Sub-arc mantle fugacity shifted by sediment recycling across the Great Oxidation Event

Abstract

The chemical exchange between the atmosphere, crust and mantle depends on sediment recycling via subduction. However, it remains unclear how atmospherically modified sediment may affect mantle oxygen fugacity through time. The Great Oxidation Event, among the most important atmospheric changes on Earth, offers an opportunity to investigate changes in magmatism related to surface–mantle interactions. Here we use sulfur K-edge micro X-ray absorption near-edge structure spectroscopy to measure the relative abundances of S6+, S4+ and S2− state in apatite inclusions hosted in 2.4–2.1-billion-year-old igneous zircons from the Mineiro Belt, Brazil. The host magmas record intracrustal melting of juvenile crust and the involvement of recycled sediments in the sub-arc mantle wedge. Unaltered apatite inclusions reveal a change from reduced to more oxidized magmas from pre- to post-Great Oxidation Event during the early Proterozoic. We argue that this change is a direct result of deep subduction of oxidized sediments and thus evidence of mantle–atmosphere interaction across the Great Oxidation Event. This suggests that the onset of sediment recycling in the Archaean provided atmospheric access to the mantle, and early ‘whiffs’ of oxygen may have already contributed to a localized increase of calc-alkaline magmatism and related ore deposits on Earth.