Dynamic sulfur and carbon cycling through the end-Ordovician extinction revealed by paired sulfate-pyrite δ34S

Geochemical records of the end-Ordovician Hirnantian Stage show parallel positive excursions in the stable isotope compositions of sedimentary pyrite sulfur (δ34Spyr), organic carbon (δ13Corg), and carbonate carbon (δ13Ccarb); these isotope excursions coincide with the end Ordovician glaciation and mass extinction. A relative increase in pyrite burial (fpyr) attributed to marine anoxia has been invoked to explain the sulfur isotope excursion and link oceanic redox conditions to the extinction of marine fauna. An increase in fpyr would necessarily generate a parallel excursion of equal magnitude in the isotopic composition of coeval marine sulfate (δ34SSO4). Here we present new high-resolution paired sulfur isotope data from carbonate-associated sulfate (δ34SCAS) and pyrite from the Hirnantian Stage of western Anticosti Island (Québec, Canada). These data document a positive 20‰ enrichment in δ34Spyr (comparable in magnitude to previous reports), but no parallel excursion in δ34SCAS. This pattern provides new constraints on the origin of the δ34Spyr excursion and the nature of carbon-sulfur coupling through Hirnantian time. Specifically, these observations preclude enhanced pyrite burial as the cause of the Hirnantian δ34Spyr excursion and suggest the possible role of anoxia in the mass extinction may need to be reevaluated. Rather, the global δ34Spyr excursion is best explained by a transient reduction in the isotopic fractionations expressed during microbial sulfur cycling (εpyr). The εpyr record shows a strong inverse correlation with δ13C, suggesting a mechanistic link between carbon cycling and processes controlling εpyr during the Hirnantian. Changes in sea level or marine redox state associated with glaciation could further impact the expression of the biological fractionation (e.g., through syndepositional sediment reworking and/or chemocline migration and resultant restricted exchange of porewater sulfate). The magnitude of isotopic fractionation during microbial sulfate reduction is partially controlled by metabolic rates, which are sensitive to the abundance, type, and lability of metabolically relevant substrates. Environmental change associated with the end Ordovician glaciation may have elevated the flux of organic material to marine sediments or caused an increase in physical reworking of sediments, leading to increased microbial sulfate reduction rates and reduced εpyr. As such, the Hirnantian δ34Spyr excursion may be viewed as a dynamic biological response to global climate change, highlighting the connections between the carbon and sulfur biogeochemical cycles.

► New paired δ34SCAS-δ34Spyr data from end Ordovician of Anticosti Island. ► Positive δ34Spyr and δ13C excursions with no change in δ34SCAS. ► Time-varying isotope model precludes pyrite burial as driver of changes. ► Lower fractionation of S isotopes from sulfate reduction during glaciation. ► Increased availability of organic substrates may have driven S and C excursions.