It is widely assumed that atmospheric oxygen concentrations remained persistently low (less than 10(-5) times present levels) for about the first 2 billion years of Earth's history. The first long-term oxygenation of the atmosphere is thought to have taken place around 2.3 billion years ago, during the Great Oxidation Event. Geochemical indications of transient atmospheric oxygenation, however, date back to 2.6-2.7 billion years ago. Here we examine the distribution of chromium isotopes and redox-sensitive metals in the approximately 3-billion-year-old Nsuze palaeosol and in the near-contemporaneous Ijzermyn iron formation from the Pongola Supergroup, South Africa. We find extensive mobilization of redox-sensitive elements through oxidative weathering. Furthermore, using our data we compute a best minimum estimate for atmospheric oxygen concentrations at that time of 3 × 10(-4) times present levels. Overall, our findings suggest that there were appreciable levels of atmospheric oxygen about 3 billion years ago, more than 600 million years before the Great Oxidation Event and some 300-400 million years earlier than previous indications for Earth surface oxygenation.
The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3–2.9 Gyr ago. 3.8–3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8–3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology.
The lower Cambrian Sirius Passet Lagerst€ atte (518 Ma) consists of mudstones about 8 m thick located in the Franklinian Basin of North Greenland. We analyzed major and trace elements plus the S, C, Cu, Fe, Zn, and Mo isotope compositions. Factor analysis allowed the lithology of the mudstone to be broken down into variable proportions of two inputs, a dry felsic component and a hydrous mafic component (smectite or chlorite). Zircons U-Pb ages indicate multiple sources, the local Proterozoic basement of Northern Greenland (1250-2400 Ma) and Pan-African felsic magmas (620-650 Ma) from across the Iapetus ocean. Diagenesis involved the reduction of Fe, S, and Mo from seawater and pyritization. The Sirius Passet Lagerst€ atte formed in oxygen-starved muds inhibiting degradation of organic matter underneath a wellventilated water column. The chemistry of the samples, their very fine grain size, their apparent lack of graded bedding, and the age of zircons suggest that the Lagerst€ atte may represent wind-blown dust deposited on the continental slope.
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