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Exchange between a magma ocean and vapor produced Earth’s earliest atmosphere. Its speciation depends on the oxygen fugacity (fO2) set by the Fe3+/Fe2+ ratio of the magma ocean at its surface. Here, we establish the relationship between fO2 and Fe3+/Fe2+ in quenched liquids of silicate Earth-like composition at 2173 K and 1 bar. Mantle-derived rocks have Fe3+/(Fe3++Fe2+) = 0.037 ± 0.005, at which the magma ocean defines an fO2 0.5 log units above the iron-wüstite buffer. At this fO2, the solubilities of H-C-N-O species in the magma ocean produce a CO-rich atmosphere. Cooling and condensation of H2O would have led to a prebiotic terrestrial atmosphere composed of CO2-N2, in proportions and at pressures akin to those observed on Venus. Present-day differences between Earth’s atmosphere and those of her planetary neighbors result from Earth’s heliocentric location and mass, which allowed geologically long-lived oceans, in-turn facilitating CO2 drawdown and, eventually, the development of life.

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Sub-lithospheric diamonds from the Juina-5 and Collier-4 kimberlites and the Machado River alluvial deposit in Brazil have carbon isotopic compositions that co-vary with the oxygen isotopic compositions of their inclusions, which implies that they formed by a mixing process. The proposed model for this mixing process, based on interaction of slab-derived carbonate melt with reduced (carbide-or metalbearing) ambient mantle, explains these isotopic observations. It is also consistent with the observed trace element chemistries of diamond inclusions from these localities and with the experimental phase relations of carbonated subducted crust. The 18 O-enriched nature of the inclusions demonstrates that they incorporate material from crustal protoliths that previously interacted with seawater, thus confirming the subduction-related origin of superdeep diamonds. These samples also provide direct evidence of an isotopically anomalous reservoir in the deep (≥ 350 km) mantle.

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