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We investigated the properties of Al-bearing SiO2 (with 4 or 6 wt% Al2O3) at pressures and temperatures corresponding to the lowermost mantle, using laser-heated diamond-anvil cell coupled with synchrotron-based in situ X-ray diffraction. The phase transition from CaCl2-structured to α-PbO2- structured (seifertite) polymorphs occurs between 113 and 119 GPa at 2500 K. The range of pressure where the two phases coexist is small. There is a slight decrease of the transition pressure with increasing Al-content. We propose a tentative phase diagram reporting the minerals composition as a function of pressure in the SiO2-Al2O3 system. We also refine the P-V-T equation of state of Al-bearing seifertite based on volume measurements up to more than 160 GPa and 4000 K [V0 = 92.73(10) Å3, K0 = 304.2(3.0) GPa, K'0 = 4.59 (fixed), ɵD0 = 1130 K (fixed), γ0 = 1.61(3)]. At 300 K, the volume decrease at the CaCl2 to α-PbO2 transition is 0.5(1)%, a value slightly lower than the 0.6% reported previously for Al-free samples. At high temperature, the Grüneisen parameter of seifertite is found to be similar to that of stishovite. Nevertheless, the ▵ V/V across the CaCl2-form to seifertite transition is found to increase slightly with increasing temperature. Across the phase transition, volume changes can be translated into density changes only when the Al substitution mechanisms in both CaCl2-form and seifertite are defined. The analysis of all available data sets suggests different substitution mechanisms for the two SiO2 polymorphs. Al-substitution could occur via O-vacancies in the CaCl2-form and via extra interstitial Al in seifertite. This would result in a density increase of 2.2(3)% at 300 K for SiO2 in basaltic lithologies. Alternatively, the same Alsubstitution mechanism in both of the SiO2-dominated phases would yield a density increase of 0.5(1)%. [ABSTRACT FROM AUTHOR]

Unit-cell lattice parameters have been measured to ~8 GPa in a diamond anvil cell for two single crystals of CaIrO3: one with the perovskite (Pbnm) and the other with the post-perovskite (Cmcm) structure. The CaIrO3 post-perovskite structure is more compressible than the perovskite. A third-order Birch Murnaghan equation of state has been used to fit the measured P-V data with the following redefined parameters: V0 = 229.463(8) ų, K0 = 198(3) GPa, K' = 1.2(8); and V0 = 226.38(1) ų, K0 = 181(3) GPa, K' = 2.3(8) for CaIrO3 perovskite and post-perovskite, respectively. The compressibility of the unit-cell axes of the perovskite structure is highly anisotropic with βa >> βc >> βb. In contrast, the b axis is the most compressible in the post-perovskite structure, whereas the a and c axes have similar compressibilities (with c slightly less compressible than a) and are much stiffer. A comparison between the compressibility of CaIrO3 perovskite and post-perovskite with the isostructural MgSiO3 phases, reveals a similar general behavior, although in detail CaIrO3 perovskite is more and the post-perovskite less anisotropic than the corresponding MgSiO3 compounds. [ABSTRACT FROM AUTHOR]

Abstract: The thermodynamic properties of perovskite (pv) and post-perovskite (ppv) of CaIrO3 are derived from total energy calculations using density functional theory. Negative molar volume and enthalpy changes of 0.40cm3 mol−1 and 11.8kJmol−1 for the pv to ppv transition at 0K stabilize ppv at low temperatures and high-pressures. Vibrational entropies calculated in the harmonic approximation, using the direct method, favour pv with increasing temperatures (105.5JK−1 mol−1 for pv versus 99.2JK−1 mol−1 for ppv at 298K). A main reason for the lower entropy of post-perovskite compared to perovskite is probably related to constraints on certain vibrational modes imposed by edge-sharing of octahedra in post-perovskite. The Clapeyron slope of the pv–ppv phase boundary is deduced from the calculated enthalpy and volume of transition in conjunction with an experimental transition temperature. The resulting dp/dT of 18MPaK−1 is in good agreement with experimental determinations reported in literature. The high-pressure properties were calculated from the variation of the total energy with volume using the Murnaghan (M) and the Birch–Murnaghan (B–M) equations-of-state. The two methods give the same values for the bulk modulus but somewhat different values for the pressure derivative of the bulk modulus: K 0 =178GPa and and 3.3 (B–M) for pv compared to K 0 =164GPa and and 4.0 (B–M) for ppv. By holding for pv fixed at 4.0, K 0 is reduced to 172GPa. The bulk moduli at zero pressure were also derived through calculation of the elastic constants giving K 0 =172GPa for pv compared to K 0 =157GPa for ppv. In order to compare the changes in the bulk and shear moduli across the pv–ppv phase transition, also the shear moduli were derived from the elastic constants. Whereas the bulk modulus decreases by about 9% from perovskite to post-perovskite, the shear modulus increases by about 15% across the transition. The elastic parameters obtained for the CaIrO3 polymorphs are consistent with those of MgSiO3 and with seismic velocity variations in the lowermost mantle. Our DFT-results demonstrate that CaIrO3 may be a useful low-pressure analogue for studies of the general properties of the pv–ppv-transition relevant to the D″ layer since the negative and positive changes in bulk and shear moduli, respectively, across the pv- to ppv-transition boundary appear to be strongly linked to the nature of the two crystal structures. [Copyright &y& Elsevier]

Abstract: Experimentally determined phase relations in the system MgO–AlO1.5–SiO2 at pressures relevant to the upper part of the lower mantle indicate that Mg–silicate perovskite incorporates aluminum into its structure almost exclusively by a charge-coupled reaction. MgSiO3-rich bulk compositions along the joins MgSiO3–MgAlO2.5 and MgSiO3–MgAl2O4 crystallize assemblages of perovskite coexisting with periclase. MgO-saturated perovskites along these joins have ambient unit cell volumes consistent with those measured and calculated for aluminous perovskite along the charge-coupled substitution join, MgSiO3–AlO1.5. The compressibility of aluminous perovskite along the MgO-saturated joins is not anomalously low as predicted for oxygen-defect perovskites. The bulk moduli, however, are consistent with previous measurements made for aluminous perovskites along the charge-coupled substitution join. These results agree with first-principles calculations showing very limited stability of O-defects in Mg-perovskite at pressures and temperatures corresponding to lower mantle conditions, but are inconsistent with earlier experimental results showing unusually compressive aluminous perovskite. The maximum solubility of alumina in perovskite is ∼25 mol% along the MgSiO3–AlO1.5 join within the ternary MAS-system (i.e. pyrope composition), and the join is apparently binary. Although primitive mantle peridotite compositions are MgO-saturated and fall nearly on the oxygen vacancy join, alumina substitution into perovskite is expected to occur primarily by charge-coupled substitution throughout the lower mantle. The compressibility of aluminous perovskite in primitive mantle is expected to be only a few percent lower than for end member MgSiO3 perovskite. [Copyright &y& Elsevier]

We report on the occurrence of a new high-pressure Ca-Al-silicate in localized shock melt pockets found in the feldspatic lunar meteorite Oued Awlitis 001 and discuss the implications of our discovery. The new mineral crystallized as tiny, micrometer-sized, acicular grains in shock melt pockets of roughly anorthitic bulk composition. Transmission electron microscopy based three-dimensional electron diffraction (3D ED) reveals that the CaAl4Si2O11 crystals are identical to the calcium aluminum silicate (CAS) phase first reported from static pressure experiments. The new mineral has a hexagonal structure, with a space group of P63/mmc and lattice parameters of a = 5.42(1) Å; c = 12.70(3) Å; V = 323(4) Å3; Z = 2. This is the first time 3D ED was applied to structure determination of an extraterrestrial mineral. The International Mineralogical Association (IMA) has approved this naturally formed CAS phase as the new mineral "donwilhelmsite" [CaAl4Si2O11], honoring the U.S. lunar geologist Don E. Wilhelms. On the Moon, donwilhelmsite can form from the primordial feldspathic crust during impact cratering events. In the feldspatic lunar meteorite Oued Awlitis 001, needles of donwilhelmsite crystallized in ~200 mm sized shock melt pockets of anorthositic-like chemical composition. These melt pockets quenched within milliseconds during declining shock pressures. Shock melt pockets in meteorites serve as natural crucibles mimicking the conditions expected in the Earth's mantle. Donwilhelmsite forms in the Earth's mantle during deep recycling of aluminous crustal materials, and is a key host for Al and Ca of subducted sediments in most of the transition zone and the uppermost lower mantle (460-700 km). Donwilhelmsite bridges the gap between kyanite and the Ca-component of clinopyroxene at low pressures and the Al-rich Ca-ferrite phase and Ca-perovskite at high-pressures. In ascending buoyant mantle plumes, at about 460 km depth, donwilhelmsite is expected to break down into minerals such as garnet, kyanite, and clinopyroxene. This process may trigger minor partial melting, releasing a range of incompatible minor and trace elements and contributing to the enriched mantle (EM1 and EM2) components associated with subducted sedimentary lithologies. [ABSTRACT FROM AUTHOR]

Kevin Burke's original and thought-provoking contributions have been published steadily for the past 60 years, and more than a decade ago he set out to resolve how plate tectonics and mantle plumes interact by proposing a simple conceptual model, which we will refer to as the Burkian Earth. On the Burkian Earth, mantle plumes take us from the deepest mantle to sub-lithospheric depths, where partial melting occurs, and to the surface, where hotspot lavas erupt today, and where large igneous provinces and kimberlites have erupted episodically in the past. The arrival of a plume head contributes to continental break-up and punctuates plate tectonics by creating and modifying plate boundaries. Conversely, plate tectonics makes an essential contribution to the mantle through subduction. Slabs restore mass to the lowermost mantle and are the triggering mechanism for plumes that rise from the margins of the two large-scale low shear-wave velocity structures in the lowermost mantle, which Burke christened TUZO and JASON. Situated just above the core-mantle boundary, beneath Africa and the Pacific, these are stable and antipodal thermochemical piles, which Burke reasons represent the immediate after-effect of the moon-forming event and the final magma ocean crystallization. [ABSTRACT FROM AUTHOR]