Rising oceanic and atmospheric oxygen levels through time have been crucial to enhanced habitability of surface Earth environments. Few redox proxies can track secular variations in dissolved oxygen concentrations around threshold levels for metazoan survival in the upper ocean. We present an extensive compilation of iodine-to-calcium ratios (I/Ca) in marine carbonates. Our record supports a major rise in the partial pressure of oxygen in the atmosphere at ~400 million years (Ma) ago and reveals a step change in the oxygenation of the upper ocean to relatively sustainable near-modern conditions at ~200 Ma ago. An Earth system model demonstrates that a shift in organic matter remineralization to greater depths, which may have been due to increasing size and biomineralization of eukaryotic plankton, likely drove the I/Ca signals at ~200 Ma ago.

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Recurrent mass extinction events (at "biomere"-a biostratigraphic unit-boundaries) characterize the middle Cambrian to Early Ordovician (Tremadocian) time interval that is between the major Cambrian and Ordovician radiations of animal life. A role for anoxia in maintaining elevated extinction rates in the late Cambrian has been proposed based on coincidence of an extinction with positive excursions in d 13 C carb and d 34 S CAS (CAS-carbonate-associated sulfate). Here we examine an Early Ordovician extinction event at the base of the North American Stairsian Stage (upper Tremadocian), and demonstrate concurrent onset of positive excursions in d 13 C and d 34 S inferred to reflect enhanced organic matter burial under anoxic waters. Sea-level rise may have brought anoxic waters onto the shelf to initiate extinctions. The evidence for d 13 C excursions and elevated extinction rates appears to wane in the Tremadocian, consistent with progressive oxygenation of the oceans reaching a threshold that helped facilitate initial stages of the Great Ordovician Biodiversification Event.

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The Ordovician 87 Sr/ 86 Sr isotope seawater curve is well established and shows a decreasing trend until the mid-Katian. However, uncertainties in calibration of this curve to biostratigraphy and geochronology have made it diffi cult to determine how the rates of 87 Sr/ 86 Sr decrease may have varied, which has implications for both the stratigraphic resolution possible using Sr isotope stratigraphy and efforts to model the effects of Ordovician geologic events. We measured 87 Sr/ 86 Sr in conodont apatite in North American Ordovician sections that are well studied for conodont biostratigraphy, primarily in Nevada, Oklahoma, the Appalachian region, and Ohio Valley. Our results indicate that conodont apatite may provide an accurate medium for Sr isotope stratigraphy and strengthen previous reports that point toward a signifi cant increase in the rate of fall in seawater 87 Sr/ 86 Sr during the Middle Ordovician Darriwilian Stage. Our 87 Sr/ 86 Sr results suggest that Sr isotope stratigraphy will be most useful as a high-resolution tool for global correlation in the mid-Darriwilian to mid-Sandbian, when the maximum rate of fall in 87 Sr/ 86 Sr is estimated at ~5.0-10.0 × 10 -5 per m.y. Variable preservation of conodont elements limits the precision for individual stratigraphic horizons. Replicate conodont analyses from the same sample differ by an average of ~4.0 × 10 -5 (the 2σ standard deviation is 6.2 × 10 -5 ), which in the best case scenario allows for subdivision of Ordovician time intervals characterized by the highest rates of fall in 87 Sr/ 86 Sr at a maximum resolution of ~0.5-1.0 m.y. Links between the increased rate of fall in 87 Sr/ 86 Sr beginning in the mid-late Darriwilian (Phragmodus polonicus to Pygodus serra conodont zones) and geologic events continue to be investigated, but the coincidence with a long-term rise in sea level (Sauk-Tippecanoe megasequence boundary) and tectonic events (Taconic orogeny) in North America provides a plausible explanation for the changing magnitude and 87 Sr/ 86 Sr of the riverine Sr fl ux to the oceans.