Heterogeneity in Earth’s mantle is a record of chemical and dynamic processes over Earth’s history. The geophysical signatures of heterogeneity can only be interpreted with quantitative constraints on effects of major elements such as iron on physical properties including density, compressibility, and electrical conductivity. However, deconvolution of the effects of multiple valence and spin states of iron in bridgmanite (Bdg), the most abundant mineral in the lower mantle, has been challenging. Here we show through a study of a ferric-iron-only (Mg_0.46Fe³⁺_0.53)(Si_0.49Fe³⁺_0.51)O₃Bdg that Fe³⁺in the octahedral site undergoes a spin transition between 43 and 53 GPa at 300 K. The resolved effects of the spin transition on density, bulk sound velocity, and electrical conductivity are smaller than previous estimations, consistent with the smooth depth profiles from geophysical observations. For likely mantle compositions, the valence state of iron has minor effects on density and sound velocities relative to major cation composition.

Large Low Shear Velocity Provinces (LLSVPs) in the lowermost mantle are key to understanding the chemical composition and thermal structure of the deep Earth, but their origins have long been debated. Bridgmanite, the most abundant lower-mantle mineral, can incorporate extensive amounts of iron (Fe) with effects on various geophysical properties. Here our high-pressure experiments and ab initio calculations reveal that a ferric-iron-rich bridgmanite coexists with an Fe-poor bridgmanite in the 90 mol% MgSiO₃–10 mol% Fe₂O₃ system, rather than forming a homogeneous single phase. The Fe³⁺-rich bridgmanite has substantially lower velocities and a higher V_P/V_S ratio than MgSiO₃ bridgmanite under lowermost-mantle conditions. Our modeling shows that the enrichment of Fe³⁺-rich bridgmanite in a pyrolitic composition can explain the observed features of the LLSVPs. The presence of Fe³⁺-rich materials within LLSVPs may have profound effects on the deep reservoirs of redox-sensitive elements and their isotopes.

Significance: Some studies suggested that the Earth’s mantle transition zone (MTZ) consists of hydrous silicates while others proposed that it contains iron metal. Here we show that the metallic iron dehydrates hydrous silicates at MTZ conditions, implying that global hydration of silicates and metal saturation are incompatible. Comparing iron production in and water injection to the MTZ, we found that the hydration of MTZ silicates is likely limited to <0.1 wt %, while large amount of the hydrogen can be stored as iron hydride and hydrogen fluid instead. Water-rich domains may still exist near the modern active subducted slabs. Our finding connects the water content to the oxidation state of the MTZ, thus providing a different perspective on volatile cycles in the mantle.

We report experimental constraints on the melting curve of potassium chloride (KCl) between 3.2 and 9 GPa from in situ ionic conduction measurements using a multi-anvil apparatus. On the basis of concurrent measurements of KCl and sodium chloride (NaCl) at 1 bar using the differential thermal analysis (DTA) method and Pt sphere marker, we show that the peak rate of increase in ionic current with temperature upon heating coincides with latent heat ledge and fall of Pt sphere, thus establishing the criterion for melting detection from ionic conduction measurements. Applying this criterion to high pressures, we found that the melting point of KCl rose steeply with increasing pressure to exceed 2443 ± 100 K at 9 GPa. Fitting the results of this study together with existing data at pressures below 4 GPa and above 20 GPa, we obtained the Simon’s melting equation for KCl in the simple cubic B2 structure between 1.8 and 50 GPa: $T_m=1323{\left(\frac{P-1.87}{2.2\left(1\right)}+1\right)}^{\frac{1}{2.7\left(1\right)}}$ , where T is in K and P is in GPa. Starting at 1 bar, the melting point of KCl increases at an average rate of ~150 K/GPa to cross that of Pt near 9 GPa. The highly refractory nature of KCl makes it a sensitive pressure calibrant for the large-volume pressure at moderate pressures and a potential sample container for experiments at moderate pressures and very high temperatures.

Superdeep diamonds contain unique information from the sublithospheric regions of Earth's interior. Recent studies suggest that reaction between subducted carbonate and iron metal in the mantle plays an important role in the production of superdeep diamonds. It is unknown if this reaction is kinetically feasible in cold slabs subducted into the deep mantle. Here we present experimental data on real‐time tracking of the magnesite‐iron reaction at high pressures and high temperatures to demonstrate the production of diamond at the surface conditions of cold slabs in the transition zone and lower mantle. Our data reveal that the diamond production rate has a positive temperature dependence and a negative pressure dependence, and along a slab geotherm it decreases by a factor of three at pressures from 14.4 to 18.4 GPa. This rate reduction provides an explanation for the rarity of superdeep diamonds from the interior of the mantle transition zone.