Author Correction: Constraining the rise of oxygen with oxygen isotopes.

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Constraining the rise of oxygen with oxygen isotopes.

After permanent atmospheric oxygenation, anomalous sulfur isotope compositions were lost from sedimentary rocks, demonstrating that atmospheric chemistry ceded its control of Earth's surficial sulfur cycle to weathering. However, mixed signals of anoxia and oxygenation in the sulfur isotope record between 2.5 to 2.3 billion years (Ga) ago require independent clarification, for example via oxygen isotopes in sulfate. Here we show <2.31 Ga sedimentary barium sulfates (barites) from the Turee Creek Basin, W. Australia with positive sulfur isotope anomalies of ∆33S up to + 1.55‰ and low δ18O down to -19.5‰. The unequivocal origin of this combination of signals is sulfide oxidation in meteoric water. Geochemical and sedimentary evidence suggests that these S-isotope anomalies were transferred from the paleo-continent under an oxygenated atmosphere. Our findings indicate that incipient oxidative continental weathering, ca. 2.8-2.5 Ga or earlier, may be diagnosed with such a combination of low δ18O and high ∆33S in sulfates.

Sulfur isotope's signal of nanopyrites enclosed in 2.7 Ga stromatolitic organic remains reveal microbial sulfate reduction.

Microbial sulfate reduction (MSR) is thought to have operated very early on Earth and is often invoked to explain the occurrence of sedimentary sulfides in the rock record. Sedimentary sulfides can also form from sulfides produced abiotically during late diagenesis or metamorphism. As both biotic and abiotic processes contribute to the bulk of sedimentary sulfides, tracing back the original microbial signature from the earliest Earth record is challenging. We present in situ sulfur isotope data from nanopyrites occurring in carbonaceous remains lining the domical shape of stromatolite knobs of the 2.7-Gyr-old Tumbiana Formation (Western Australia). The analyzed nanopyrites show a large range of δ34 S values of about 84‰ (from -33.7‰ to +50.4‰). The recognition that a large δ34 S range of 80‰ is found in individual carbonaceous-rich layers support the interpretation that the nanopyrites were formed in microbial mats through MSR by a Rayleigh distillation process during early diagenesis. An active microbial cycling of sulfur during formation of the stromatolite may have facilitated the mixing of different sulfur pools (atmospheric and hydrothermal) and explain the weak mass independent signature (MIF-S) recorded in the Tumbiana Formation. These results confirm that MSR participated actively to the biogeochemical cycling of sulfur during the Neoarchean and support previous models suggesting anaerobic oxidation of methane using sulfate in the Tumbiana environment.

A diagenetic control on the Early Triassic Smithian-Spathian carbon isotopic excursions recorded in the marine settings of the Thaynes Group (Utah, USA).

In the aftermath of the end-Permian mass extinction, Early Triassic sediments record some of the largest Phanerozoic carbon isotopic excursions. Among them, a global Smithian-negative carbonate carbon isotope excursion has been identified, followed by an abrupt increase across the Smithian-Spathian boundary (SSB; ~250.8 Myr ago). This chemostratigraphic evolution is associated with palaeontological evidence that indicate a major collapse of terrestrial and marine ecosystems during the Late Smithian. It is commonly assumed that Smithian and Spathian isotopic variations are intimately linked to major perturbations in the exogenic carbon reservoir. We present paired carbon isotopes measurements from the Thaynes Group (Utah, USA) to evaluate the extent to which the Early Triassic isotopic perturbations reflect changes in the exogenic carbon cycle. The δ(13) Ccarb variations obtained here reproduce the known Smithian δ(13) Ccarb -negative excursion. However, the δ(13) C signal of the bulk organic matter is invariant across the SSB and variations in the δ(34) S signal of sedimentary sulphides are interpreted here to reflect the intensity of sediment remobilization. We argue that Middle to Late Smithian δ(13) Ccarb signal in the shallow marine environments of the Thaynes Group does not reflect secular evolution of the exogenic carbon cycle but rather physicochemical conditions at the sediment-water interface leading to authigenic carbonate formation during early diagenetic processes.

Extreme 15N-enrichments in 2.72-Gyr-old sediments: evidence for a turning point in the nitrogen cycle.

Although nitrogen is a key element in organic molecules such as nucleic acids and proteins, the timing of the emergence of its modern biogeochemical cycle is poorly known. Recent studies on the antiquity of the nitrogen cycle and its interaction with free oxygen suggests the establishment of a complete aerobic N biogeochemical cycle with nitrification, denitrification, and nitrogen fixation at about 2.68 Gyr. Here, we report new bulk nitrogen isotope data for the 2.72 billion-year-old sedimentary succession of the Tumbiana Formation (Pilbara Craton, Western Australia). The nitrogen isotopic compositions vary widely from +8.6‰ up to +50.4‰ and are inversely correlated with the very low δ(13)C values of associated organic matter defining the Fortescue excursion (down to about -56‰). We propose that this (15)N-enrichment records the onset of nitrification coupled to the continuous removal of its derivatives (nitrite and nitrate) by denitrification. This finding implies an increase in the availability of electron acceptors and probably oxygen in the Tumbiana depositional environment, 300 million years before the oxygenation of the Earth's atmosphere.