Catalysis of the olivine to spinel transformation by high clinoenstatite

Although enstatite is a major constituent of the Earth's upper mantle and subducting lithosphere, most kinetic studies of olivine phase transformations have typically involved single-phase polycrystalline aggregates. Transmission electron microscopy investigations of olivine to spinel and modified spinel (beta phase) reactions in the (Mg, Fe)(2)SiO(4)-(Mg,Fe)SiO(3) system show that transformation of olivine in the stability field of spinel plus phase begins with coherent nucleation of spinel on high-clinoenstatite grains. These observations demonstrate that high clinoenstatite can catalyze the transformation by enhancing nucleation kinetics and therefore imply that secondary phases can influence reaction kinetics during high-pressure mineral transformations.     

Single-crystal elastic properties of the modified spinel (Beta) phase of magnesium orthosilicate

The single-crystal elastic moduli of the modified spinel structure (beta phase) of magnesium orthosilicate (Mg(2)SiO(4)) have been measured by Brillouin spectroscopy under ambient conditions. Single crystals with dimensions up to 500 micrometers were grown at 22 gigapascals and 2000 degrees C over a period of 1 hour. Growth of crystals larger than 100 micrometers was achieved only when the pressure was within 5 percent of the pressure of the phase boundary separating the beta- and gamma-phase stability fields. A comparison of the elastic properties of the modified spinel phase with those of the olivine phase suggests that the 400-kilometer seismic discontinuity in the earth's mantle can be described by a mantle with 40 percent olivine. These results confirm that the 400-kilometer discontinuity can be due to the transition from olivine to modified spinel. The amount of olivine that must be present is less than that in a pyrolite model, although the results do not exclude pyrolite as a possible mantle model.     

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.     

Electrical conductivity of olivine, wadsleyite, and ringwoodite under upper-mantle conditions

Geophysical models show that electrical conductivity in Earth's mantle rises about two orders of magnitude through the transition zone in the depth range 410 to 660 kilometers. Impedance measurements obtained on Mg1.8Fe0.2SiO4 olivine, wadsleyite, and ringwoodite at up to 20 gigapascals and 1400 degreesC show that the electrical conductivities of wadsleyite and ringwoodite are similar and are almost two orders of magnitude higher than that of olivine. A conductivity-depth profile to 660 kilometers, based on these laboratory data, shows a conductivity increase of almost two orders of magnitude across the 410-kilometer discontinuity; such a profile favors a two-layer model for the upper mantle. Activation enthalpies of 1.2 to 1.7 electron volts permit appreciable lateral variations of conductivity with lateral temperature variations.     

Sound velocities in olivine at Earth mantle pressures

The independent elastic constants of an upper mantle mineral, San Carlos olivine [(Mg(1.8)Fe(0.2))SiO(4)], were measured from 0 to 12.5 gigapascals. Evidence is offered in support of the proposition that the explicit temperature dependence of the bulk modulus is small over the range of temperatures and pressures thought to prevail above the 400-kilometer discontinuity, and thus the data can be extrapolated to estimate the properties of olivine under mantle conditions at a depth of 400 kilometers. In the absence of high-temperature data at high pressures, estimates are made of the properties of olivine under mantle conditions to a depth of 400 kilometers. In contrast with low-pressure laboratory data, the predicted covariance of shear and compressional velocities as a function of temperature nearly matches the seismically estimated value for the lower mantle.     

Olivine-garnet transformation in a meteorite

Garnet has been identified for the first time as a meteorite mineral in the Coorara chondrite from Western Australia. It replaces olivine grains in a 1-millimeter veinlet traversing the body of the meteorite. The associated olivine has abnormally low birefringence, which suggests a highly shocked condition. Microprobe analyses do not distinguish the garnet from the associated olivine, which has the composition (Mg(.75)Fe(.25))(2) SiO(4); the garnet may have the composition Mg(3)Fe(2)Si(3)O(12) but be unresolvable from the accompanying olivine, or alternatively is nonstoichiometric. Transformation of olivine to garnet under high pressure could have significant implications for the phase composition of the Earth's mantle.     

Splitting of the 520-kilometer seismic discontinuity and chemical heterogeneity in the mantle

Seismic studies indicate that beneath some regions the 520-kilometer seismic discontinuity in Earth's mantle splits into two separate discontinuities (at approximately 500 kilometers and approximately 560 kilometers). The discontinuity near 500 kilometers is most likely caused by the (Mg,Fe)2SiO4 beta-to-gamma phase transformation. We show that the formation of CaSiO3 perovskite from garnet can cause the deeper discontinuity, and by determining the temperature dependence for this reaction we demonstrate that regional variations in splitting of the discontinuity arise from variability in the calcium concentration of the mantle rather than from temperature changes. This discontinuity therefore is sensitive to large-scale chemical heterogeneity. Its occurrence and variability yield regional information on the fertility of the mantle or the proportion of recycled oceanic crust.     

Diffusion creep in perovskite: implications for the rheology of the lower mantle

High-temperature creep experiments on polycrystalline perovskite (CaTiO(3)), an analog of (Mg,Fe)SiO(3) perovskite of the lower mantle, suggest that (grain size-sensitive) diffusion creep is important in the lower mantle and show that creep rate is enhanced by the transformation from the orthorhombic to the tetragonal structure. These observations suggest that grain-size reduction after a subducting slab passes through the 670-kilometer discontinuity or after a phase transformation from orthorhombic to tetragonal in perovskite will result in rheological softening in the top portions of the lower mantle.     

Seismic evidence for olivine phase changes at the 410- and 660-kilometer discontinuities

The view that the seismic discontinuities bounding the mantle transition zone at 410- and 660-kilometer depths are caused by isochemical phase transformations of the olivine structure is debated. Combining converted-wave measurements in East Asia and Australia with seismic velocities from regional tomography studies, we observe a correlation of the thickness of, and wavespeed variations within, the transition zone that is consistent with olivine structural transformations. Moreover, the seismologically inferred Clapeyron slopes are in agreement with the mineralogical Clapeyron slopes of the (Mg,Fe)2SiO4 spinel and postspinel transformations.     

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.     

Thermoelasticity of Silicate Perovskite and Magnesiowustite and Stratification of the Earth's Mantle

Analyses of x-ray-diffraction measurements on (Mg,Fe)SiO(3) perovskite and (Mg,Fe)O magnesiowüstite at simultaneous high temperature and pressure are used to determine pressure-volume-temperature equations of state and thermoelastic properties of these lower mantle minerals. Detailed comparison with the seismically observed density and bulk sound velocity profiles of the lower mantle does not support models of this region that assume compositions identical to that of the upper mantle. The data are consistent with lower mantle compositions consisting of nearly pure perovskite (>85 percent), which would indicate that the Earth's mantle is compositionally, and by implication, dynamically stratified.     

(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.     

Oxygen diffusion in perovskite: implications for electrical conductivity in the lower mantle

Experimental determination of oxygen self-diffusion in CaTiO(3) perovskite, a structural analog of (Mg,Fe)SiO(3) perovskite, confirms a theoretical relation between diffusion constants and anion porosity. Oxygen diffusion rates in (Mg,Fe)SiO(3) perovskite calculated with this relation increase by about eight orders of magnitude through the lower mantle. Electrical conductivity values calculated from these diffusion rates are consistent with inferred conductivity values for the lower mantle. This result suggests that the dominant conductivity mechanism in the deep mantle is ionic.     

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).     

Shock-produced olivine glass: first observation

Transmission electron microscope (TEM) observations of an experimentally shock-deformed single crystal of natural peridot, (Mg(0.88)Fe(0.12))(2)SiO(4), recovered from peak pressures of about 56 x 10(9) pascals revealed the presence of amorphous zones located within crystalline regions with a high density of tangled dislocations. This is the first reported observation of olivine glass. The shocked sample exhibits a wide variation in the degree of shock deformation on a small scale, and the glass appears to be intimately associated with the highest density of dislocations. This study suggests that olivine glass may be formed as a result of shock at pressures above about 50 to 55 x 10(9) pascals and that further TEM observations of naturally shocked olivines may demonstrate the presence of glass.     

Iron partitioning in Earth's mantle: toward a deep lower mantle discontinuity

We measured the spin state of iron in ferropericlase (Mg0.83Fe0.17)O at high pressure and found a high-spin to low-spin transition occurring in the 60- to 70-gigapascal pressure range, corresponding to depths of 2000 kilometers in Earth's lower mantle. This transition implies that the partition coefficient of iron between ferropericlase and magnesium silicate perovskite, the two main constituents of the lower mantle, may increase by several orders of magnitude, depleting the perovskite phase of its iron. The lower mantle may then be composed of two different layers. The upper layer would consist of a phase mixture with about equal partitioning of iron between magnesium silicate perovskite and ferropericlase, whereas the lower layer would consist of almost iron-free perovskite and iron-rich ferropericlase. This stratification is likely to have profound implications for the transport properties of Earth's lowermost mantle.     

Comparative Compressibilities of Silicate Spinels: Anomalous Behavior of (Mg,Fe)2SiO4

Compressibilities of five silicate spinels, including gamma-Mg(2)SiO(4), gamma-Fe(2)SiO(4), Ni(2)SiO(4) and two ferromagnesian compositions, were determined on crystals positioned in the same high-pressure mount. Subjection of all crystals simultaneously to the same pressure revealed differences in compressibility that resulted from compositional differences. Ferromagnesian silicate spinels showed an anomalous 13 percent increase in bulk modulus with increasing iron content, from Mg(2)SiO(4) (184 gigapascals) to Fe(2)SiO(4) (207 gigapascals). This result suggests that ferrous iron and magnesium, which behave similarly under crustal conditions, are chemically more distinct at high pressures characteristic of the transition zone and lower mantle.     

The effect of alumina on the electrical conductivity of silicate perovskite

Measurements of the electrical conductivity of silicate perovskite at 25 gigapascals and 1400 degrees to 1600 degreesC show that the conductivity of (Mg,Fe)SiO3 perovskite containing 2.89 weight percent Al2O3 is about 3.5 times greater than that of aluminum-free (Mg0.915Fe0.085)SiO3 perovskite. The conduction mechanism in perovskite between 1400 degrees and 1600 degreesC is most likely by polarons, because Mossbauer studies show that the aluminum-bearing perovskite has about 3.5 times the amount of Fe3+ as the aluminum-free sample. A conductivity-depth profile from 660 to 2900 kilometers based on aluminum-bearing perovskite is consistent with geophysical models.     

Kornerupine: its crystal structure

Three-dimensional analysis of the crystal structure of kornerupine reveals the crystallochemical formula Mg(VI)(2)Mg(VI)AlVI(6)[Si(2)O(7)] [(Al,Si)(2) SiO(10)]O(4)(OH), with four formula units in the structure cell of a = 16.100 (2) A, b = 13.767(2) A, c = 6.735(2) A; space group, Cmcm. The unusual crystal structure includes walls of Al-O edge and corner-sharing octahedra, and chains of alternating Mg-O and Al-O octahedra fused to the walls by further edge-sharing to form dense slabs. These slabs are held together by [Si(2)O(7)] corner-sharing tetrahedral pairs and [(Al,Si)(2)SiO(10)] corner-sharing tetrahedral triplets.