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.     

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.     

(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.     

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.     

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.     

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.     

Synthesis and Equation of State of (Mg,Fe) SiO3 Perovskite to Over 100 Gigapascals

Silicate perovskite of composition (Mg(0.88)Fe(0.12)) SiO(3) has been synthesized in a laser-heated diamond-anvil cell to a pressure of 127 gigapascals at temperatures exceeding 2000 K. The perovskite phase was identified and its unit-cell dimensions measured by in situ x-ray diffraction at elevated pressure and room temperature. An analysis of these data yields the first high-precision equation of state for this mineral, with values of the zero-pressure isothermal bulk modulus and its pressure derivative being K(0T) = 266 +/- 6 gigapascals and K'(0T) = 3.9 +/- 0.4. In addition, the orthorhombic distortion of the silicate-perovskite structure away from ideal cubic symmetry remains constant with pressure: the lattice parameter ratios are b/a = 1.032 +/- 0.002 and c/a = 1.444 +/- 0.006. These results, which prove that silicate perovskite is stable to ultrahigh pressures, demonstrate that perovskite can exist throughout the pressure range of the lower mantle and that it is therefore likely to be the most abundant mineral in Earth.     

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.     

Elasticity of MgSiO3 in the Perovskite Structure

The single-crystal elastic moduli of MgSiO(3) in the perovskite structure, the high-pressure polymorph of MgSiO(3) pyroxene, have been determined. The data indicate that a mantle with either pyrolite or pyroxene stoichiometry is compatible with the seismic models appropriate to the earth's lower mantle, provided that the shear modulus of MgSiO(3) perovskite exhibits a strong negative temperature derivative. Such a temperature derivative falls outside of the range expected for a well-behaved refractory ceramic and could result if the pressure-temperature regime of the earth's lower mantle is near that required for a ferroelastic phase transformation of the perovskite phase.     

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.     

Negative Pressure-Temperature Slopes for Reactions Formign MgSiO3 Perovskite from Calorimetry

A new and sensitive differential drop solution calorimetric technique was developed for very small samples. A single experiment using one 5.18-milligram sample of perovskite, synthesized at 25 gigapascals and 1873 Kelvin, gave 110.1 +/- 4.1 kilojoules per mole for the enthalpy of the ilmenite-pervoskite transition in MgSiO(3). The thermodynamics of the reaction of MgSiO(3) (ilmenite) to MgSiO(3) (perovskite) and of Mg(2)SiO(4) (spinel) to MgSiO(3) (pervoskite) and MgO (periclase) were assessed. Despite uncertainties in heat capacity and molar volume at high pressure and temperature, both reactions clearly have negative pressure-temperature slopes, -0.005 +/- 0.002 and -0.004 +/- 0.002 gigapascals per Kelvin, respectively. The latter may be insufficiently negative to preclude whole-mantle convection.     

Twinning in MgSiO3 Perovskite

Crystals of MgSiO(3) perovskite synthesized at high pressures and temperatures have orthorhombic symmetry under ambient conditions. Examination by transmission electron microscopy shows that the microstructure of crystals synthesized at 26 gigapascals and 1600 degrees C is dominated by a large number of twin domains that are related by reflection operations with respect to {112} and {110} planes. These twins may be associated with the transformations of MgSiO(3) perovskite from the cubic to tetragonal and tetragonal to orthorhombic phases, respectively, upon decreasing pressure and temperature. These observations suggest that under the experimental synthesis conditions, and perhaps in the earth's lower mantle, the stable phase of MgSiO(3) might have the cubic perovskite structure.     

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.     

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.     

Synchrotron Infrared Absorbance Measurements of Hydrogen in MgSiO3 Perovskite

Micro-infrared spectroscopic measurements on single crystals of MgSiO(3) perovskite document two pleochroic hydroxyl absorbance peaks at 3483 and 3423 centimeter(-1). These measurements were obtained with the use of a synchrotron infrared source for spectroscopy. These data are consistent with a trace hydrogen content of 700 +/- 170 hydrogen atoms per 10(6) silicon atoms in the nominally anhydrous MgSiO(3) perovskite. When integrated over the volume of the lower mantle, this concentration is comparable to 12 percent of the mass of hydrogen in the Earth's hydrosphere.     

Pressure Dependence of Elastic Wave Velocity for beta-Mg2SiO4 and the Composition of the Earth's Mantle

The pressure dependence of the elastic wave velocities for hot-pressed, elastically isotropic polycrystals of the beta (modified spinel) phase of magnesium orthosilicate (Mg(2)SiO(4)) has been determined at room temperature to 3 gigapascals (GPa) by ultrasonic pulse interferometry. Pressure derivatives of the bulk (dK/dP = 4.8) and shear (dG/dP = 1.7) moduli derived from the travel times of the compressional (P) and shear (S) waves clearly demonstrate that the velocity contrast between the olivine and beta phases of Mg(2)SiO(4) decreases with increasing pressure. When combined with plausible values for the (as yet unmeasured) temperature derivatives, these new data can be used to calculate the contrast in P and S wave velocities across an olivine-beta phase transformation occuaring at pressure-temperature conditions corresponding to about 400 kilometers depth in the earth. The seismologically observed contrasts DeltaV in both P and S wave velocities constrain the percentage of orthosilicate in a model mantle of uniform chemical composition for appropriate relative magnitudes of the temperature (T) derivatives of the bulk and shear moduli for the beta phase. Allowed combinations of orthosilicate content (percent), dK/dT, and dG/dT (both in gigapascals per Kelvin) for a pair of recent seismological models with DeltaV(p) = DeltaV(s) 4.6% include (65, -0.018, -0.020), (55, -0.015, -0.018), and (45, -0.012, -0.016).     

The postspinel phase boundary in Mg2SiO4 determined by in situ X-ray diffraction

The phase boundary between spinel (gamma phase) and MgSiO3 perovskite + MgO periclase in Mg2SiO4 was determined by in situ x-ray measurements by a combination of the synchrotron radiation source (SPring-8) and a large multianvil high-pressure apparatus. The boundary was determined at temperatures between 1400 degrees to 1800 degreesC, demonstrating that the postspinel phase boundary has a negative Clapeyron slope as estimated by quench experiments and thermodynamic analyses. The boundary was located at 21.1 (+/-0.2) gigapascals, at 1600 degreesC, which is approximately 2 gigapascals lower than earlier estimates based on other high-pressure studies.     

Thermal equation of state of aluminum-enriched silicate perovskite

Inferences of the chemical homogeneity of Earth's mantle depend on comparing laboratory-derived equations of state of mantle phases with seismically determined properties of the material in situ. A uniform chemical composition of the entire mantle has been found to be consistent with measurements, to date, of these properties for the end-member MgSiO3 perovskite phase. New pressure-volume-temperature data for silicate perovskite containing 5 mole percent Al2O3 has yielded different values of the equation of state parameters, with the bulk modulus being significantly smaller at lower mantle conditions than for aluminum-free perovskite, thus requiring adjustments in other components to match seismic observations.     

Solidus of Earth's deep mantle

The solidus of a pyrolite-like composition, approximating that of the lower mantle, was measured up to 59 gigapascals by using CO2 laser heating in a diamond anvil cell. The solidus temperatures are at least 700 kelvin below the melting temperatures of magnesiowustite, which in the deep mantle has the lowest melting temperatures of the three major components-magnesiowustite, Mg-Si-perovskite, and Ca-Si-perovskite. The solidus in the deep mantle is more than 1500 kelvin above the average present-day geotherm, but at the core-mantle boundary it is near the core temperature. Thus, partial melting of the mantle is possible at the core-mantle boundary.     

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.