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Earth and planetary science letters 604, 118015 (2023). doi:10.1016/j.epsl.2023.118015, The ‘660’ discontinuity is often associated with a phase transitions in pyrolite at about 24 GPa. There are ubiquitous reports of seismic anisotropy below the ‘660’ which are difficult to explain from a mineralogical point of view. In this study, we implement multigrain crystallography X-ray diffraction in the laser-heated diamond anvil cell in order to track microstructures induced by phase transitions at the pressure and temperature conditions of the discontinuity. Before the onset of transformation, garnet is isotropic with ringwoodite displaying a weak 001 texture. After the transformation, bridgmanite displays strong 001 transformation textures which we attribute to growth under stress. Davemaoite exhibits weak maxima in 101 and 111 orientations with ferropericlase displaying no texture. The results are used to model anisotropy in a subducting slab, with a prediction of no anisotropy above the ‘660’ and up to 1.28% (0.08 km/s) shear wave splitting below the ‘660’. In addition, we predict $V_{SV} > V_{SH}$ for horizontally traveling waves and near-vertical subduction and $V_{SV} < V_{SH}$ in the case a slab impinging below the boundary layer., Published by Elsevier, Amsterdam [u.a.]

Microstructures in mantle rocks impact the way seismic waves travel through the Earth and are dependent on the pressure, temperature, and deformation applied to the rock. At approximately 660 km depth, an increase in seismic wave velocities mark a distinct boundary that separates the upper and lower mantle. Another boundary is found at approximately 2700 km depth and marks the beginning of the D" layer. Furthermore, observations of seismic anisotropy at these discontinuities have been made. These boundaries are largely believed to be related to phase transitions from ringwoodite [(Mg,Fe)2SiO4, space group Fd3m] to bridgmanite [(Mg,Fe)SiO3, space group Pbnm] to post-perovskite [(Mg,Fe)SiO3, space group Cmcm]. In order to make interpretations of these seismic observations, however, a sound understanding of what generates these microstructures is required.Here, we approach this problem through high pressure and high temperature experiments. We identify microstructures in polycrysalline mantle minerals resulting from in-situ transformation and deformation using radial and multigrain X-ray diffraction in the diamond anvil cell. In the first study we transform a bridgmanite analogue, NaCoF3, from a perovskite to post-perovskite structure. The following two studies investigate the transformation of an average mantle composition, pyrolite, at conditions relevant to the 660 km discontinuity and further deformation at pressures and temperatures corresponding to depths between 500 and 2400 km. In the final study, we test an aluminum rich 'pyrolite' composition (pyrolite minus olivine) in order to compare transformation and deformation microstructures to those observed in experiments on pure pyrolite.Results from radial diffraction experiments show the transformation from perovskite to post-perovskite in NaCoF3 are reconstructive in nature and for which we identify the orientation relationships. Major takeaways from the multigrain X-ray diffraction experiments are as follows: i) the decomposition from (ringwoodite + garnet) to (bridgmanite + davemaoite + ferropericlase) result in non-reconstructive 001 transformation textures in bridgmanite, 101 and 111 textures in davemaoite, and no preferred orientation in ferropericlase. ii) With further deformation, bridgmanite changes to 100 and 010 orientations with no change in either davemaoite or ferropericlase. iii) Textures in bridgmanite and davemaoite in pyrolite minus olivine are similar to those observed in our experiments on pure pyrolite.Finally, we use the results of these experiments to build a model for S and P-wave seismic anisotropy within a subducting slab and the surrounding mantle for multiple scenarios and compare our results to those of the literature. This interplay between experiments and seismic models are important in order to provide constraints on deformation, dynamics, and history of the Earth's interior.; Les microstructures des roches du manteau affectent la propagation des ondes sismiques dans la Terre. Elles dépendent de la pression, de la température et de la déformation appliquées à la roche. À environ 660 km de profondeur, un saut de vitesses des ondes sismiques marque la frontière qui sépare le manteau supérieur du manteau inférieur. Une autre frontière se trouve à environ 2700 km de profondeur et marque le début de la couche D". Ces frontières sont communément associées à des transformations de phase de la ringwoodite [(Mg,Fe)2SiO4, groupe d'espace Fd3m] à la bridgmanite [(Mg,Fe)SiO3, groupe d'espace Pbnm] puis la post-perovskite [(Mg,Fe)SiO3, groupe d'espace Cmcm]. Cependant, une bonne compréhension de ce qui génère les microstructures associées à la déformation ou les transformations de phase est nécessaire pour interpréter les observations sismiques et les associer aux processus dynamiques dans le manteau.Ici, nous abordons cette question par le biais d'expériences à haute pression et à haute température en cellule à enclume de diamant. Nous identifions des microstructures résultant de transformations de phase ou de déformation dans des matériaux polycristallins pertinent pour le manteau, in situ, à l'aide de la diffraction des rayons X radiale ou multi-grains. Dans la première étude, nous transformons un analogue de bridgmanite, NaCoF3, d'une structure pérovskite à une structure post-pérovskite. Les deux études suivantes se concentrent sur la transformation d'une composition moyenne du manteau, la pyrolite, dans des conditions pertinentes pour la discontinuité à 660 km et une déformation supplémentaire à des pressions et des températures correspondant à des profondeurs comprises entre 500 et 2400 km. Dans le dernier chapitre, nous testons une composition 'pyrolite' riche en aluminium (pyrolite-minus-olivine) afin de comparer les microstructures de transformation et de déformation à celles observées expérimentalement sur la pyrolite pure.Les résultats d'expériences de diffraction radiale montrent que la transformation de pérovskite en post-pérovskite dans NaCoF3 est de nature reconstructive et nous identifions les relations d'orientation qui entrent en jeu. Les principales conclusions des expériences de diffraction des rayons X multigrains sont les suivantes : i) la décomposition de (ringwoodite + grenat) en (bridgmanite + davemaoite + ferropériclase) donne des textures de transformation non reconstructives 001 dans la bridgmanite, 101 et 111 dans la davemaoite, et aucune orientation préférentielle dans la ferro-périclase. ii) Avec une déformation supplémentaire, la bridgmanite passe à des orientations de type 100 puis 010 sans changement de texture observé, ni dans la davemaoite, ni dans la ferro-périclase. iii) Les textures de la bridgmanite et de la davemaoite dans la composition pyrolite-minus-olivine sont similaires à celles observées dans nos expériences sur la pyrolite pure.Enfin, nous utilisons les résultats de ces expériences pour construire un modèle d'anisotropie sismique des ondes S et P dans une plaque en subduction et dans le manteau environnant pour plusieurs scénarios et comparons nos résultats à ceux de la littérature. Cette combinaison entre les expériences et les modèles sismiques est importante pour fournir des contraintes sur la déformation, la dynamique et l'histoire de l'intérieur de la Terre.

Plots of chondrite-normalised rare earth element (REE) patterns often appear as smooth curves. These curves can be decomposed into orthogonal polynomial functions (shape components), each of which captures a feature of the total pattern. The coefficients of these components (known as the lambda coefficients—$$\lambda $$ λ ) can be derived using least-squares fitting, allowing quantitative description of REE patterns and dimension reduction of parameters required for this. The tetrad effect is similarly quantified using least-squares fitting of shape components to data, resulting in the tetrad coefficients ($$\tau $$ τ ). Our method allows fitting of all four tetrad coefficients together with tetrad-independent $$\lambda $$ λ curvature. We describe the mathematical derivation of the method and two tools to apply the method: the online interactive application BLambdaR, and the Python package pyrolite. We show several case studies that explore aspects of the method, its treatment of redox-anomalous REE, and possible pitfalls and considerations in its use.

The chemistry of bridgmanite (Brg), especially the oxidation state of iron, is important for understanding the physical and chemical properties, as well as putting constraints on the redox state, of the Earth’s lower mantle. To investigate the controls on the chemistry of Brg, the Fe3+ content of Brg was investigated experimentally as a function of composition and oxygen fugacity (fo2) at 25 GPa. The Fe3+/∑Fe ratio of Brg increases with Brg Al content and fo2 and decreases with increasing total Fe content and with temperature. The dependence of the Fe3+/∑Fe ratio on fo2 becomes less steep with increasing Al content. Thermodynamic models were calibrated to describe Brg and ferropericlase (Fp) compositions as well as the inter-site partitioning of trivalent cations in Brg in the Al–Mg–Si–O, Fe–Mg–Si–O and Fe–Al–Mg–Si–O systems. These models are based on equilibria involving Brg components where the equilibrium thermodynamic properties are the main adjustable parameters that are fit to the experimental data. The models reproduce the experimental data over wide ranges of fo2 with a relatively small number of adjustable terms. Mineral compositions for plausible mantle bulk compositions can be calculated from the models as a function of fo2 and can be extrapolated to higher pressures using data on the partial molar volumes of the Brg components. The results show that the exchange of Mg and total Fe (i.e., ferric and ferrous) between Brg and Fp is strongly fo2 dependent, which allows the results of previous studies to be reinterpreted. For a pyrolite bulk composition with an upper mantle bulk oxygen content, the fo2 at the top of the lower mantle is −0.86 log units below the iron–wustite buffer (IW) with a Brg Fe3+/∑Fe ratio of 0.50 and a bulk rock ratio of 0.28. This requires the formation of 0.7 wt.% Fe–Ni alloy to balance the raised Brg ferric iron content. With increasing pressure, the model predicts a gradual increase in the Fe3+/∑Fe ratio in Brg in contrast to several previous studies, which levels off by 50 GPa. Oxygen vacancies in Brg decrease to practically zero by 40 GPa, potentially influencing elasticity, diffusivity and rheology in the top portion of the lower mantle. The models are also used to explore the fo2 recorded by inclusions in diamonds, which likely crystallized as Brg in the lower mantle, revealing oxygen fugacities which likely preclude the formation of some diamonds directly from carbonates, at least at the top of the lower mantle.

The electrical conductivity of mineral aggregates depends both on the properties of the constitutive minerals and the ways those minerals are assembled. Mixing, or average models combine the conductivity of single phases to give bulk conductivity of rocks, thereby linking experimental measurements to geophysical observations. In order to compare these mixing models and allow an informed choice, several popular approaches, including bounds and average models, have been used to estimate the conductivity of a typical dry upper mantle and transition zone with a pyrolite composition. All the estimations calculated using the various average models lie between the rigorous constraint that is given by the HS bounds. The average models in this study are found to give similar bulk conductivities with the difference of less than 0.5 orders of magnitude, except the geometric mean, implying that the choice of the average models is insignificant. The effective electrical conductivity of pyrolite mantle has been derived from the conductivity of dry mantle minerals using the effective medium theory, and was found consistent with observed conductivity values for some subsurface regions of the Earth which we expect to be relatively dry. This provides us with baseline conductivity for a dry mantle, which is helpful to understand the water distribution in the deep earth.

The recycling of oceanic crust, with distinct isotopic and chemical signature from the pyrolite mantle, plays a critical role in the chemical evolution of the Earth with insights into mantle circulation. However, the role of the mantle transition zone during this recycling remains ambiguous. We here combine the unique resolution reflected body waves (P410P and P660P) retrieved from ambient noise interferometry with mineral physics modeling, to shed new light on transition zone physics. Our joint analysis reveals a generally sharp 660-km discontinuity and the existence of a localized accumulation of oceanic crust at the bottom mantle transition zone just ahead of the stagnant Pacific slab. The basalt accumulation is plausibly derived from the segregation of oceanic crust and depleted mantle of the adjacent stagnant slab. Our findings provide direct evidence of segregated oceanic crust trapped within the mantle transition zone and new insights into imperfect whole mantle circulation., By combining ambient noise interferometry with mineral physics modeling, this work sheds new light on mantle transition zone physics. Their findings provide new evidence of segregated oceanic crust subducted and trapped within the mantle transition zone, implying complex mantle circulation modes.

Using an iterative numerical approach, we have obtained the self-consistent thermal expansion, heat capacity, and Grüneisen parameters of diopside (MgCaSi2O6) over wide pressure and temperature ranges based on experimental data from the literature. Our results agree well with the published experimental and theoretical data. The determined thermodynamic parameters exhibit nonlinear dependences with increasing pressure. Compared with other minerals in the upper mantle, we found that the adiabatic temperature gradient obtained using the thermodynamic data of diopside is larger than that of garnet while lower than that of olivine, when ignoring the Fe incorporation. Combining our results with thermodynamic parameters of garnet obtained in previous studies, we have estimated the adiabatic temperature gradient and geotherm of an eclogitic upper mantle in a depth range of 200–450 km. The results show that the estimated adiabatic temperature gradient of the eclogite model is ~16% and ~3% lower than that of the pyrolite model at a depth of 200 km and 410 km, respectively. However, the high mantle potential temperature of the eclogite model leads to a similar temperature as the pyrolite model in a depth range of 200–410 km.

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With ab initio molecular dynamics simulations on a Na‐, Ca‐, Fe‐, Mg‐, and Al‐bearing silicate melt of pyrolite composition, we examine the detailed changes in elemental coordination as a function of pressure and temperature. We consider the average coordination as well as the proportion and distribution of coordination environments at pressures and temperatures encompassing the conditions at which molten silicates may exist in present‐day Earth and those of the Early Earth's magma ocean. At ambient pressure and 2,000 K, we find that the average coordination of cations with respect to oxygen is 4.0 for Si‐O, 4.0 for Al‐O, 3.7 for Fe‐O, 4.6 for Mg‐O, 5.9 for Na‐O, and 6.2 for Ca‐O. Although the coordination for iron with respect to oxygen may be underestimated, the coordination number for all other cations are consistent with experiments. By 15 GPa (2,000 K), the average coordination for Si‐O remains at 4.0 but increases to 4.1 for Al‐O, 4.2 for Fe‐O, 4.9 for Mg‐O, 8.0 for Na‐O, and 6.8 for Ca‐O. The coordination environment for Na‐O remains approximately constant up to core‐mantle boundary conditions (135 GPa and 4000 K) but increases to about 6 for Si‐O, 6.5 for Al‐O, 6.5 for Fe‐O, 8 for Mg‐O, and 9.5 for Ca‐O. We discuss our results in the context of the metal‐silicate partitioning behavior of siderophile elements and the viscosity changes of silicate melts at upper mantle conditions. Our results have implications for melt properties, such as viscosity, transport coefficients, thermal conductivities, and electrical conductivities, and will help interpret experimental results on silicate glasses., Key Points The proportion and distribution of cation‐to‐oxygen coordination environments in a pyrolite melt have been determined as a function of depthWe examine the distribution of lifetimes of cation‐oxygen species at select pressure‐temperature conditionsOur results are compared to previous ab initio calculations on mafic silicate melts and to experiments on various silicate phases

Based on study of partial melting in the model pyrolite, it is shown that garnets synthesized at 7.0 GPa in a temperature range of 1400–1800°C are characterized by an excessive Si content (in relation to 3 f.u.), stable admixture of Cr2O3, and, thus, represent a solid solution of the pyrope–majorite–knorringite composition. Increase in the Cr/Al value in the starting composition results in increase of this ratio in garnet. With increasing temperature, the concentration of Cr2O3 decreases in restite and increases in melt. Cr/Al increases in all garnets from the zone of restite and from the quenched melt aggregate. Estimates of the bulk compositions of restite formed by partial melting of the model pyrolite at 2.5 and 3.0 GPa show that the concentration of Cr in it is higher than that in the starting composition. All minerals from the zone of restite are characterized by the high Cr concentrations, and upon partial melting in the spinel-depth facies, Cr is redistributed to restite. Our results show that the formation of high-chromium garnets relates to the protolith with the high Cr/Al value formed as a residue from partial melting in the spinel-depth facies and further transported to the garnet facies.

The study of partial melting of model pyrolite showed that garnets synthesized at 7 GPa within the temperature range of 1400–1800°C were characterized by an excess in Si content (>3 f.u.) and a stable admixture of Cr2O3, and thus are pyrope–majorite–knorringite solid solutions. An increase in the Cr/Al ratio in the starting composition results in an increase of Cr/Al in garnet. With increasing temperature, the concentration of Cr2O3 in restite from partial melting decreases, whereas the chromium content in the melt increases. This is accompanied by an increase in the Cr/Al ratio in all garnets (from the zones of restite and quenched melt). Estimates of the bulk compositions of restite produced via partial melting of model pyrolite at 2.5 and 3.0 GPa showed that the concentration of chromium in restite was higher than that in the starting material. All minerals from the restite zone are characterized by high chromium concentrations, since partial melting within the spinel-depth facies results in redistribution of chromium into restite. The results we obtained show that the origin of high-Cr garnets is related to the protolith with a high Cr/Al ratio formed as a residue from partial melting in the field of spinel stability and further removed into the garnet-depth facies.

Velocity and density jumps across the 410-km seismic discontinuity generally indicate olivine contents of ∼30 to 50 vol.% on the basis of the elastic properties of anhydrous olivine and wadsleyite, which is considerably less than the ∼60% olivine in the widely accepted pyrolite model for the upper mantle. A possible explanation for this discrepancy is that water dissolved in olivine and wadsleyite affects their elastic properties in ways that can reconcile the pyrolitic model with seismic observations. In order to more fully constrain the olivine content of the upper mantle near the 410-km discontinuity, and to place constraints on the mantle water content at this depth, we determined the full elasticity of hydrous wadsleyite at the P-T conditions of the discontinuity based on density functional theory calculations. Together with previous determinations for the effect of water on olivine elasticity, we simultaneously modeled the density and seismic velocity jumps (Δρ, Δ V P , Δ V S ) across the olivine-wadsleyite transition. Our models allow for several scenarios that can well reproduce the density and seismic velocity jumps across the 410-km discontinuity when compared to globally averaged seismic models. When the water content of olivine and wadsleyite is assumed to be equal as in a simple binary system, our modeling indicates a best fit for low water contents (

The early Earth was marked by at least one global magma ocean. Melt buoyancy played a major role for its evolution. Here we model the composition of the magma ocean using a six‐component pyrolite melt, to which we add volatiles in the form of carbon as molecular CO or CO2 and hydrogen as molecular H2O or through substitution for magnesium. We compute the density relations from first‐principles molecular dynamics simulations. We find that the addition of volatiles renders all the melts more buoyant compared to the reference volatile‐free pyrolite. The effect is pressure dependent, largest at the surface, decreasing to about 20 GPa, and remaining roughly constant to 135 GPa. The increased buoyancy would have enhanced convection and turbulence, and thus promoted the chemical exchanges of the magma ocean with the early atmosphere. We determine the partial molar volume of both H2O and CO2 throughout the magma ocean conditions. We find a pronounced dependence with temperature at low pressures, whereas at megabar pressures the partial molar volumes are independent of temperature. At all pressures, the polymerization of the silicate melt is strongly affected by the amount of oxygen added to the system while being only weakly affected by the specific type of volatile added., Key Points The addition of volatiles to pyrolite melts renders them buoyant at all pressures and temperaturesDepolymerization of the melt increases with the addition of oxygen and is mostly independent of the type of volatile (i.e., CO, CO2, and H2O)Volatiles would have enhanced the circulation in the magma ocean and promoted volatile exchange and equilibration with the early atmosphere

The core-mantle boundary (CMB) at ~2900 km depth and ~135 GPa is the interface between the solid silicate mantle and the liquid metallic outer core. The temperature at CMB (TCMB) is a key parameter in assessing the heat flow out of the core and is thus important for our understanding of the geodynamo and mantle convection. The upper bound on TCMB is constrained by the solidus temperature (onset of melting) of pyrolite, a chemical proxy of the mantle rock, at ~135 GPa because the lowermost mantle is predominantly solid. Previous laser-heated diamond anvil cell (LH DAC) studies reported pyrolite solidus temperatures of 3430–4180 K (±

We present two-dimensional thermo-mechanical numerical models of coupled lithosphere-mantle deformation, considering the upper mantle down to a depth of 660 km. We consider visco-elasto-plastic deformation and for the lithospheric and upper mantle a combination of diffusion, dislocation and Peierls creep. Mantle densities are calculated from petrological phase diagrams (Perple_X) for a Hawaiian pyrolite. The model generates a 120 Myrs long geodynamic cycle of subsequent extension (30 Myrs), cooling (70 Myrs) and convergence (20 Myrs) in a single and continuous simulation with explicitly modelling convection in the upper mantle. During lithosphere extension, the models generate an approximately 400 km wide basin of exhumed mantle bounded by hyper-extended passive margins. The models show that considering only the thermal effects of upper mantle convection by using an effective thermal conductivity generates results of lithosphere hyper-extension that are similar to the ones of models that explicitly model the convective flow. Applying a lower viscosity limit of 5 × 1020 Pa s suppresses convection and generates results different to the ones for simulations with a low viscosity asthenosphere having minimal viscosity of approximately 1019 Pa s. During cooling without far-field deformation, no subduction of the exhumed mantle is spontaneously initiated. Density differences between lithosphere and mantle are too small to generate a buoyancy force exceeding the mechanical strength of the lithosphere. The extension and cooling stages generate self-consistently a structural and thermal inheritance for the subsequent convergence stage. Convergence initiates subduction of the exhumed mantle at the transition to the hyper-extended margins. The main mechanism of subduction initiation is thermal softening for a plate driving force (per unit length) of approximately 15 TN m−1. If convection in the mantle is suppressed by high effective thermal conductivities or high, lower viscosity limits, then subduction initiates at both margins leading to divergent double-slab subduction. Convection in the mantle assists to generate a single-slab subduction at only one margin, likely due to mantle flow which exerts an additional suction force on the lithosphere. The first-order geodynamic processes simulated in the geodynamic cycle of subsequent extension, cooling and convergence are applicable to orogenies that resulted from the opening and closure of embryonic oceans bounded by magma-poor hyper-extended passive margins, which might have been the case for the Alpine orogeny.

Knowledge of thermal conductivity of mantle minerals is crucial for understanding heat transport from the Earth's core to mantle. At the pressure-temperature conditions of the Earth's core-mantle boundary, calculations of lattice thermal conductivity based on atomistic models have determined values ranging from 1 to 14 W/m/K for bridgmanite and bridgmanite-rich mineral assemblages. Previous studies have been performed at room temperature up to the pressures of the core-mantle boundary, but correcting these to geotherm temperatures may introduce large errors. Here we present the first measurements of lattice thermal conductivity of mantle minerals up to pressures and temperatures near the base of the mantle, 120 GPa and 2500 K. We use a combination of continuous and pulsed laser heating in a diamond anvil cell to measure the lattice thermal conductivity of pyrolite, the assemblage of minerals expected to make up the lower mantle. We find a value of 3.9 + 1.4 − 1.1 W/m/K at 80 GPa and 2000 to 2500 K and 5.9 + 4.0 − 2.3 W/m/K at 124 GPa and 2000 to 3000 K. These values rule out the highest calculations of thermal conductivity of the Earth's mid-lower mantle (i.e. k 6 W/m/K at 80 GPa), and are consistent with both the high and low calculations of thermal conductivity near the base of the lower mantle.

A better understanding of the Earth’s compositional structure is needed to place the geochemical record of surface rocks into the context of Earth accretion and evolution. Cosmochemical constraints imply that lower-mantle rocks may be enriched in silica relative to upper-mantle pyrolite, whereas geophysical observations support whole-mantle convection and mixing. To resolve this discrepancy, it has been suggested that subducted mid-ocean ridge basalt (MORB) segregates from subducted harzburgite to accumulate in the mantle transition zone (MTZ) and/or the lower mantle. However, the key parameters that control basalt segregation and accumulation remain poorly constrained. Here, we use global-scale 2D thermochemical convection models to investigate the influence of mantle-viscosity profile, planetary-tectonic style and bulk composition on the evolution and distribution of mantle heterogeneity. Our models robustly predict that, for all cases with Earth-like tectonics, a basalt-enriched reservoir is formed in the MTZ, and a harzburgite-enriched reservoir is sustained at 660~800 km depth, despite ongoing whole-mantle circulation. The enhancement of basalt and harzburgite in and beneath the MTZ, respectively, are laterally variable, ranging from ~30% to 50% basalt fraction, and from ~40% to 80% harzburgite enrichment relative to pyrolite. Models also predict an accumulation of basalt near the core mantle boundary (CMB) as thermochemical piles, as well as moderate enhancement of most of the lower mantle by basalt. While the accumulation of basalt in the MTZ does not strongly depend on the mantle-viscosity profile (explained by a balance between basalt delivery by plumes and removal by slabs at the given MTZ capacity), that of the lowermost mantle does: lower-mantle viscosity directly controls the efficiency of basalt segregation (and entrainment) near the CMB; upper-mantle viscosity has an indirect effect through controlling slab thickness. Finally, the composition of the bulk-silicate Earth may be shifted relative to that of upper-mantle pyrolite, if indeed significant reservoirs of basalt exist in the MTZ and lower mantle.

The aluminium incorporation mechanism of perovskite was explored by means of quantum mechanics in combination with equilibrium/off-equilibrium thermodynamics under the pressure-temperature conditions of the Earth's lower mantle (from 24 to 80 GPa). Earth's lower mantle was modelled as a geochemically non-primitive object because of an enrichment by 3 wt% of recycled crustal material (MORB component). The compositional modelling takes into account both chondrite and pyrolite reference models. The capacity of perovskite to host Al was modelled through an Al2O3 exchange process in an unconstrained Mg-perovskite + Mg-Al-perovskite + free-Al2O3(corundum) system. Aluminium is globally incorporated principally via an increase in the amount of Al bearing perovskite [Mg-Al-pv(80 GPa)/Mg-Al-pv(24 GPa) ≈ 1.17], rather than by an increase in the Al2O3 content of the average chemical composition which changes little (0.11–0.13, mole fraction of Al2O3) and tends to decrease in Al. The Al2O3 distribution in the lower mantle was described through the probability of the occurrence of given compositions of Al bearing perovskite. The probability of finding Mg-Al-perovskite is comparable to Mg-perovskites. Perovskite with Al2O3 mole fraction up to 0.15 has an occurrence probability of ∼28% at 24 GPa, increasing up to ∼43% at 80 GPa; on the contrary, perovskite compositions in the range 0.19–0.30 Al2O3 mole fraction drop their occurrence probability from 9.8 to 2.0%, over the same P-range. In light of this, the distribution of Al in the lower mantle shows that, among the possible Al bearing perovskite phases, the (Mg0.89Al0.11)(Si0.89Al0.11)O3 composition is the likeliest, providing from 5 to 8% of the bulk perovskite in the pressure range from 24 to 80 GPa. The occurrence of the most Al rich composition, i.e. (Mg0.71Al0.29)(Si0.71Al0.29)O3, is a rare event (probability of occurrence < 1.7%). This study predicts that perovskite may globally host Al2O3 in terms of 4.3 and 4.8 wt% (with respect to the non-primitive lower mantle mass), thus accounting for ∼90% and 100% of the bulk Al2O3 estimated in the framework of pyrolite and chondrite reference models, respectively. A calcium-ferrite type phase (on the MgAl2O4-NaAlSiO4 join) seems to be the only candidate that can compensate for the 10% gap of the perovskite Al incorporation capacity, in the case of a pyrolite non-primitive lower mantle model.

Current estimates of the carbon flux between the surface and mantle are highly variable, and the total amount of carbon stored in closed hidden reservoirs is unknown. Understanding the forms in which carbon existed in the molten early Earth is a critical step towards quantifying the carbon budget of Earth's deep interior. Here we employ first-principles molecular dynamics to study the evolution of carbon species as a function of pressure in a pyrolite melt. We find that with increasing pressure, the abundance of CO2 and CO3 species decreases at the expense of CO4 and complex oxo-carbon polymers (CxOy) displaying multiple C-C bonds. We anticipate that polymerized oxo-carbon species were a significant reservoir for carbon in the terrestrial magma ocean. The presence of Fe-C clusters suggests that upon segregation, Fe-rich metal may partition a significant fraction of carbon from the silicate liquid, leading to carbon transport into the Earth's core., The amount of carbon stored in closed hidden reservoirs is unknown. Here the authors use a computational approach to study the evolution of carbon species and observe polymerization of carbon atoms at high pressures, illustrating the potential for a significant carbon reservoir in the Earth’s deep interior.

We investigated phase relations, mineral chemistry, and density of lunar highland anorthosite at conditions up to 125 GPa and 2000 K. We used a multi-anvil apparatus and a laser-heated diamond-anvil cell for this purpose. In-situ X-ray diffraction measurements at high pressures and composition analysis of recovered samples using an analytical transmission electron microscope showed that anorthosite consists of garnet, CaAl4Si2O11-rich phase (CAS phase), and SiO2 phases in the upper mantle and the mantle transition zone. Under lower mantle conditions, these minerals transform to the assemblage of bridgmanite, Ca-perovskite, corundum, stishovite, and calcium ferrite-type aluminous phase through the decomposition of garnet and CAS phase at around 700 km depth. Anorthosite has a higher density than PREM and pyrolite in the upper mantle, while its density becomes comparable or lower under lower mantle conditions. Our results suggest that ancient anorthosite crust subducted down to the deep mantle was likely to have accumulated at 660–720 km in depth without coming back to the Earth's surface. Some portions of the anorthosite crust might have circulated continuously in the Earth's deep interior by mantle convection and potentially subducted to the bottom of the lower mantle when carried within layers of dense basaltic rocks. Keywords: Anorthosite, Phase transformation, Multi-anvil apparatus, Diamond-anvil cell, Mantle dynamics

The phase relations, mineral chemistry and density of KREEP basalt were investigated at pressures of 12–125 GPa and temperatures up to 2810 K by a combination of large volume multi-anvil press experiments and in situ synchrotron X-ray diffraction measurements in a laser-heated diamond anvil cell. Our results showed that grossular-rich majorite garnet, liebermannite and Al-bearing stishovite are dominant in the upper-to-middle part of the upper mantle while in the lowermost transition zone a dense Ti-rich CaSiO3 perovskite exsoluted from the garnet, which becomes more pyropic with increasing pressure. At lower mantle conditions, these minerals transform into an assemblage of bridgmanite, Ca-perovskite, Al-stishovite, the new aluminium-rich (NAL) phase and the calcium-ferrite type (CF) phase. At pressures higher than 50 GPa, NAL phase completely dissolved into the CF phase, which becomes the main deposit of alkali metals in the lower mantle. The density of KREEP estimated from phase compositions obtained by energy dispersive X-ray spectroscopy (EDS) in scanning (SEM) and transmission (TEM) electron microscopes, was found substantially denser than pyrolite suggesting that the Earth primordial crust likely subducted deep into the Earth’s mantle after or slightly before the final solidification of magma ocean at 4.53 Ga. Radiogenic elements U, Th and 40K which were abundant in the final residue of magma ocean were brought down along the subduction of the primordial crust and generate heat by decay after the settlement of the primordial crust on top of the CMB, suggesting the non-homogeneous distribution of radiogenic elements in the Hadean mantle with implications for the thermal history of the Earth.

We determined phase relations of pyrolite at 12–28 GPa and 1600–2200 °C using a 6–8 Kawai-type multianvil apparatus. A large number of high pressure and high temperature experiments were conducted to constrain the phase relations especially around 660-km depth, compared with previous studies. The phase relations drastically change between 19 and 23 GPa with temperature as follows. At 19–22 GPa, a phase transition of ringwoodite (Rw) to garnet (Gt) + magnesiowustite (Mw) occurs at 1800 °C, and no Rw is observed at 2200 °C. The mineral proportion of Gt increases with increasing temperature due to this decomposition reaction and becomes larger than that of Rw above 1800 °C. At 23 GPa, pyrolite crystallizes to a mineral assemblage of bridgmanite (Bm) + Mw + Gt + calcium perovskite by the post-spinel (pSp) transition at 1600–2000 °C and the post-garnet (pGt) transition at 2100–2200 °C, the latter of which is defined as a phase transition of a part of Gt to Bm. Clapeyron slopes of the pSp transition and the pGt transition are determined to be −1 and 5 MPa/°C, respectively, in this study. Gt is stable at any temperatures around the 660-km discontinuity (D660), and Gt-disappearance reaction occurs at 25 GPa with no temperature dependence. Densities of pyrolite were calculated in various pressure and temperature conditions by using the mineral proportions and available data of equations of state. The density at 1600 °C is higher than that at 1800–2200 °C at any pressure-temperature conditions in this study. In particular, the drastic density drop occurs at 19–24 GPa between 1600 and 1800–2200 °C because of increase of Gt proportion with increasing temperature. These suggest that upwelling hot plumes composed of pyrolite from the lower mantle do not stagnate and their ascent is promoted across D660. The mineral proportions and the density changes also suggest that the phase transition which causes D660 changes around 1800 °C from the pSp to the pGt transitions because of the mineral proportion inversion between Rw and Gt.

The compositions of mantle-derived magmas indicate a substantial variety in the abundances of volatiles in the upper mantle. CO2 and H2O depress the melting point of mantle peridotites considerably, delineating a pressure-temperature region of incipient melting where small degrees of melt exist over a large temperature range (~300 °C) before major melting begins. However, the chemical characterization of these melts in high-pressure experiments is challenging at low melt fractions (melt pockets may occupy volumes of only 10–50 μm3) because of analytical uncertainties related to the ubiquitous formation of metastable phases during quenching. This systematic partial melting study presents carefully determined compositions of incipient melts of a range of peridotites in the presence of CO2 + H2O mixtures at 2.5 to 7 GPa. Four different fertile and depleted peridotites were used: Hawaiian pyrolite, K2O-enriched pyrolite, MORB pyrolite and depleted lherzolite. To arrive at accurate melt compositions, we introduce the melt tomography method that integrates multiple area scans of melt pockets polished to several depths. Results confirm that incipient and low degree melts progress abruptly (within 25 °C) from carbonatitic towards melilititic-nephelinitic compositions at 2.5 GPa, whereas they progress gradually from carbonate-rich to carbonated silicate (aillikitic) compositions at 4–5 GPa. Melt compositions at near-solidus conditions are mainly controlled by the breakdown of carbonate, and hydrous phases such as pargasite and phlogopite, and become less siliceous and slightly more magnesian with increasing pressure at given melt fractions. Melts exhibit strong increases in SiO2 (2.75 to 44 wt%) with increasing temperature, whereas TiO2, Na2O and K2O decrease. The generally strongly potassic (K2O ≤ 6.63 wt%) and sodic (Na2O ≤ 3.06 wt%) character of the volatile-rich, incipient and low-degree melts indicate that these would act as reactive metasomatic agents that may transport large amounts of energy and induce chemical changes in large volumes of the upper mantle.