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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

The electrical conductivity of post-perovskite in Earth's D' layer

Recent discovery of a phase transition from perovskite to post-perovskite suggests that the physical properties of Earth's lowermost mantle, called the D' layer, may be different from those of the overlying mantle. We report that the electrical conductivity of (Mg0.9Fe0.1)SiO3 post-perovskite is >10(2) siemens per meter and does not vary greatly with temperature at the conditions of the D' layer. A post-perovskite layer above the core-mantle boundary would, by electromagnetic coupling, enhance the exchange of angular momentum between the fluid core and the solid mantle, which can explain the observed changes in the length of a day on decadal time scales. Heterogeneity in the conductivity of the lowermost mantle is likely to depend on changes in chemistry of the boundary region, not fluctuations in temperature.     

(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.     

Electronic transitions in perovskite: possible nonconvecting layers in the lower mantle

We measured the spin state of iron in magnesium silicate perovskite (Mg(0.9),Fe(0.1))SiO(3) at high pressure and found two electronic transitions occurring at 70 gigapascals and at 120 gigapascals, corresponding to partial and full electron pairing in iron, respectively. The proportion of iron in the low spin state thus grows with depth, increasing the transparency of the mantle in the infrared region, with a maximum at pressures consistent with the D" layer above the core-mantle boundary. The resulting increase in radiative thermal conductivity suggests the existence of nonconvecting layers in the lowermost mantle.     

The Effect of H2O on the 410-Kilometer Seismic Discontinuity

The 410-kilometer seismic discontinuity is generally considered to be caused by a phase transformation of the main constituent of the upper mantle, olivine, alpha-(Mg,Fe)(2)SiO(4), to beta-(Mg,Fe)(2)SiO(4). Recent data show that H(2)O dissolves in olivine and other nominally anhydrous mantle minerals and that the partitioning of H(2)O between olivine and beta-(Mg,Fe)(2)SiO(4) is about 1:10. Such behavior strongly affects the region over which the alpha to beta phase transformation occurs and hence the seismic discontinuity that results. The observed width of the discontinuity constrains the maximum H(2)O content of upper mantle olivine to about 200 parts per million by weight.     

Multivariable dependence of Fe-Mg partitioning in the lower mantle

High-pressure diamond-cell experiments indicate that the iron-magnesium partitioning between (Fe,Mg)SiO3-perovskite and magnesiowustite in Earth's lower mantle depends on the pressure, temperature, bulk iron/magnesium ratio, and ferric iron content. The perovskite stability field expands with increasing pressure and temperature. The ferric iron component preferentially dissolves in perovskite and raises the apparent total iron content but had little effect on the partitioning of the ferrous iron. The ferrous iron depletes in perovskite at the top of the lower mantle and gradually increases at greater depth. These changes in iron-magnesium composition should affect geochemical and geophysical properties of the deep interior.     

The Phase Boundary Between agr- and beta-Mg2SiO4 Determined by in Situ X-ray Observation

The stability of Mg(2)SiO(4), a major constituent in the Earth's mantle, has been investigated experimentally by in situ observation with synchrotron radiation. A cubic-type high-pressure apparatus equipped with sintered diamond anvils has been used over pressures of 11 to 15 gigapascals and temperatures of 800 degrees to 1600 degrees C. The phase stability of alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) was determined by taking account of the kinetic behavior of transition. The phase boundary between alpha-Mg(2)SiO(4) and beta-Mg(2)SiO(4) is approximated by the linear expression P = (9.3 +/- 0.1) + (0.0036 +/- 0.0002)T where P is pressure in gigapascals and T is temperature in degrees Celsius.     

Earth's Core-Mantle Boundary: Results of Experiments at High Pressures and Temperatures

Laboratory experiments document that liquid iron reacts chemically with silicates at high pressures (>/=2.4 x 10(10) Pascals) and temperatures. In particular, (Mg,Fe)SiO(3) perovskite, the most abundant mineral of Earth's lower mantle, is expected to react with liquid iron to produce metallic alloys (FeO and FeSi) and nonmetallic silicates (SiO(2) stishovite and MgSiO(3) perovskite) at the pressures of the core-mantle boundary, 14 x 10(10) Pascals. The experimental observations, in conjunction with seismological data, suggest that the lowermost 200 to 300 kilometers of Earth's mantle, the D" layer, may be an extremely heterogeneous region as a result of chemical reactions between the silicate mantle and the liquid iron alloy of Earth's core. The combined thermal-chemical-electrical boundary layer resulting from such reactions offers a plausible explanation for the complex behavior of seismic waves near the core-mantle boundary and could influence Earth's magnetic field observed at the surface.     

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.     

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.     

Cooling history of orthopyroxenes

Order-disorder transitions between ferrous iron and magnesium in orthopyroxenes [minerals close to the composition (Fe, Mg) SiO(3)] occur rapidly between approximately 480 degrees and 1000 degrees C. Disordering and ordering have been studied experimentally. The determination of the metastable ferrous iron site occupancy in orthopyroxenes from rapidly cooled volcanic rocks provides information on the cooling rates, especially from 600 degrees to 480 degrees C.     

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.     

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.