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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This content will become publicly available on February 1, 2027
Differentiating persistent and intermittent euxinia from the molecular derivatives of green sulfur bacteria carotenoids
Green sulfur bacteria biomarkers that indicate euxinia within the photic zone sometimes co-occur with evidence of contradictory depositional redox conditions, such as oxygen-requiring fossils or bioturbation. Intermittent euxinia may explain this apparent contradiction, and recent studies of modern environments show that green sulfur bacteria dwell in transiently euxinic settings. As a result, new approaches are needed to distinguish green sulfur bacteria biomarkers indicative of persistent versus intermittent euxina in ancient sedimentary samples, which this study addresses by investigating how the distribution of isorenieratene derivatives relates to depositional redox conditions. To accomplish this objective, this study focuses on two drill cores through the Upper Cretaceous Mowry Shale and the Eagle Ford Group. These drill cores are comparably thermally immature according to vitrinite reflectance data, and these formations in these cores capture a spectrum of depositional redox conditions according to multiple organic and inorganic proxies, including newly acquired iron speciation and kerogen organic sulfur data. The results presented here reveal that higher molecular weight diagenetic products of isorenieratene are preferentially preserved under persistent euxinia compared to intermittently euxinic intervals that contain isorenieratene derivatives that are shifted to lower molecular weights. Further, the total inventory of aromatic carotenoid diagenetic products contains features that can be used to identify green sulfur bacteria biomarkers from reworked petrogenic sources. Accordingly, the diagenetic fate of isorenieratene and the distribution of its diagenetic products distinguish persistent versus intermittent euxinia, which can be used to sharpen our evaluation of euxinia in the geologic record.
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- Award ID(s):
- 2143164
- PAR ID:
- 10679094
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Geochimica et Cosmochimica Acta
- Volume:
- 415
- Issue:
- C
- ISSN:
- 0016-7037
- Page Range / eLocation ID:
- 130-145
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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