Extreme redox variations in a superdeep diamond from a subducted slab.

The introduction of volatile-rich subducting slabs to the mantle may locally generate large redox gradients, affecting phase stability, element partitioning and volatile speciation1. Here we investigate the redox conditions of the deep mantle recorded in inclusions in a diamond from Kankan, Guinea. Enstatite (former bridgmanite), ferropericlase and a uniquely Mg-rich olivine (Mg# 99.9) inclusion indicate formation in highly variable redox conditions near the 660 km seismic discontinuity. We propose a model involving dehydration, rehydration and dehydration in the underside of a warming slab at the transition zone-lower mantle boundary. Fluid liberated by dehydration in a crumpled slab, driven by heating from the lower mantle, ascends into the cooler interior of the slab, where the H2O is sequestered in new hydrous minerals. Consequent fractionation of the remaining fluid produces extremely reducing conditions, forming Mg-end-member ringwoodite. This fractionating fluid also precipitates the host diamond. With continued heating, ringwoodite in the slab surrounding the diamond forms bridgmanite and ferropericlase, which is trapped as the diamond grows in hydrous fluids produced by dehydration of the warming slab.

Evidence for complex iron oxides in the deep mantle from FeNi(Cu) inclusions in superdeep diamond.

The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth's mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth's mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)Σ=3.95O5 We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.