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It is clear from modern analogue studies that O2-deficient conditions favor preservation of organic matter (OM) in fine-grained sedimentary rocks (black shales). It is also clear that appreciable productivity and OM flux to the sediment are required to establish and maintain these conditions. However, debates regarding redox controls on OM accumulation in black shales have mainly focused on oxic versus anoxic conditions, and the implications of different anoxic redox states remain unexplored. Here, we present detailed multi-proxy sedimentary geochemical studies of major Paleozoic and Mesozoic North American black shale units to elucidate their depositional redox conditions. This is the first broad-scale study to use a consistent geochemical methodology and to incorporate data from Fe-speciation – presently the only redox proxy able to clearly distinguish anoxic depositional conditions as ferruginous (H2S-limited) or euxinic (H2S-replete, Fe-limited). These data are coupled with total organic carbon (TOC), programmed pyrolysis, and redox-sensitive trace element proxies, with almost all measurements analyzed using the same geochemical methodology. Consistent with expectations based on previous geochemical and paleontological/ichnological studies, these analyses demonstrate that the study units were almost exclusively deposited under anoxic bottom waters. These analyses also demonstrate that there is wide variance in the prevalence of euxinic versus ferruginous conditions, with many North American black shale units deposited under predominantly ferruginous or oscillatory conditions. TOC is significantly higher under euxinic bottom waters in analyses of both preserved (present day) TOC and reconstructed initial TOC values, although sediments deposited under both redox states do have economically viable TOC content. While this correlation does not reveal the mechanism behind higher organic enrichment in euxinic environments, which may be different in different basins, it does open new research avenues regarding resource exploration and the biogeochemistry of ancient reducing environments.
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Holocene Spatiotemporal Redox Variations in the Southern Baltic Sea
Low oxygen conditions in the modern Baltic Sea are exacerbated by human activities; however, anoxic conditions also prevailed naturally over the Holocene. Few studies have characterized the specific paleoredox conditions (manganous, ferruginous, euxinic) and their frequency in southern Baltic sub-basins during these ancient events. Here, we apply a suite of isotope systems (Fe, Mo, S) and associated elemental proxies (e.g., Fe speciation, Mn) to specifically define water column redox regimes through the Baltic Holocene in a sill-proximal to sill-distal transect (Lille Belt, Bornholm Basin, Landsort Deep) using samples collected during the Integrated Ocean Drilling Program Expedition 347. At the sill-proximal Lille Belt, there is evidence for anoxic manganous/ferruginous conditions for most of the cored interval following the transition from the Ancylus Lake to Littorina Sea but with no clear excursion to more reducing or euxinic conditions associated with the Holocene Thermal Maximum (HTM) or Medieval Climate Anomaly (MCA) events. At the sill-distal southern sub-basin, Bornholm Basin, a combination of Fe speciation, pore water Fe, and solid phase Mo concentration and isotope data point to manganous/ferruginous conditions during the Ancylus Lake-to-Littorina Sea transition and HTM but with only brief excursions to intermittently or weakly euxinic conditions during this interval. At the western Baltic Proper sub-basin, Landsort Deep, new Fe and S isotope data bolster previous Mo isotope records and Fe speciation evidence for two distinct anoxic periods but also suggest that sulfide accumulation beyond transient levels was largely restricted to the sediment-water interface. Ultimately, the combined data from all three locations indicate that Fe enrichments typically indicative of euxinia may be best explained by Fe deposition as oxides following events likely analogous to the periodic incursions of oxygenated North Sea waters observed today, with subsequent pyrite formation in sulfidic pore waters. Additionally, the Mo isotope data from multiple Baltic Sea southern basins argue against restricted and widespread euxinic conditions, as has been demonstrated in the Baltic Proper and Bothnian Sea during the HTM or MCA. Instead, similar to today, each past Baltic anoxic event is characterized by redox conditions that become progressively more reducing with increasing distance from the sill.
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- Award ID(s):
- 1923218
- PAR ID:
- 10251371
- Date Published:
- Journal Name:
- Frontiers in Earth Science
- Volume:
- 9
- ISSN:
- 2296-6463
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.3389/feart.2021.671401
