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The disappearance of mass-independent sulfur isotope fractionation (S-MIF) within the c. 2.3-billion-year-old (Ga) Rooihoogte Formation has been heralded as a chemostratigraphic marker of permanent atmospheric oxygenation. Reports of younger S-MIF, however, question this narrative, leaving significant uncertainties surrounding the timing, tempo, and trajectory of Earth’s oxygenation. Leveraging a new bulk quadruple S-isotope record, we return to the South African Transvaal Basin in search of support for supposed oscillations in atmospheric oxygen beyond 2.3 Ga. Here, as expected, within the Rooihoogte Formation, our data capture a collapse in Δ 3× S values and a shift from Archean-like Δ 36 S/Δ 33 S slopes to their mass-dependent counterparts. Importantly, the interrogation of a Δ 33 S-exotic grain reveals extreme spatial variability, whereby atypically large Δ 33 S values are separated from more typical Paleoproterozoic values by a subtle grain-housed siderophile-enriched band. This isotopic juxtaposition signals the coexistence of two sulfur pools that were able to escape diagenetic homogenization. These large Δ 33 S values require an active photochemical sulfur source, fingerprinting atmospheric S-MIF production after its documented cessation elsewhere at ∼2.4 Ga. By contrast, the Δ 33 S monotony observed in overlying Timeball Hill Formation, with muted Δ 33 S values (<0.3‰) and predominantly mass-dependent Δ 36 S/Δ 33 S systematics, remains in stark contrast to recent reports of pronounced S-MIF within proximal formational equivalents. If reflective of atmospheric processes, these observed kilometer-scale discrepancies disclose heterogenous S-MIF delivery to the Transvaal Basin and/or poorly resolved fleeting returns to S-MIF production. Rigorous bulk and grain-scale analytical campaigns remain paramount to refine our understanding of Earth’s oxygenation and substantiate claims of post-2.3 Ga oscillations in atmospheric oxygen. 

We apply a new approach for the δ¹³C analysis of single organic‐walled microfossils (OWM) to three sites in the Appalachian Basin of New York (AB) that span the Late Devonian Biotic Crisis (LDBC). Our data provide new insights into the nature of the Frasnian–Famennian carbon cycle in the AB and also provide possible constraints on the paleoecology of enigmatic OWM ubiquitous in Paleozoic shale successions. The carbon isotope compositions of OWM are consistent with normal marine organic matter of autochthonous origins and range from −32 to −17‰, but average −25‰ across all samples and are consistently¹³C‐enriched compared to bulk sediments (δ¹³C_bulk) by ~0–10‰. We observe no difference between the δ¹³C_OWMof leiospheres (smooth‐walled) and acanthomorphic (spinose) acritarch OWM, indicating that our data are driven by ecological rather than taxonomic signals. We hypothesize that the offset between δ¹³C_OWMand δ¹³C_bulkis in part due to a large δ¹³C gradient in the AB water column where OWM utilized relatively¹³C‐enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating¹³C‐depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ¹³C_OWMand δ¹³C_bulkof 3‰ from shoreward to open‐ocean facies that may reflect the effect of¹³C‐enriched dissolved inorganic carbon (DIC) derived from riverine sources in the relatively enclosed AB. The hypothesized steep carbon isotope gradient in the AB could be due to a strong biological pump; this in turn may have contributed to low oxygen bottom water conditions during the LDBC. This is the first time single‐microfossil δ¹³C_organalyses of eukaryotes have been directly compared to bulk δ¹³C_orgin the deep‐time fossil record.

 

The degree to which ocean deoxygenation will alter the function of marine communities remains unclear but may be best constrained by detailed study of intervals of rapid warming in the geologic past. The Paleocene–Eocene Thermal Maximum (PETM) was an interval of rapid warming that was the result of increasing contents of greenhouse gases in the atmosphere that had wide ranging effects on ecosystems globally. Here, we present stable nitrogen isotope data from the Eastern Peri-Tethys Ocean that record a significant transition in the nitrogen cycle. At the initiation of the PETM, the nitrogen isotopic composition of sediments decreased by ~6‰ to as low as −3.4‰, signaling reorganization of the marine nitrogen cycle. Warming, changes in ocean circulation, and deoxygenation caused a transition to nitrogen cycle to conditions that were most similar to those experienced during Oceanic Anoxic Events of the Mesozoic.