Melting of (Mg,Fe)2SiO4 at the Core-Mantle Boundary of the Earth

The lower mantle of the Earth is believed to be largely composed of (Mg,Fe)O (magnesiowustite) and (Mg,Fe)SiO3 (perovskite). Radiative temperatures of single-crystal olivine [(Mg0.9,Fe0.1)2SiO4] decreased abruptly from 7040 +/- 315 to 4300 +/- 270 kelvin upon shock compression above 80 gigapascals. The data indicate that an upper bound to the solidus of the magnesiowustite and perovskite assemblage at 4300 +/- 270 kelvin is 130 +/- 3 gigapascals. These conditions correspond to those for partial melting at the base of the mantle, as has been suggested occurs within the ultralow-velocity zone beneath the central Pacific.     

Ultrasonic shear wave velocities of MgSiO3 perovskite at 8 GPa and 800 K and lower mantle composition

Ultrasonic interferometric measurements of the shear elastic properties of MgSiO3 perovskite were conducted on three polycrystalline specimens at conditions up to pressures of 8 gigapascals and temperatures of 800 kelvin. The acoustic measurements produced the pressure (P) and temperature (T) derivatives of the shear modulus (G), namely ( partial differentialG/ partial differentialP)T = 1.8 +/- 0.4 and ( partial differentialG/ partial differentialT)P = -2.9 +/- 0.3 x 10(-2) gigapascals per kelvin. Combining these derivatives with the derivatives that were measured for the bulk modulus and thermal expansion of MgSiO3 perovskite provided data that suggest lower mantle compositions between pyrolite and C1 carbonaceous chondrite and a lower mantle potential temperature of 1500 +/- 200 kelvin.     

Stability and structure of MgSiO3 perovskite to 2300-kilometer depth in Earth's mantle

Unexplained features have been observed seismically near the middle (approximately 1700-kilometer depth) and bottom of the Earth's lower mantle, and these could have important implications for the dynamics and evolution of the planet. (Mg,Fe)SiO3 perovskite is expected to be the dominant mineral in the deep mantle, but experimental results are discrepant regarding its stability and structure. Here we report in situ x-ray diffraction observations of (Mg,Fe)SiO3 perovskite at conditions (50 to 106 gigapascals, 1600 to 2400 kelvin) close to a mantle geotherm from three different starting materials, (Mg0.9Fe0.1)SiO enstatite, MgSiO3 glass, and an MgO+SiO2 mixture. Our results confirm the stability of (Mg,Fe)SiO3 perovskite to at least 2300-kilometer depth in the mantle. However, diffraction patterns above 83 gigapascals and 1700 kelvin (1900-kilometer depth) cannot presently rule out a possible transformation from Pbnm perovskite to one of three other possible perovskite structures with space group P2(1)/m, Pmmn, or P4(2)/nmc.     

(Mg,Fe)SiO3-perovskite stability under lower mantle conditions

In three different experiments up to 100 gigapascals and 3000 kelvin, (Mg,Fe)SiO3-perovskite, the major component of the lower mantle, remained stable and did not decompose to its component oxides (Mg, Fe)O and SiO2. Perovskite was formed from these oxides when heated in a diamond anvil cell at pressures up to 100 gigapascals. Both MgSiO3 crystals and glasses heated to 3000 kelvin at 75 gigapascals also formed perovskite as a single phase, as evident from Raman spectra. Moreover, fluorescence measurements on chromium-doped samples synthesized at these conditions gave no indication of the presence of MgO.     

Stability of Perovskite (MgSiO3) in the Earth's Mantle

Available thermodynamic data and seismic models favor perovskite (MgSiO3) as the stable phase in the mantle. MgSiO3 was heated at temperatures from 1900 to 3200 kelvin with a Nd-YAG laser in diamond-anvil cells to study the phase relations at pressures from 45 to 100 gigapascals. The quenched products were studied with synchrotron x-ray radiation. The results show that MgSiO3 broke down to a mixture of MgO (periclase) and SiO2 (stishovite or an unquenchable polymorph) at pressures from 58 to 85 gigapascals. These results imply that perovskite may not be stable in the lower mantle and that it might be necessary to reconsider the compositional and density models of the mantle.     

High-Temperature Phase Transition and Dissociation of (Mg, Fe)SiO3 Perovskite at Lower Mantle Pressures

To study the crystallography of Earth's lower mantle, techniques for measuring synchrotron x-ray diffraction from a laser-heated diamond anvil cell have been developed. Experiments on samples of (Mg, Fe)SiO(3) show that silicate perovskite maintains its orthorhombic symmetry at 38 gigapascals and 1850 kelvin. Measurements at 65 and 70 gigapascals provide evidence for a temperature-induced orthorhombic-to-cubic phase transition and dissociation to an assemblage of perovskite and mixed oxides. If these phase transitions occur in Earth, they will require a significant change in mineralogical models of the lower mantle.     

A surface-tailored, purely electronic, mott metal-to-insulator transition

Mott transitions, which are metal-insulator transitions (MITs) driven by electron-electron interactions, are usually accompanied in bulk by structural phase transitions. In the layered perovskite Ca(1.9)Sr(0.1)RuO4, such a first-order Mott MIT occurs in the bulk at a temperature of 154 kelvin on cooling. In contrast, at the surface, an unusual inherent Mott MIT is observed at 130 kelvin, also on cooling but without a simultaneous lattice distortion. The broken translational symmetry at the surface causes a compressional stress that results in a 150% increase in the buckling of the Ca/Sr-O surface plane as compared to the bulk. The Ca/Sr ions are pulled toward the bulk, which stabilizes a phase more amenable to a Mott insulator ground state than does the bulk structure and also energetically prohibits the structural transition that accompanies the bulk MIT.     

Post-perovskite phase transition in MgSiO3

In situ x-ray diffraction measurements of MgSiO3 were performed at high pressure and temperature similar to the conditions at Earth's core-mantle boundary. Results demonstrate that MgSiO3 perovskite transforms to a new high-pressure form with stacked SiO6-octahedral sheet structure above 125 gigapascals and 2500 kelvin (2700-kilometer depth near the base of the mantle) with an increase in density of 1.0 to 1.2%. The origin of the D" seismic discontinuity may be attributed to this post-perovskite phase transition. The new phase may have large elastic anisotropy and develop preferred orientation with platy crystal shape in the shear flow that can cause strong seismic anisotropy below the D" discontinuity.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

Grain Growth Rates of MgSiO3 Perovskite and Periclase Under Lower Mantle Conditions

The grain growth rates of MgSiO3 perovskite and periclase in aggregates have been determined at 25 gigapascals and 1573 to 2173 kelvin. The average grain size (G) was fitted to the rate equation, and the grain growth rates of perovskite and periclase were G10.6 = 1 x 10(-57.4) t exp(-320.8/RT) and G10.8 = 1 x 10(-62.3) t exp(-247.0/RT), respectively, where t is the time, R is the gas constant, and T is the absolute temperature. These growth rates provide insight into the mechanism for grain growth in minerals relevant to the Earth's lower mantle that will ultimately help define the rheology of the lower mantle.     

Fe-Mg interdiffusion in (Mg,Fe)SiO3 Perovskite and lower mantle reequilibration

Fe-Mg interdiffusion coefficients for (Mg,Fe)SiO3 perovskite have been measured at pressures of 22 to 26 gigapascals and temperatures between 1973 and 2273 kelvin. Perovskite Fe-Mg interdiffusion is as slow as Si self-diffusion and is orders of magnitude slower than Fe-Mg diffusion in other mantle minerals. Length scales over which chemical heterogeneities can homogenize, throughout the depth range of the lower mantle, are limited to a few meters even on time scales equivalent to the age of Earth. Heterogeneities can therefore only equilibrate chemically when they are stretched and thinned by intense deformation.     

Compressibility, Phase Transitions, and Oxygen Migration in Zirconium Tungstate, ZrW2O8

In situ neutron diffraction experiments show that at pressures above 2 kilobars, cubic zirconium tungstate (ZrW2O8) undergoes a quenchable phase transition to an orthorhombic phase, the structure of which has been solved from powder diffraction data. This phase transition can be reversed by heating at 393 kelvin and 1 atmosphere and involves the migration of oxygen atoms in the lattice. The high-pressure phase shows negative thermal expansion from 20 to 300 kelvin. The relative thermal expansion and compressibilities of the cubic and orthorhombic forms can be explained in terms of the "cross-bracing" between polyhedra that occurs as a result of the phase transition.     

Spin transition zone in Earth's lower mantle

Mineral properties in Earth's lower mantle are affected by iron electronic states, but representative pressures and temperatures have not yet been probed. Spin states of iron in lower-mantle ferropericlase have been measured up to 95 gigapascals and 2000 kelvin with x-ray emission in a laser-heated diamond cell. A gradual spin transition of iron occurs over a pressure-temperature range extending from about 1000 kilometers in depth and 1900 kelvin to 2200 kilometers and 2300 kelvin in the lower mantle. Because low-spin ferropericlase exhibits higher density and faster sound velocities relative to the high-spin ferropericlase, the observed increase in low-spin (Mg,Fe)O at mid-lower mantle conditions would manifest seismically as a lower-mantle spin transition zone characterized by a steeper-than-normal density gradient.     

Phase Transition and Thermal Expansion of MgSiO3 Perovskite

Results from in situ x-ray diffraction experiments with a DIA-type cubic anvil apparatus (SAM 85) reveal that MgSiO(3) perovskite transforms from the orthorhombic Pbnm symmetry to another perovskite-type structure above 600 kelvin (K) at pressures of 7.3 gigapascals; the apparent volume increase across the transition is 0.7%. Unit-cell volume increased linearly with temperature, both below (1.44 x 10(-5) K(-1)) and above (1.55 x 10(-5) K(-1)) the transition. These results indicate that the physical properties measured on the Pbnm phase should be used with great caution because they may not be applicable to the earth's lower mantle. A density analysis based on the new data yields an iron content of 10.4 weight percent for a pyrolite composition under conditions corresponding to the lower mantle. All current equation-of-state data are compatible with constant chemical composition in the upper and lower mantle; thus, these data imply that a chemically layered mantle is unnecessary, and whole-mantle convection is possible.     

Seismostratigraphy and thermal structure of Earth's core-mantle boundary region

We used three-dimensional inverse scattering of core-reflected shear waves for large-scale, high-resolution exploration of Earth's deep interior (D') and detected multiple, piecewise continuous interfaces in the lowermost layer (D') beneath Central and North America. With thermodynamic properties of phase transitions in mantle silicates, we interpret the images and estimate in situ temperatures. A widespread wave-speed increase at 150 to 300 kilometers above the coremantle boundary is consistent with a transition from perovskite to postperovskite. Internal D' stratification may be due to multiple phase-boundary crossings, and a deep wave-speed reduction may mark the base of a postperovskite lens about 2300 kilometers wide and 250 kilometers thick. The core-mantle boundary temperature is estimated at 3950 +/- 200 kelvin. Beneath Central America, a site of deep subduction, the D' is relatively cold (DeltaT = 700 +/- 100 kelvin). Accounting for a factor-of-two uncertainty in thermal conductivity, core heat flux is 80 to 160 milliwatts per square meter (mW m(-2)) into the coldest D' region and 35 to 70 mW m(-2) away from it. Combined with estimates from the central Pacific, this suggests a global average of 50 to 100 mW m(-2) and a total heat loss of 7.5 to 15 terawatts.     

Phase transition of FeO and stratification in Earth's outer core

Light elements such as oxygen in Earth's core influence the physical properties of the iron alloys that exist in this region. Describing the high-pressure behavior of these materials at core conditions constrains models of core structure and dynamics. From x-ray diffraction measurements of iron monoxide (FeO) at high pressure and temperature, we show that sodium chloride (NaCl)-type (B1) FeO transforms to a cesium chloride (CsCl)-type (B2) phase above 240 gigapascals at 4000 kelvin with 2% density increase. The oxygen-bearing liquid in the middle of the outer core therefore has a modified Fe-O bonding environment that, according to our numerical simulations, suppresses convection. The phase-induced stratification is seismologically invisible but strongly affects the geodynamo.     

Elasticity of single-crystal MgO to 8 gigapascals and 1600 kelvin

The cross pressure (P) and temperature (T) dependence of the elastic moduli (Cij) of single-crystal samples of periclase (MgO) from acoustic wave travel times was measured with ultrasonic interferometry: partial differential2C11/ partial differentialP partial differentialT = (-1.3 +/- 0.4) x 10(-3) per kelvin; partial differential2C110/ partial differentialP partial differentialT = (1. 7 +/- 0.7) x 10(-3) per kelvin; and partial differential2C44/ partial differentialP partial differentialT = (-0.2 +/- 0.3) x 10(-3) per kelvin. The elastic anisotropy of MgO decreases with increasing pressure at ambient temperature, but then increases as temperature is increased at high pressure. An assumption of zero cross pressure and temperature derivatives for the elastic moduli underestimates the elastic anisotropy and overestimates the acoustic velocities of MgO at the extrapolated high-pressure and high-temperature conditions of Earth's mantle.     

Electrical conductivity and the red shift of absorption in olivine and spinel at high pressure

Above 100 kilobars the apparent absorption edges (approximately 3 electron volts) of single-crystal and polycrystalline samples of the metastable olivine and stable spinel forms of Fe(2)SiO(4) shift rapidly with pressure from the near-ultraviolet into the lower-energy infrared region. Simultaneously, an exponential increase in electrical conductivity occurs. These effects are reversible as pressure is reduced or reapplied and are not accompanied by a first-order phase change in olivine or spinel. These observations relate to fundamental concepts of electrical conductivity and photon absorption in complex transition-metal silicates in that they cannot be readily interpreted in terms of an intrinsic band-gap model. The intensity and energy changes are too great and the effect occurs at too low a pressure to be explained by processes such as spin-pairing and other crystal-field effects. The results suggest that a new mechanism of conduction, perhaps symbiotic and employing an efficient charge-transfer process, is induced at high pressure.     

Structure of the hydrated alpha-Al(2)O(3) (0001) surface

The physical and chemical properties of the hydrated alpha-Al(2)O(3) (0001) surface are important for understanding the reactivity of natural and synthetic aluminum-containing oxides. The structure of this surface was determined in the presence of water vapor at 300 kelvin by crystal truncation rod diffraction at a third-generation synchrotron x-ray source. The fully hydrated surface is oxygen terminated, with a 53% contracted double Al layer directly below. The structure is an intermediate between alpha-Al(2)O(3) and gamma-Al(OH)(3), a fully hydroxylated form of alumina. A semiordered oxygen layer about 2.3 angstroms above the terminal oxygen layer is interpreted as adsorbed water. The clean alpha-Al(2)O(3) (0001) surface, in contrast, is Al terminated and significantly relaxed relative to the bulk structure. These differences explain the different reactivities of the clean and hydroxylated surfaces.     

Temperatures in Earth's Core Based on Melting and Phase Transformation Experiments on Iron

Experiments on melting and phase transformations on iron in a laser-heated, diamond-anvil cell to a pressure of 150 gigapascals (approximately 1.5 million atmospheres) show that iron melts at the central core pressure of 363.85 gigapascals at 6350 +/- 350 kelvin. The central core temperature corresponding to the upper temperature of iron melting is 6150 kelvin. The pressure dependence of iron melting temperature is such that a simple model can be used to explain the inner solid core and the outer liquid core. The inner core is nearly isothermal (6150 kelvin at the center to 6130 kelvin at the inner core-outer core boundary), is made of hexagonal closest-packed iron, and is about 1 percent solid (MgSiO(3) + MgO). By the inclusion of less than 2 percent of solid impurities with iron, the outer core densities along a thermal gradient (6130 kelvin at the base of the outer core and 4000 kelvin at the top) can be matched with the average seismic densities of the core.