Low-spin ferric iron in primordial bridgmanite crystallized from a deep magma ocean

The crystallization of the magma ocean resulted in the present layered structure of the Earth's mantle. An open question is the electronic spin state of iron in bridgmanite (the most abundant mineral on Earth) crystallized from a deep magma ocean, which has been neglected in the crystallization history of the entire magma ocean. Here, we performed energy-domain synchrotron Mössbauer spectroscopy measurements on two bridgmanite samples synthesized at different pressures using the same starting material (Mg_0.78Fe_0.13Al_0.11Si_0.94O₃). The obtained Mössbauer spectra showed no evidence of low-spin ferric iron (Fe³⁺) from the bridgmanite sample synthesized at relatively low pressure of 25 gigapascals, while that directly synthesized at a higher pressure of 80 gigapascals contained a relatively large amount. This difference ought to derive from the large kinetic barrier of Fe³⁺ rearranging from pseudo-dodecahedral to octahedral sites with the high-spin to low-spin transition in experiments. Our results indicate a certain amount of low-spin Fe³⁺ in the lower mantle bridgmanite crystallized from an ancient magma ocean. We therefore conclude that primordial bridgmanite with low-spin Fe³⁺ dominated the deeper part of an ancient lower mantle, which would contribute to lower mantle heterogeneity preservation and call for modification of the terrestrial mantle thermal evolution scenarios.