Marine redox variability from Baltica during extinction events in the latest Ordovician-early Silurian

It is well documented that Upper Ordovician and Silurian successions record multiple marine turnover events including the second-largest mass extinction in the Phanerozoic - widespread glaciation, and multiple global carbon cycle perturbations. Whereas causal mechanisms for the Late Ordovician major mass extinction event involving climate, paleoceanographic variation, and delta C-13 records have been published, similar records remain poorly constrained for subsequent extinction events in the early Silurian. Here, we present new organic matter carbon isotope (delta C-13(org)) chemostratigraphy and corresponding paleoredox proxies (Fe speciation, [Mn, V, Mo], and pyrite sulfur isotopes) from two organic-rich drill core sections in Sweden and Latvia that span the upper Katian through lower Wenlock stages (446-431 Ma). Pyritized Fe and bulk sedimentary Mn concentrations from Upper Ordovician strata in southern Sweden suggest a local redox shift to more reducing conditions in the late Hirnantian, possibly including euxinic (anoxic and sulfidic water column) conditions that coincide with the second mass extinction pulse. The new high-resolution delta C-13(org) and delta S-34(pyr) datasets from the late Aeronian (early Silurian) interval within both drill cores show positive excursions that are broadly coincident with the associated Sandvika and sedgwickii extinction events. Independently, Fe speciation and bulk sedimentary trace metal data from this late Aeronian interval record locally euxinic conditions in both the deep basinal (Sweden) and distal shelf (Latvia) settings before and during the late Aeronian positive delta C-13 excursion. This multiproxy paleoredox dataset provides the first direct evidence for local to regional expansion of reducing marine conditions coincident with this early Silurian (late Aeronian) biotic event and positive delta C-13 excursion. Additionally, new delta S-34(pyr) values spanning the Llandovery/Wenlock boundary interval in the Latvia core show a positive excursion coincident with Fe speciation and trace metal enrichments that imply a local redox perturbation with intermittently euxinic bottom waters during the rising limb of the Ireviken positive delta C-13 excursion. The combination of these geochemical data for local-to regional-scale (more data required for global interpretations) changes in marine redox conditions with paleobiological records and evidence for eustatic sea-level rise indicate that environmental stresses related to an expansion of anoxic to euxinic conditions were a probable driver for several extinction events during the latest Ordovician-early Silurian.