An official website of the United States government
The Toarcian Oceanic Anoxic Event (T-OAE; ~183 Mya) was a globally significant carbon-cycle perturbation linked to widespread deposition of organic-rich sediments, massive volcanic CO2release, marine faunal extinction, sea-level rise, a crisis in carbonate production related to ocean acidification, and elevated seawater temperatures. Despite recognition of the T-OAE as a potential analog for future ocean deoxygenation, current knowledge on the severity of global ocean anoxia is limited largely to studies of the trace element and isotopic composition of black shales, which are commonly affected by local processes. Here, we present the first carbonate-based uranium isotope (δ238U) record of the T-OAE from open marine platform limestones of the southeastern Tethys Ocean as a proxy for global seawater redox conditions. A significant negative δ238U excursion (~0.4‰) is recorded just prior to the onset of the negative carbon isotope excursion comprised within the T-OAE, followed by a long-lived recovery of δ238U values, thus confirming that the T-OAE represents a global expansion of marine anoxia. Using a Bayesian inverse isotopic mass balance model, we estimate that anoxic waters covered ~6 to 8% of the global seafloor during the peak of the T-OAE, which represents 28 to 38 times the extent of anoxia in the modern ocean. These data, combined with δ238U-based estimates of seafloor anoxic area for other CO2-driven Phanerozoic OAEs, suggest a common response of ocean anoxia to carbon release, thus improving prediction of future anthropogenically induced ocean deoxygenation.
more »
« less
Uranium Isotope Fractionation in Non‐sulfidic Anoxic Settings and the Global Uranium Isotope Mass Balance
Abstract Uranium isotopes (238U/235U) have been used widely over the last decade as a global proxy for marine redox conditions. The largest isotopic fractionations in the system occur during U reduction, removal, and burial. Applying this basic framework, global U isotope mass balance models have been used to predict the extent of ocean floor anoxia during key intervals throughout Earth's history. However, there are currently minimal constraints on the isotopic fractionation that occurs during reduction and burial in anoxic and iron‐rich (ferruginous) aquatic systems, despite the consensus that ferruginous conditions are thought to have been widespread through the majority of our planet's history. Here we provide the first exploration of δ238U values in natural ferruginous settings. We measured δ238U in sediments from two modern ferruginous lakes (Brownie Lake and Lake Pavin), the water column of Brownie Lake, and sedimentary rocks from the Silurian‐Devonian boundary that were deposited under ferruginous conditions. Additionally, we provide new δ238U data from core top sediments from anoxic but nonsulfidic settings in the Peru Margin oxygen minimum zone. We find that δ238U values from sediments deposited in all of these localities are highly variable but on average are indistinguishable from adjacent oxic sediments. This forces a reevaluation of the global U isotope mass balance and how U isotope values are used to reconstruct the evolution of the marine redox landscape.
more »
« less
- Award ID(s):
- 1660691
- PAR ID:
- 10375568
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Global Biogeochemical Cycles
- Volume:
- 34
- Issue:
- 8
- ISSN:
- 0886-6236
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The greenhouse gas methane (CH4) contributed to a warm climate that maintained liquid water and sustained Earth’s habitability in the Precambrian despite the faint young sun. The viability of methanogenesis (ME) in ferruginous environments, however, is debated, as iron reduction can potentially outcompete ME as a pathway of organic carbon remineralization (OCR). Here, we document that ME is a dominant OCR process in Brownie Lake, Minnesota (midwestern United States), which is a ferruginous (iron-rich, sulfate-poor) and meromictic (stratified with permanent anoxic bottom waters) system. We report ME accounting for ≥90% and >9% ± 7% of the anaerobic OCR in the water column and sediments, respectively, and an overall particulate organic carbon loading to CH4 conversion efficiency of ≥18% ± 7% in the anoxic zone of Brownie Lake. Our results, along with previous reports from ferruginous systems, suggest that even under low primary productivity in Precambrian oceans, the efficient conversion of organic carbon would have enabled marine CH4 to play a major role in early Earth’s biogeochemical evolution.more » « less
-
Abstract The Early Mississippian (Tournaisian) positive δ13C excursion (mid-Tournaisian carbon isotope excursion [TICE]) was one of the largest in the Phanerozoic, and the organic carbon (OC) burial associated with its development is hypothesized to have enhanced late Paleozoic cooling and glaciation. We tested the hypothesis that expanded ocean anoxia drove widespread OC burial using uranium isotopes (δ238U) of Lower Mississippian marine limestone as a global seawater redox proxy. The δ238U trends record a large Tournaisian negative excursion lasting ∼1 m.y. The lack of covariation between δ238U values and facies changes and proxies for local depositional and diagenetic influences suggests that the δ238U trends represent a global seawater redox signal. The negative δ238U excursion is coincident with the first TICE positive excursion, supporting the hypothesis that an expanded ocean anoxic event controlled OC burial. These results provide the first evidence from a global seawater redox proxy that an ocean anoxic event drove Tournaisian OC burial and controlled Early Mississippian cooling and glaciation. Uranium and carbon modeling results indicate that (1) there was an ∼6× increase in euxinic seafloor area, (2) OC burial was initially driven by expanded euxinia followed by expanded anoxic/suboxic conditions, and (3) OC burial mass was ∼4–17× larger than that sequestered during other major ocean anoxic events.more » « less
-
Redox-sensitive elements figure prominently in studies of the evolution of Earth’s surface redox state, including the first major rise in atmospheric O2, the Paleoproterozoic Great Oxidation Event. Most Precambrian rocks endured multistage tectonothermal histories, however, adding ambiguity to interpretation of their chemistry. Here, we apply U-Th-Pb isotope geochronology to the highly oxidized ~2.06 Ga Kuetsjärvi Volcanic Formation, Pechenga Greenstone Belt, Russia, to constrain the age and extent of U oxidation. By contrasting the relative mobility of U and Th using Pb isotopes, we find that complete to near-complete oxidation and removal of U occurred shortly after eruption. We argue that this likely indicates relatively high atmospheric O2, where oxidative weathering and alteration produced a global pulse of U to the oceans. Such a pulse could explain widespread shifts in the U-Th-Pb isotope character of mantle reservoirs at ~2 Ga, including a decrease in the232Th/238U ratio of the mid-ocean ridge basalt source and inception of the high-238U/204Pb (HIMU) source to ocean island basalts, underscoring the connections between the redox character of the Paleoproterozoic surface and deep Earth. Using207Pb-206Pb,238U-206Pb,235U-207Pb, and232Th-208Pb geochronology, ~2.06 Ga oxidative loss of U may be distinguished from reintroduction of U at ~1.8 Ga during regional metamorphism, as well as Pb loss during a Phanerozoic tectonothermal event. Our results therefore establish the complex history of redox-sensitive element behavior in the rocks, highlighting the fact that elemental abundances, by themselves, are unlikely to capture straightforward proxy information in rocks that have seen multistage geologic histories.more » « less
-
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.more » « less
