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Phase relations in the MgSiO3–MgAl2O4–Al2O3 system are investigated at 27 GPa and 2000–2600 K using a multi‐anvil apparatus. The AlAlO3 content in the bridgmanite increases from 8.6 to 20.0 mol% with increasing temperature from 2000 to 2600 K, while the MgAlO2.5 content remains nearly constant, that is, 3–4 mol% at these temperatures. Therefore, the presence of an additional Al‐bearing phase suppresses the oxygen vacancy substitution for Al3+ in bridgmanite. Conversely, significant amounts of the Al8/3O4 component can be dissolved into the calcium‐ferrite type MgAl2O4–Mg2SiO4–Al8/3O4 phase (CF‐phase), implying that the CF‐phase likely contains some amount of vacancies. Therefore, the CF‐phase could also be a candidate mineral for transporting volatiles into the lower mantle. Our results, combined with previous studies on Al‐bearing bridgmanite, indicate that, once the Al per formula unit exceeds 0.12 in bridgmanite, the MgAlO2.5 content remains nearly constant and the AlAlO3 component becomes dominant. Plain Language Summary: Bridgmanite, the most abundant mineral in the Earth's mantle, can contain Al3+ in the forms of MgAlO2.5 and AlAlO3. To constrain the substitution mechanism of Al3+ in bridgmanite, we investigate the MgAlO2.5 and AlAlO3 contents in bridgmanite coexisting with a calcium‐ferrite type phase and corundum at different temperatures. Our results demonstrate that the MgAlO2.5 content reaches saturation (3–4 mol%) when an additional Al‐bearing phase exists in the system. Key Points: The MgAlO2.5 content in bridgmanite remains constant with temperature when bridgmanite coexists with corundum and the CF‐phaseThe MgAlO2.5 content in bridgmanite reaches a solubility of 3–4 mol% when bridgmanite coexists with an additional Al‐bearing phaseA significant amount of the Al8/3O4 component can be dissolved into the CF‐phase [ABSTRACT FROM AUTHOR]

As evidenced by isotope geochemistry, the persistence of primitive reservoirs indicates that the earth's lower mantle is likely to be heterogeneous. Such heterogeneity could be a legacy from magma‐ocean (MO) solidification. The viscosity of MO is a key parameter to constrain the solidification type of MO. Here we directly measure the viscosity of peridotite (an analog of MO composition) melt at the pressure‐temperature conditions of the deep mantle, using the in situ falling sphere method. The viscosity of peridotite melt along liquidus is in the range of 38–17 mPa s at pressures from 7 to 25 GPa, which is 0.9–0.4 times of the estimation based on the viscosity of endmember compositions. Low viscosity favors fractional solidification and chemically layering of the early mantle at least to the top lower mantle, which could be a source of heterogeneity for the present mantle. Plain Language Summary: The earth experiences a large‐scale melting and forms a deep magma ocean in its early history. The viscosity of peridotite melt is a key parameter for understanding the solidification type of magma ocean, which leads to the primitive mantle structure. This study directly measured the viscosity of peridotite melt to deep mantle conditions and revealed that peridotite melt has a lower value of viscosity than expected. The low viscosity of peridotite melt suggests a fractional solidification of the magma ocean, which supports a heterogeneous primitive mantle. Key Points: The viscosity of peridotite melt has been measured down to lower‐mantle conditions by in situ falling sphere viscometryPeridotite melt has a lower viscosity than expected from the viscosity of the endmembersThe low viscosity of peridotite melt suggests a fractional solidification in the magma ocean, supporting a heterogeneous primitive mantle [ABSTRACT FROM AUTHOR]

Ferric iron can be incorporated into the crystal structure of bridgmanite by either oxygen vacancy substitution (MgFeO2.5 component) or charge‐coupled substitution (FeFeO3 component) mechanisms. We investigated the concentrations of MgFeO2.5 and FeFeO3 in bridgmanite in the MgO‐SiO2‐Fe2O3 system at 27 GPa and 1700–2300 K using a multianvil apparatus. The FeFeO3 content increases from 1.6 to 7.6 mol.% and from 5.7 to 17.9 mol.% with and without coexistence of (Mg,Fe)O, respectively, with increasing temperature from 1700 to 2300 K. In contrast, the MgFeO2.5 content does not show clear temperature dependence, that is, ~2–3 and < 2 mol.% with and without the coexistence of (Mg,Fe)O, respectively. Therefore, the presence of (Mg,Fe)O enhances the oxygen vacancy substitution for Fe3+ in bridgmanite. It is predicted that Fe3+ is predominantly substituted following the oxygen vacancy mechanism in (Mg,Fe)O‐saturated Al‐free bridgmanite when Fe3+ is below ~0.025 pfu, whereas the charge‐coupled mechanism occurs when Fe3+ > 0.025 pfu. Plain Language Summary: Bridgmanite, the most abundant mineral of the Earth's lower mantle, can contain Fe3+ although the valance of iron is 2+ in general. An important question is how Fe3+ is substituted in the crystal structure of bridgmanite. It may form the MgFeO2.5 component, in which oxygen anions are partly missing. Or it may form the FeFeO3 component, which has no missing cations or anions. Since bridgmanite is present in the lower mantle together with (Mg,Fe)O, we investigated the MgFeO2.5 and FeFeO3 contents in Al‐free bridgmanite that coexists with and without (Mg,Fe)O under the topmost lower mantle conditions. The results show that the presence of (Mg,Fe)O enhances the formation of MgFeO2.5. The solubility of MgFeO2.5 component is about 2.5 mol.% in bridgmanite that coexists with (Mg,Fe)O, whereas it is nearly zero when (Mg,Fe)O is absent. Key Points: The presence of (Mg,Fe)O enhances the formation of the MgFeO2.5 component in Al‐free bridgmaniteFe3+ substitution predominantly follows the oxygen vacancy mechanism in (Mg,Fe)O‐saturated Al‐free bridgmanite when Fe3+ content is lowThe solubility of the MgFeO2.5 component in Al‐free bridgmanite is about 0.025 pfu, and relatively insensitive to temperature [ABSTRACT FROM AUTHOR]

Oxygen vacancies (OVs), that charge‐balance the replacement of octahedrally coordinated Si4+ by Al3+ in the mineral bridgmanite, will influence transport properties in the lower mantle but little is known about their stability and local structure. Using 27Al nuclear magnetic resonance (NMR) spectroscopy we have characterized OVs within six aluminous bridgmanite samples. In the resulting NMR spectra sixfold, fivefold, and fourfold coordinated Al species are resolved, in addition to near eightfold coordinated Al substituting for Mg. Fivefold coordinated Al is formed by single OV sites but fourfold coordination must result from short range ordering of OVs, producing OV clusters that may form through migration into twin domain walls. Characterizing the occurrence of such OV structures is an important prerequisite for understanding how transport properties change with depth and composition in the lower mantle. Plain Language Summary: The lower mantle encompasses the largest region of the Earth's interior and is mainly composed of the perovskite‐structured mineral (Mg,Fe,Al)(Al,Si)O3 bridgmanite. Its properties, therefore, control both the diffusive transport of elements and solid state flow in the lower mantle, which will be strongly influenced by point defects. We have identified and quantified defects in bridgmanite that arise from the replacement of silicon by aluminum and result in the creation of a vacant oxygen site. These oxygen defects are also found to form clusters in the structure, which in other perovskite structured minerals have been shown to strongly affect physical properties. As defect formation and ordering is dependent on composition and pressure, strong variations in physical properties may be expected within the upper 300 km of the lower mantle. Key Points: Al substitution in bridgmanite is dominated by the oxygen vacancy mechanism for peridotite mantle compositionsShort‐range ordering of oxygen vacancies takes place forming oxygen vacancy clusters possibly due to migration into twin domain wallsOxygen vacancy clusters are expected to have a major influence on transport properties of the lower mantle, such as the electrical conductivity [ABSTRACT FROM AUTHOR]