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1. Patterns of local and global redox variability during the Cenomanian–Turonian Boundary Event (Oceanic Anoxic Event 2) recorded in carbonates and shales from central Italy

   https://doi.org/10.1111/sed.12352  

   Owens, Jeremy D. ; Lyons, Timothy W. ; Hardisty, Dalton S. ; Lowery, Chris M. ; Lu, Zunli ; Lee, Bridget ; Jenkyns, Hugh C. ; Heimhofer, ed., Ulrich ( January 2017 , Sedimentology)

   Careful evaluation of the local geochemical conditions in past marine settings can provide a window to the average redox state of the global ocean during episodes of extensive organic carbon deposition. These comparisons aid in identifying the interplay between climate and biotic feedbacks contributing to and resulting from these events. Well‐documented examples are known from the Mesozoic Era, which is characterized by episodes of widespread organic carbon deposition known as Oceanic Anoxic Events. This organic carbon burial typically leads to coeval positive carbon‐isotope excursions. Geochemical data are presented here for several palaeoredox proxies (Cr/Ti, V, Mo, Zn, Mn, Fe speciation, I/Ca and sulphur isotopes) from a section exposed at Furlo in the Marche–Umbrian Apennines of Italy that spans the Cenomanian–Turonian boundary. Here, Oceanic Anoxic Event 2 is represented by aca1 m thick radiolarian‐rich millimetre‐laminated organic‐rich shale known locally as the Bonarelli Level. Iron speciation data for thin organic‐rich intervals observed below the Bonarelli Level imply a local redox shift going into the Oceanic Anoxic Event, with ferruginous conditions (i.e. anoxic with dissolved ferrous iron) transiently developed prior to the event and euxinia (i.e. anoxic and sulphidic bottom waters) throughout the event itself. Pre‐Oceanic Anoxic Event enrichments of elements sensitive to anoxic water columns were due to initial development of locally ferruginous bottom waters as a precursor to the event. However, the greater global expanse of dysoxic to euxinic conditions during the Oceanic Anoxic Event greatly reduced redox‐sensitive trace‐metal concentrations in seawater. Pyrite sulphur isotopes document a positive excursion during the Oceanic Anoxic Event. Carbonate I/Ca ratios were generally low, suggesting locally reduced bottom‐water oxygen conditions preceding the event and relatively increased oxygen concentrations post‐event. Combined, the Furlo geochemical data suggest a redox‐stratified water column with oxic surface waters and a shallow chemocline overlying locally ferruginous bottom waters preceding the event, globally widespread euxinic bottom waters during the Oceanic Anoxic Event, followed by chemocline shallowing but sustained local redox stratification following the event.

    

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2. A long-term record of early to mid-Paleozoic marine redox change

   https://doi.org/10.1126/sciadv.abf4382  

   Sperling, Erik A. ; Melchin, Michael J. ; Fraser, Tiffani ; Stockey, Richard G. ; Farrell, Una C. ; Bhajan, Liam ; Brunoir, Tessa N. ; Cole, Devon B. ; Gill, Benjamin C. ; Lenz, Alfred ; et al ( July 2021 , Science Advances)

   null (Ed.)

   The extent to which Paleozoic oceans differed from Neoproterozoic oceans and the causal relationship between biological evolution and changing environmental conditions are heavily debated. Here, we report a nearly continuous record of seafloor redox change from the deep-water upper Cambrian to Middle Devonian Road River Group of Yukon, Canada. Bottom waters were largely anoxic in the Richardson trough during the entirety of Road River Group deposition, while independent evidence from iron speciation and Mo/U ratios show that the biogeochemical nature of anoxia changed through time. Both in Yukon and globally, Ordovician through Early Devonian anoxic waters were broadly ferruginous (nonsulfidic), with a transition toward more euxinic (sulfidic) conditions in the mid–Early Devonian (Pragian), coincident with the early diversification of vascular plants and disappearance of graptolites. This ~80-million-year interval of the Paleozoic characterized by widespread ferruginous bottom waters represents a persistence of Neoproterozoic-like marine redox conditions well into the Phanerozoic. 

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3. Evidence for the development of local anoxia during the Cambrian SPICE event in eastern North America

   https://doi.org/10.1111/gbi.12334  

   LeRoy, Matthew A. ; Gill, Benjamin C. ( February 2019 , Geobiology)

   The later Cambrian Steptoean Positive Carbon Isotope Excursion (SPICE) event was an episode marked by pronounced changes to the global biogeochemical cycles of carbon and sulfur and significant extinctions on several paleocontinents including Laurentia (North America). While the exact cause(s) of these events remains debated, various lines of evidence suggest an increase in the areal extent of anoxia at the seafloor was a likely feature. Here, we explore whether changes in local oxygenation accompanied the onset of theSPICEin southern Laurentia using cores of the Nolichucky and Eau Claire Formations from Ohio and Kentucky,USA, that represent a transect into the Rome Trough/Conasauga intrashelf basin. At our study locations, the initial positive δ¹³C shift of theSPICEoccurs in conjunction with increases in the abundance and δ³⁴S of sedimentary pyrite. Further local redox conditions, tracked using iron speciation analysis, indicate anoxic conditions developed at the two proximal locations after the start of the paired isotopic excursions. However, the location near the basin center shows no indication for anoxia before or during the onset of theSPICE. While this signal may reflect the structure of local redox conditions within the basin, with the development of anoxia limited to the basin margins, we argue that authigenic iron enrichments were muted by sedimentary dilution and/or the enhanced authigenesis of iron‐bearing sheet silicates near the basin center, masking the signal for anoxia there. Regardless of the areal extent of anoxia within the basin, in either scenario the timing of the development of anoxic bottom waters was concurrent with local faunal turnover, features broadly consistent with a global expansion of anoxia playing a role in driving the isotopic trends and extinctions observed during the event.

    

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4. What the ~1.4 Ga Xiamaling Formation can and cannot tell us about the mid‐Proterozoic ocean

   https://doi.org/10.1111/gbi.12282  

   Diamond, C. W. ; Planavsky, N. J. ; Wang, C. ; Lyons, T. W. ( March 2018 , Geobiology)

   Despite a surge of recent work, the evolution of mid‐Proterozoic oceanic–atmospheric redox remains heavily debated. Constraining the dynamics of Proterozoic redox evolution is essential to determine the role, if any, that anoxia played in protracting the development of eukaryotic diversity. We present a multiproxy suite of high‐resolution geochemical measurements from a drill core capturing the ~1.4 Ga Xiamaling Formation, North China Craton. Specifically, we analyzed major and trace element concentrations, sulfur and molybdenum isotopes, and iron speciation not only to better understand the local redox conditions but also to establish how relevant our data are to understanding the contemporaneous global ocean. Our results suggest that throughout deposition of the Xiamaling Formation, the basin experienced varying degrees of isolation from the global ocean. During deposition of the lower organic‐rich shales (130–85 m depth), the basin was extremely restricted, and the reservoirs of sulfate and trace metals were drawn down almost completely. Above a depth of 85 m, shales were deposited in dominantly euxinic waters that more closely resembled a marine system and thus potentially bear signatures of coeval seawater. In the most highly enriched sample from this upper interval, the concentration of molybdenum is 51 ppm with a δ⁹⁸Mo value of +1.7‰. Concentrations of Mo and other redox‐sensitive elements in our samples are consistent with a deep ocean that was largely anoxic on a global scale. Our maximum δ⁹⁸Mo value, in contrast, is high compared to published mid‐Proterozoic data. This high value raises the possibility that the Earth's surface environments were transiently more oxygenated at ~1.4 Ga compared to preceding or postdating times. More broadly, this study demonstrates the importance of integrating all available data when attempting to reconstruct surface O₂dynamics based on rocks of any age.

    

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5. Isotopes to ice: Constraining provenance of glacial deposits and ice centers in west-central Gondwana

   Griffis, N.P. ; Montañez, I.P. ; Fedorchuk, N. ; Isbell, J. ; Mundil, R. ; Vesely, F. ; Weinshultz, L. ; Iannuzzi, R. ; Gulbranson, E. ; Taboada, A. ; et al ( April 2018 , Palaeogeography, palaeoclimatology, palaeoecology)

   The timing and geographic distribution of glaciers in high-latitude southern Gondwana during the Late Paleozoic Ice Age remain poorly constrained, ultimately precluding our ability to estimate ice volume and associated climate teleconnections and feedbacks during Earth's penultimate icehouse. Current aerial extents of glaciers, constrained by sedimentary flow directions, near exclusively infer paleo-glaciation to be highland-driven and may underestimate potential ice sources in continental regions from which ice sheets may have emanated. Here, we report new U-Pb ages and Hf isotope compositions of detrital zircons recovered from diamictites in two key mid- to high-latitude Gondwanan basins (Paraná, Brazil and Tepuel, Argentine Patagonia). The results indicate regional sediment sources for both basins during the early period of late Paleozoic glaciation evolving into more distal sources during the final deglaciation along southern and western Gondwana. Similar age sediment sourced from diamictites in the Congo Basin, that require an ice center in eastern Africa suggest the possibility of a large ice sheet in this area of Africa proximal to the Carboniferous-Permian boundary, which may have sourced sediments to the Paraná Basin. An inferred distal southern source of glacial sediment for the Tepuel Basin argues for the presence of an ice sheet(s) in the Ellsworth Block of Antarctica towards the end of the glaciation history in Patagonia. These findings indicate an evolution during the Late Paleozoic Ice Age from proximally to extrabasinally sourced sediment reflecting continental-scale glaciation and subsequent drainage from the Windhoek Highlands, Ellsworth Block and an east African source in west-central Gondwana. Coincidence with a long-term fall in atmospheric pCO2 during the Pennsylvanian to a minimum across the Carboniferous-Permian boundary and a subsequent rise in the early Permian suggests a primary CO2-driver for deglaciation in the Paraná Basin. Additional boundary conditions including availability of moisture and paleogeography likely further contributed to the timing of nucleation, growth and demise of these Gondwanan glaciers. 

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