Bulk and grain-scale minor sulfur isotope data reveal complexities in the dynamics of Earth's oxygenation.

SignificanceThe permanent disappearance of mass-independent sulfur isotope fractionation (S-MIF) from the sedimentary record has become a widely accepted proxy for atmospheric oxygenation. This framework, however, neglects inheritance from oxidative weathering of pre-existing S-MIF-bearing sedimentary sulfide minerals (i.e., crustal memory), which has recently been invoked to explain apparent discrepancies within the sulfur isotope record. Herein, we demonstrate that such a crustal memory effect does not confound the Carletonville S-isotope record; rather, the pronounced Δ33S values identified within the Rooihoogte Formation represent the youngest known unequivocal oxygen-free photochemical products. Previously observed 33S-enrichments within the succeeding Timeball Hill Formation, however, contrasts with our record, revealing kilometer-scale heterogeneities that highlight significant uncertainties in our understanding of the dynamics of Earth's oxygenation.

Reconciling discrepant minor sulfur isotope records of the Great Oxidation Event.

Understanding the timing and trajectory of atmospheric oxygenation remains fundamental to deciphering its causes and consequences. Given its origin in oxygen-free photochemistry, mass-independent sulfur isotope fractionation (S-MIF) is widely accepted as a geochemical fingerprint of an anoxic atmosphere. Nevertheless, S-MIF recycling through oxidative sulfide weathering-commonly termed the crustal memory effect (CME)-potentially decouples the multiple sulfur isotope (MSI) record from coeval atmospheric chemistry. Herein, however, after accounting for unrecognised temporal and spatial biases within the Archaean-early-Palaeoproterozoic MSI record, we demonstrate that the global expression of the CME is barely resolvable; thereby validating S-MIF as a tracer of contemporaneous atmospheric chemistry during Earth's incipient oxygenation. Next, utilising statistical approaches, supported by new MSI data, we show that the reconciliation of adjacent, yet seemingly discrepant, South African MSI records requires that the rare instances of post-2.3-billion-year-old S-MIF are stratigraphically restricted. Accepting others' primary photochemical interpretation, our approach demands that these implied atmospheric dynamics were ephemeral, operating on sub-hundred-thousand-year timescales. Importantly, these apparent atmospheric relapses were fundamentally different from older putative oxygenation episodes, implicating an intermediate, and potentially uniquely feedback-sensitive, Earth system state in the wake of the Great Oxidation Event.

Carbon cycle dynamics and ecology revealed by the carbon isotopic composition of single organic microfossils during the Late Devonian Biotic Crisis.

We apply a new approach for the δ13 C 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 consistently 13 C-enriched compared to bulk sediments (δ13 Cbulk ) by ~0-10‰. We observe no difference between the δ13 COWM of 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 δ13 COWM and δ13 Cbulk is in part due to a large δ13 C gradient in the AB water column where OWM utilized relatively 13 C-enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating 13 C-depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ13 COWM and δ13 Cbulk of 3‰ from shoreward to open-ocean facies that may reflect the effect of 13 C-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 δ13 Corg analyses of eukaryotes have been directly compared to bulk δ13 Corg in the deep-time fossil record.

Perturbation to the nitrogen cycle during rapid Early Eocene global warming.

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.