from lamellar to equigranular with increasing temperature at the same pressure condition. This is in accord with the observations of synthetic samples recovered from high-pressure and high-temperature experiments. Equigranular (Mg,Fe)SiO(3) Pv and Mw have 50-100 nm in diameter, and lamellar (Mg,Fe)SiO(3) Pv and Mw have approximately 20 and approximately 10 nm in thickness, respectively. Partitioning coefficient, K(Pv/Mw) = [FeO/MgO]/[FeO/MgO](Mw), between (Mg,Fe)SiO(3) Pv and Mw in equigranular and lamellar textures are approximately 0.15 and approximately 0.78, respectively. The dissociation of olivine implies that the pressure and temperature conditions recorded in the shock melt vein and melt pockets during the dynamic event were approximately 25 GPa but 700 °C at least.

Crystallographic preferred orientation of akimotoite and seismic anisotropy of Tonga slab.

The mineral akimotoite, ilmenite-structured MgSiO(3), exists at the bottom of the Earth's mantle transition zone and within the uppermost lower mantle, especially under low-temperature conditions. Akimotoite is thought to be a major constituent of the harzburgite layer of subducting slabs, and the most anisotropic mineral in the mantle transition zone. It has been predicted that if akimotoite crystals are preferentially oriented by plastic deformation, a cold subducted slab would be extremely anisotropic. However, there have been no studies of crystallographic preferred orientations and very few reports of plastic deformation experiments for MgSiO(3) ilmenite. Here we present plastic deformation experiments on polycrystalline akimotoite, which were conducted at confining pressures of 20-22 GPa and temperatures of 1,000-1,300 degrees C. We found a change in crystallographic preferred orientation pattern of akimotoite with temperature, where the c-axis maximum parallel to the compression direction develops at high temperature, whereas the c axes are preferentially oriented parallel to the shear direction or perpendicular to the compression direction at lower temperature. The previously reported difference in compressional-wave seismic anisotropy between the northern and southern segments of the Tonga slab at depths of the mantle transition zone can conceivably be attributed to the difference in the crystallographic preferred orientation pattern of akimotoite at varying temperature within the slab.

Evidence for fractional crystallization of wadsleyite and ringwoodite from olivine melts in chondrules entrained in shock-melt veins.

Peace River is one of the few shocked members of the L-chondrites clan that contains both high-pressure polymorphs of olivine, ringwoodite and wadsleyite, in diverse textures and settings in fragments entrained in shock-melt veins. Among these settings are complete olivine porphyritic chondrules. We encountered few squeezed and flattened olivine porphyritic chondrules entrained in shock-melt veins of this meteorite with novel textures and composition. The former chemically unzoned (Fa(24-26)) olivine porphyritic crystals are heavily flattened and display a concentric intergrowth with Mg-rich wadsleyite of a very narrow compositional range (Fa(6)-Fa(10)) in the core. Wadsleyite core is surrounded by a Mg-poor and chemically stark zoned ringwoodite (Fa(28)-Fa(38)) belt. The wadsleyite-ringwoodite interface denotes a compositional gap of up to 32 mol % fayalite. A transmission electron microscopy study of focused ion beam slices in both regions indicates that the wadsleyite core and ringwoodite belt consist of granoblastic-like intergrowth of polygonal crystallites of both ringwoodite and wadsleyite, with wadsleyite crystallites dominating in the core and ringwoodite crystallites dominating in the belt. Texture and compositions of both high-pressure polymorphs are strongly suggestive of formation by a fractional crystallization of the olivine melt of a narrow composition (Fa(24-26)), starting with Mg-rich wadsleyite followed by the Mg-poor ringwoodite from a shock-induced melt of olivine composition (Fa(24-26)). Our findings could erase the possibility of the resulting unrealistic time scales of the high-pressure regime reported recently from other shocked L-6 chondrites.

The post-stishovite phase transition in hydrous alumina-bearing SiO2 in the lower mantle of the earth.

Silica is the most abundant oxide component in the Earth mantle by weight, and stishovite, the rutile-structured (P4(2)/mnm) high-pressure phase with silica in six coordination by oxygen, is one of the main constituents of the basaltic layer of subducting slabs. It may also be present as a free phase in the lower mantle and at the core-mantle boundary. Pure stishovite undergoes a displacive phase transition to the CaCl(2) structure (Pnnm) at approximately 55 GPa. Theory suggests that this transition is associated with softening of the shear modulus that could provide a significant seismic signature, but none has ever been observed in the Earth. However, stishovite in natural rocks is expected to contain up to 5 wt % Al(2)O(3) and possibly water. Here we report the acoustic velocities, densities, and Raman frequencies of aluminum- and hydrogen-bearing stishovite with a composition close to that expected in the Earth mantle at pressures up to 43.8(3) GPa [where (3) indicates an uncertainty of 0.3 GPa]. The post-stishovite phase transition occurs at 24.3(5) GPa (at 298 K), far lower than for pure silica at 50-60 GPa. Our results suggest that the rutile-CaCl(2) transition in natural stishovite (with 5 wt % Al(2)O(3)) should occur at approximately 30 GPa or approximately 1,000-km depth at mantle temperatures. The major changes in elastic properties across this transition could make it visible in seismic profiles and may be responsible for seismic reflectors observed at 1,000- to 1,400-km depth.

Stability of hydrous melt at the base of the Earth's upper mantle.

Seismological observations have revealed the existence of low-velocity and high-attenuation zones above the discontinuity at 410 km depth, at the base of the Earth's upper mantle. It has been suggested that a small amount of melt could be responsible for such anomalies. The density of silicate melt under dry conditions has been measured at high pressure and found to be denser than the surrounding solid, thereby allowing the melt to remain at depth. But no experimental investigation of the density of hydrous melt has yet been carried out. Here we present data constraining the density of hydrous basaltic melt under pressure to examine the stability of melt above the 410-km discontinuity. We infer that hydrous magma formed by partial melting above the 410-km discontinuity may indeed be gravitationally stable, thereby supporting the idea that low-velocity or high-attentuation regions just above the mantle transition zone may result from the presence of melt.