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Abstract The Ordovician (Hirnantian; 445 Ma) hosts the second most severe mass extinction in Earth history, coinciding with Gondwanan glaciation and increased geochemical evidence for marine anoxia. It remains unclear whether cooling, expanded oxygen deficiency, or a combination drove the Late Ordovician Mass Extinction (LOME). Here, we present combined iodine and sulfur isotope geochemical data from three globally distributed carbonate successions to constrain changes in local and global marine redox conditions. Iodine records suggest locally anoxic conditions were potentially pervasive on shallow carbonate shelves, while sulfur isotopes suggest a reduction in global euxinic (anoxic and sulfidic) conditions. Late Katian sulfate‐sulfur isotope data show a large negative excursion that initiated during elevated sea level and continued through peak Hirnantian glaciation. Geochemical box modeling suggests a combination of decreasing pyrite burial and increasing weathering are required to drive the observed negative excursion suggesting a ∼3% decrease of global seafloor euxinia during the Late Ordovician. The sulfur datasets provide further evidence that this trend was followed by increases in euxinia which coincided with eustatic sea‐level rise during subsequent deglaciation in the late Hirnantian. A persistence of shelf anoxia against a backdrop of waning then waxing global euxinia was linked to the two LOME pulses. These results place important constraints on local and global marine redox conditions throughout the Late Ordovician and suggest that non‐sulfidic shelfal anoxia—along with glacioeustatic sea level and climatic cooling—were important environmental stressors that worsened conditions for marine fauna, resulting in the second‐largest mass extinction in Earth history and the only example during an icehouse climate. 

Thallium isotopes reveal that rapid marine oxygen fluctuations in the Late Ordovician oceans are linked to mass extinction pulses. 

Abstract The late Ludlow Lau Event was a severe biotic crisis in the Silurian, characterized by resurgent microbial facies and faunal turnover rates otherwise only documented during the “big five” mass extinctions. This asynchronous late Silurian marine extinction event preceded an associated positive carbon isotope excursion (CIE), the Lau CIE, although a mechanism for this temporal offset remains poorly constrained. Here, we report thallium isotope data from locally reducing late Ludlow strata within the Baltic Basin to document the earliest onset of global marine deoxygenation. The initial expansion of anoxia coincided with the onset of the extinction and therefore preceded the Lau CIE. Additionally, sulfur isotope data record a large positive excursion parallel to the Lau CIE, interpreted to indicate an increase in pyrite burial associated with the widely documented CIE. This suggests a possible global expansion of euxinia (anoxic and sulfidic water column) following deoxygenation. These data are the most direct proxy evidence of paleoredox conditions linking the known extinction to the Lau CIE through the progressive expansion of anoxia, and most likely euxinia, across portions of the late Silurian oceans.