Mesoproterozoic oxygenation event: From shallow marine to atmosphere

Abstract Oxygen availability is crucial for the evolution of eukaryotes in geological history, but the redox conditions of the mid-Proterozoic atmospheric-oceanic system remain vigorously debated. Previous geochemical studies suggested a very low mid-Proterozoic atmospheric oxygen level of probably below 0.1%–1% of the present atmospheric level (PAL) with weakly oxygenated surface ocean, which may have suppressed the early evolution of eukaryotes in the ocean. A recent study, however, revealed a pulsed oxygenation event that was recorded in shallow marine carbonate of the middle Gaoyuzhuang Formation (at ca. 1.57 Ga, North China) with atmospheric pO2 of up to ≥4% PAL based on iodine speciation. This event is associated with the earliest known multi-cellular eukaryotic fossils. To elucidate whether this pulsed oxygenation was limited to shallow local seawaters or could also reflect an increase in atmospheric oxygen, chromium (Cr), and carbonate-associated sulfate (CAS), sulfur isotopes in the middle Gaoyuzhuang Formation were studied in two sections of the North China Platform. The results show a positive shift in authigenic Cr isotope from −0.18‰ to +0.66‰, which was followed by a decline to −0.16‰. This suggests a rise in atmospheric oxygen sufficient to initiate oxic Cr cycling and isotope fractionation (pO2 > 0.1%–1% PAL). This positive Cr isotope excursion was associated with a transient positive shift in δ34SCAS from ~20‰ to ~50‰ and a subsequent decline to ~10‰, which provides independent evidence of atmospheric oxygenation. This oxygenation may have enhanced oxidative terrestrial weathering and increased sulfate input to the ocean, thus stimulating bacterial sulfate reduction and pyrite burial in deep anoxic seawaters. This is broadly consistent with previous results of carbonate I/(Ca + Mg) and Ce anomaly but also reveals a lag between shallow seawater and atmospheric oxygenation. Fluctuated redox conditions and decoupled oxygenation between shallow seawater and atmosphere during the mid-Proterozoic may help to account for the current debate.