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Sublithospheric diamonds and the inclusions they may carry crystallize in the asthenosphere, transition zone, or uppermost lower mantle (from 300 to ∼800 km), and are the deepest minerals so far recognized to form by plate tectonics. These diamonds are distinctive in their deformation features, low nitrogen content, and inclusions of these major mantle minerals: majoritic garnet, clinopyroxene, ringwoodite, CaSi perovskite, ferropericlase, and bridgmanite or their retrograde equivalents. The stable isotopic compositions of elements within these diamonds (δ11B, δ13C, δ15N) and their inclusions (δ18O, δ56Fe) are typically well outside normal mantle ranges, showing that these elements were either organic (C) or modified by seawater alteration (B, O, Fe) at relatively low temperatures. Metamorphic minerals in cold slabs are effective hosts that transport C as CO3 and H as H2O, OH, or CH4 below the island arc and mantle wedge. Warming of the slab generates carbonatitic melts, supercritical aqueous fluids, or metallic liquids, forming three types of sublithospheric diamonds. Diamond crystallization occurs by movement and reduction of mobile fluids as they pass through host mantle via fractures—a process that creates chemical heterogeneity and may promote deep focus earthquakes. Geobarometry of majoritic garnet inclusions and diamond ages suggest upward transport, perhaps to the base of mantle lithosphere. From there, diamonds are carried to Earth's surface by eruptions of kimberlite magma. Mineral assemblages in sublithospheric diamonds directly trace Earth's deep volatile cycle, demonstrating how the hydrosphere of a rocky planet can connect to its solid interior. Sublithospheric diamonds from the deep upper mantle, transition zone, and lower mantle host Earth's deepest obtainable mineral samples. Low-temperature seawater alteration of the ocean floor captures organic and inorganic carbon at the surface eventually to become some of the most precious gem diamonds. Subduction transports fluids in metamorphic minerals to great depth. Fluids released by slab heating migrate, react with host mantle to induce diamond crystallization, and may trigger earthquakes. Sublithospheric diamonds are powerful tracers of subduction—a plate tectonic process that deeply recycles part of Earth's planetary volatile budget. [ABSTRACT FROM AUTHOR]

Abstract We report on laser-heated diamond anvil cell (LHDAC) experiments in the FeO–MgO–SiO 2 –CO 2 (FMSC) and CaO–MgO–SiO 2 –CO 2 (CMSC) systems at lower mantle pressures designed to test for decarbonation and diamond forming reactions. Sub-solidus phase relations based on synthesis experiments are reported in the pressure range of ∼35 to 90 GPa at temperatures of ∼1600 to 2200 K. Ternary bulk compositions comprised of mixtures of carbonate and silica are constructed such that decarbonation reactions produce non-ternary phases (e.g. bridgmanite, Ca-perovskite, diamond, CO 2 –V), and synchrotron X-ray diffraction and micro-Raman spectroscopy are used to identify the appearance of reaction products. We find that carbonate phases in these two systems react with silica to form bridgmanite ±Ca-perovskite + CO 2 at pressures in the range of ∼40 to 70 GPa and 1600 to 1900 K in decarbonation reactions with negative Clapeyron slopes. Our results show that decarbonation reactions form an impenetrable barrier to subduction of carbonate in oceanic crust to depths in the mantle greater than ∼1500 km. We also identify carbonate and CO 2 –V dissociation reactions that form diamond plus oxygen. On the basis of the observed decarbonation reactions we predict that the ultimate fate of carbonate in oceanic crust subducted into the deep lower mantle is in the form of refractory diamond in the deepest lower mantle along a slab geotherm and throughout the lower mantle along a mantle geotherm. Diamond produced in oceanic crust by subsolidus decarbonation is refractory and immobile and can be stored at the base of the mantle over long timescales, potentially returning to the surface in OIB magmas associated with deep mantle plumes. Highlights • Experiments were made in the systems FMS-CO2 and CMS-CO2 at lower mantle pressures. • Carbonate in these systems react with silica in the lower mantle. • Decarbonation reactions with negative P–T slopes form CO 2 or diamond plus oxygen. • Carbonate in oceanic crust is limited to ∼1500 km depth along subduction geotherms. • Diamond is the stable form of carbon in oceanic crust at ambient mantle temperature. [ABSTRACT FROM AUTHOR]

A new Ti-bearing bridgmanite-like phase with a threefold commensurate superstructure of the ideal MgSiO3-perovskite structure was observed in a [Mg5/6Al1/6][Si1/2Ti1/3Al1/6]O3 crystal synthesized in the model system Mg3Al2Si3O12-MgTiO3 at 20 GPa and 1600 °C. The compound was found to be orthorhombic, space group Pnma, with lattice parameters a = 14.767(3), b = 6.958(1), c = 4.812(1) Å, V = 494.4(2) Å3, which represents a 3 a × b × c superstructure of the typical Pnma perovskite structure. The structure was refined to R = 0.024 using 846 independent reflections. The superstructure mainly arises from the ordering of titanium in one of the octahedral positions. Crystal-chemical details of the different polyhedra in the superstructure are discussed in comparison to pure MgSiO3. This is the first documented superstructure of a bridgmanite phase, and Ti-rich bridgmanite in the lower mantle arising from local Tienrichments may exhibit different physical properties and elemental partitioning behavior from Ti-poor, peridotitic bridgmanite. The study also shows that large amounts of Ti can stabilize bridgmanite-like compounds at considerably lower pressure than lower mantle conditions. [ABSTRACT FROM AUTHOR]

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]

Eutectic melting curves in the system MgO–SiO 2 have been experimentally determined at lower mantle pressures using laser-heated diamond anvil cell (LH-DAC) techniques. We investigated eutectic melting of bridgmanite plus periclase in the MgO–MgSiO 3 binary, and melting of bridgmanite plus stishovite in the MgSiO 3 –SiO 2 binary, as analogues for natural peridotite and basalt, respectively. The melting curve of model basalt occurs at lower temperatures, has a shallower d T / d P slope and slightly less curvature than the model peridotitic melting curve. Overall, melting temperatures detected in this study are in good agreement with previous experiments and ab initio simulations at ∼25 GPa ( Liebske and Frost, 2012 ; de Koker et al., 2013 ). However, at higher pressures the measured eutectic melting curves are systematically lower in temperature than curves extrapolated on the basis of thermodynamic modelling of low-pressure experimental data, and those calculated from atomistic simulations. We find that our data are inconsistent with previously computed melting temperatures and melt thermodynamic properties of the SiO 2 endmember, and indicate a maximum in short-range ordering in MgO–SiO 2 melts close to Mg 2 SiO 4 composition. The curvature of the model peridotite eutectic relative to an MgSiO 3 melt adiabat indicates that crystallization in a global magma ocean would begin at ∼100 GPa rather than at the bottom of the mantle, allowing for an early basal melt layer. The model peridotite melting curve lies ∼ 500 K above the mantle geotherm at the core–mantle boundary, indicating that it will not be molten unless the addition of other components reduces the solidus sufficiently. The model basalt melting curve intersects the geotherm at the base of the mantle, and partial melting of subducted oceanic crust is expected. [ABSTRACT FROM AUTHOR]