Metal Saturation and the Redistribution of Hydrogen in Earth's Mantle

Abstract

Iron disproportionation reactions in mantle silicates can produce metallic iron that drives Earth's deep mantle toward metal saturation under reduced conditions. Subducting slabs transport hydrated silicates to these depths, where interactions with metallic iron can reduce structurally bound hydrogen in silicates to reduced hydrogen-bearing phases, such as molecular hydrogen or iron hydrides, leaving mantle rocks in effect dry. Using the thermodynamic code HeFESTo with its latest self-consistent treatment of iron-bearing mantle phases, we investigate the stability and distribution of metallic iron in Earth's pyrolitic mantle across a broad range of oxidation states, represented by whole-rock Fe3+/$\Sigma$Fe ratio from 1% to 10%. We find that metallic iron is present through much of the lower mantle across this range and, under very reduced compositions of whole-rock Fe3+/$\Sigma$Fe = 1-3%, extends into the upper mantle. Where subducted water meets metal-saturated regions, hydrous melts may form and migrate upward, rehydrating the overlying mantle or pooling near the transition zone. Metal saturation can thus redistribute hydrogen internally, creating a sharp contrast between a wet shallow mantle and a dry deep mantle. This redox-driven redistribution can decrease mantle silicate water storage capacity by 64-96% today, to only 0.1-0.8 modern ocean masses, and may explain the viscosity contrast near the upper-lower mantle boundary. Although quantitative estimates of metal abundance and distribution depend on thermodynamic assumptions and remain uncertain above 50 GPa, our results reveal the role of redox reactions between disproportionated iron and subducted water in governing the speciation and redistribution of hydrogen in Earth's mantle.