Sulfur isotope evidence for low and fluctuating sulfate levels in the Late Devonian ocean and the potential link with the mass extinction event

- We present S-isotope compositions of CAS and pyrite from Late Devonian successions.
- The punctata δ13C excursion accompanies a positive shift in δ34SCAS and δ34Spy.
- The Upper Kellwasser δ13C excursion lacks a positive shift in δ34SCAS.
- Box model and multiple S-isotope data suggest low and fluctuating sulfate levels.
- Increasing sulfate levels may have contributed to the F-F mass extinction.

High amplitude positive carbon isotope excursions in the Late Devonian, the punctata and Kellwasser events, reflect major perturbations in the global carbon cycle that have been attributed to increased continental weathering and subsequent ocean eutrophication. Despite the comparable carbon isotope anomalies, however, a major extinction has been reported only for the Kellwasser Events, while the punctata Event is marked by low extinction intensity. This study presents multiple sulfur isotope records of carbonate-associated sulfate (CAS) and pyrite from Late Devonian sections in the Great Basin, USA, in order to document changes in the coupled (or decoupled) geochemical cycles of carbon and sulfur during the punctata and Upper Kellwasser events. A positive sulfur isotope shift in both CAS and pyrite accompanies the onset of the punctata Event, but to a larger extent in the latter. As a result, the sulfur isotope offset between CAS and pyrite (Δ34SCAS-py) dropped to less than 10‰. In the middle of the punctata Event, a sharp negative δ34SCAS excursion and negative Δ34SCAS-py values coincide with the Alamo impact. Unlike the rapid δ34Spy and δ34SCAS oscillations associated with the punctata Event, the Upper Kellwasser was a period of relative stability, except for a brief δ34SCAS drop before the event. Paired sulfur isotope data, aided by a simple box model, suggest that the geochemical cycle of sulfur may have been partly responsible for the contrasting biological responses that define these events. High stratigraphic δ34Spy and δ34SCAS variability, coupled with strong reservoir effect, demonstrates a relatively small oceanic sulfate pool existed during the punctata Event. Further, the Alamo impact likely triggered the rapid oxidation of microbially-produced sulfide within this event. The expansion of sulfidic bottom water thus may have been impeded during the punctata Event. In contrast, the lack of a positive shift in δ34SCAS and sizable Δ34SCAS-py values (>15‰) throughout the Upper Kellwasser Event imply higher relative sulfate levels. A larger seawater sulfate reservoir may have promoted the development of sulfidic bottom waters in the eutrophic epicontinental seas, increasing biological stress and potentially contributing to the mass extinction.