Evidence for a dominantly reducing Archaean ambient mantle from two redox proxies, and low oxygen fugacity of deeply subducted oceanic crust

Abstract

Abstract Oxygen fugacity (ƒO2) is an intensive variable implicated in a range of processes that have shaped the Earth system, but there is controversy on the timing and rate of oxidation of the uppermost convecting mantle to its present ƒO2 around the fayalite-magnetite-quartz oxygen buffer. Here, we report Fe3+/ΣFe and ƒO2 for ancient eclogite xenoliths with oceanic crustal protoliths that sampled the coeval ambient convecting mantle. Using new and published data, we demonstrate that in these eclogites, two redox proxies, V/Sc and Fe3+/ΣFe, behave sympathetically, despite different responses of their protoliths to differentiation and post-formation degassing, seawater alteration, devolatilisation and partial melting, testifying to an unexpected robustness of Fe3+/ΣFe. Therefore, these processes, while causing significant scatter, did not completely obliterate the underlying convecting mantle signal. Considering only unmetasomatised samples with non-cumulate and little-differentiated protoliths, V/Sc and Fe3+/ΣFe in two Archaean eclogite suites are significantly lower than those of modern mid-ocean ridge basalts (MORB), while a third suite has ratios similar to modern MORB, indicating redox heterogeneity. Another major finding is the predominantly low though variable estimated ƒO2 of eclogite at mantle depths, which does not permit stabilisation of CO2-dominated fluids or pure carbonatite melts. Conversely, low-ƒO2 eclogite may have caused efficient reduction of CO2 in fluids and melts generated in other portions of ancient subducting slabs, consistent with eclogitic diamond formation ages, the disproportionate frequency of eclogitic diamonds relative to the subordinate abundance of eclogite in the mantle lithosphere and the general absence of carbonate in mantle eclogite. This indicates carbon recycling at least to depths of diamond stability and may have represented a significant pathway for carbon ingassing through time.