Persistent Euxinia Research Articles

Variable local basin hydrography and productivity control the uranium isotope paleoredox proxy in anoxic black shales

Geochemical proxies—such as the isotopic compositions and abundances of redox-sensitive metals, organic biomarkers, and sedimentological indicators—can be used qualitatively and quantitatively to reconstruct marine redox landscapes through Earth history. Isotopic proxies with residence times longer than ocean mixing times, including uranium (238U/235U, commonly denoted as δ238U), are a promising but still developing approach to constrain global changes in redox conditions. Our current understanding of the controls on δ238U variability and associated isotopic fractionations is limited, complicating the interpretation of δ238U records through Earth history. With these gaps in mind, we investigate the major controls on the expression of uranium (U) isotope fractionation within two basins of the Miocene Monterey Formation (ca. 18–6 Ma) that represent contemporaneous deposition under different environmental conditions. Our finding that the isotopic offset in the productive and anoxic Santa Barbara Basin is similar to that in modern euxinic settings suggests that highly productive settings without persistent euxinia can also exert significant leverage on seawater δ238U. Distinct patterns in U concentrations and δ238U between basins demonstrate that local depositional controls can impart a strong influence on the U isotope offset in reducing settings, as has been observed in modern sediment datasets. High productivity and low sedimentation rates are predicted to result in a diagnostic inverse relationship between U enrichment and δ238U, which can partially explain the overall weak negative correlation between [U] and δ238U in the distal Naples Beach section in the Santa Barbara Basin. In a core from a more restricted proximal setting in the San Joaquin Basin, we propose that changes in basin hydrography led to a potential relationship between [U] and δ238U. These interpretations are consistent with the characteristic depositional conditions interpreted independently for each basin (e.g., persistence of anoxia, productivity, sedimentation rates, phosphate content, and basin hydrography) and are supported by modeling results of U enrichment and isotope fractionation under these conditions. In particular, our results suggest that the isotope offset of U in reducing sinks varies and has done so over Earth history and in different paleogeographic locations as a result of local productivity and basin restriction. These variations indicate the need to consider these uncertainties in quantitative models of global redox conditions from δ238U records—and specifically in using δ238U to distinguish between euxinic and oxic redox states without considering other oxygen-depleted environments as part of a continuum of settings that can impact δ238U if spatially widespread. This study also highlights the utility of using different lithologies to evaluate global versus local controls on δ238U records as well as multi-proxy approaches to constrain ancient redox landscapes.

Enhanced Arctic-Tethys connectivity ended the Toarcian Oceanic Anoxic Event in NW Europe

AbstractThe Toarcian Oceanic Anoxic Event (T-OAE, c. 182 Ma) represents a major perturbation of the carbon cycle marked by widespread black shale deposition. Consequently, the onset of the T-OAE has been linked to the combined effects of global warming, high productivity, basin restriction and salinity stratification. However, the processes that led to termination of the event remain elusive. Here, we present palynological data from Arctic Siberia (Russia), the Viking Corridor (offshore Norway) and the Yorkshire Coast (UK), all spanning the upper Pliensbachian – upper Toarcian stages. Rather than a ‘dinoflagellate cyst black-out’, as recorded in T-OAE strata of NW Europe, both the Arctic and Viking Corridor records show high abundance and dinoflagellate diversity throughout the T-OAE interval as calibrated by C-isotope records. Significantly, in the Arctic Sea and Viking Corridor, numerous species of the Parvocysta and Phallocysta suites make their first appearance in the lower Toarcian Falciferum Zone much earlier than in Europe, where these key dinoflagellate species appeared suddenly during the Bifrons Zone. Our results indicate migrations of Arctic dinoflagellate species, driven by relative sea-level rise in the Viking Corridor and the establishment of a S-directed circulation from the Arctic Sea into the Tethys Ocean. The results support oceanographic models, but are at odds with some interpretations based on geochemical proxies. The migration of Arctic dinoflagellate species coincides with the end of the T-OAE and marks the arrival of oxygenated, low-salinity Arctic waters, triggering a regime change from persistent euxinia to more dynamic oxygen conditions.

Hypoxia in the Holocene Baltic Sea: Comparing modern versus past intervals using sedimentary trace metals

Anthropogenic nutrient input has caused a rapid expansion of bottom water hypoxia in the Baltic Sea over the past century. Two earlier intervals of widespread hypoxia, coinciding with the Holocene Thermal Maximum (HTMHI; 8–4 ka before present; BP) and the Medieval Climate Anomaly (MCAHI; ~1200–750 years BP), have been identified from Baltic Sea sediments. Here we present sediment records from two sites in the Baltic Sea, and compare the trace metal (As, Ba, Cd, Cu, Mo, Ni, Pb, Re, Sb, Tl, U, V, Zn) enrichments during all three hypoxic intervals. Distinct differences are observed between the intervals and the various elements, highlighting the much stronger perturbation of trace metal cycles during the modern hypoxic interval. Both Mo and U show a strong correlation with Corg and very high absolute concentrations, indicative of frequently euxinic bottom waters during hypoxic intervals. During the modern hypoxic interval (ModernHI) comparatively less Mo is sequestered relative to Corg than in earlier intervals. This suggests partial drawdown of the water column Mo inventory in the modern water column due to persistent euxinia and only partial replenishment of Mo through North Sea inflows. Molybdenum contents in modern sediments are likely also affected by the recent slowdown in input of Mo in association with deposition of Fe and Mn oxides. Strong enrichments of U in recent sediments confirm that the ModernHI is more intense than past intervals. These results suggest that U is a more reliable indicator for the intensity of bottom water deoxygenation in the Baltic Sea than Mo. Sedimentary Re enrichment commences under mildly reducing conditions, but this element is not further enriched under more reducing conditions. Enrichments of V are relatively minor for the MCAHI and ModernHI, possibly due to strong reservoir effects on V in the water column, indicating that V is unreliable as an indicator for the intensity of bottom water hypoxia in this setting. Furthermore, Ba profiles are strongly influenced by post-depositional remobilization throughout the Holocene. The strong relationship between Corg and Ni, Tl and particularly Cu suggests that these trace metals can be used to reconstruct the Corg flux into the sediments. Profiles of As, Sb and Cd and especially Pb and Zn are strongly influenced by anthropogenic pollution.

Evolution of oceanic molybdenum and uranium reservoir size around the Ediacaran–Cambrian transition: Evidence from western Zhejiang, South China

The “Cambrian explosion” is one of the most fascinating episodes of diversification in the history of life; however, its relationship to the oxygenation of the oceans and atmosphere around the Ediacaran–Cambrian transition is not fully understood. Marine inventories of redox-sensitive trace elements reflect the relative balance of oxidative weathering on land and deposition in anoxic water masses, and can be used to explore the evolution of oceanic and atmospheric redox conditions. For this study, we conducted a series of geochemical analyses on the upper Lantian, Piyuancun, and Hetang formations in the Chunye-1 well, part of the lower Yangtze Block in western Zhejiang. Iron speciation results indicate that the entire studied interval was deposited under anoxic conditions, with three intervals of persistent euxinia occurring in the uppermost Lantian Fm., the lower Hetang Formation (Fm.), and the upper Hetang Fm. Molybdenum (Mo) and uranium (U) contents and Mo/TOC and U/TOC ratios from the anoxic/euxinic intervals of the Chunye-1 well, combined with published data from the sections in the middle and upper Yangtze Block, suggest that the oceanic Mo reservoir declined consistently from the Ediacaran to Cambrian Stage 3, while the size of the oceanic U reservoir remained relatively constant. Both metals were depleted in the ocean in lower Cambrian Stage 4, before increasing markedly at the end of Stage 4. The lack of an apparent increase in the size of the marine Mo and U reservoir from the upper Ediacaran to Cambrian Stage 3 suggests that oxic water masses did not expand until Cambrian Stage 4. The increase in marine Mo and U availability in the upper Hetang Fm. may have been due to the expansion of oxic water masses in the oceans, associated with oxygenation of the atmosphere during Cambrian Stage 4. This expansion of oxic waters in the global ocean postdates the main phase of Cambrian diversification, suggesting that pervasive oxygenation of the ocean on a large scale was not the primary control on animal diversity following the Ediacaran–Cambrian transition.

Variable Eocene-Miocene sedimentation processes and bottom water redox conditions in the Central Arctic Ocean (IODP Expedition 302)

In 2004, Integrated Ocean Drilling Program Expedition 302 (Arctic Coring Expedition, ACEX) to the Lomonosov Ridge drilled the first Central Arctic Ocean sediment record reaching the uppermost Cretaceous (~ 430 m composite depth). While the Neogene part of the record is characterized by grayish–yellowish siliciclastic material, the Paleogene part is dominated by biosiliceous black shale-type sediments. The lithological transition between Paleogene and Neogene deposits was initially interpreted as a single sedimentological unconformity (hiatus) of ~ 26 Ma duration, separating Eocene from Miocene strata. More recently, however, continuous sedimentation on Lomonosov Ridge throughout the Cenozoic was proclaimed, questioning the existence of a hiatus. In this context, we studied the elemental and mineralogical sediment composition around the Paleogene–Neogene transition at high resolution to reconstruct variations in the depositional regime (e.g. wave/current activity, detrital provenance, and bottom water redox conditions). Already below the hiatus, mineralogical and geochemical proxies imply drastic changes in sediment provenance and/or weathering intensity in the hinterland, and point to the existence of another, earlier gap in the sediment record. The sediments directly overlying the hiatus (the Zebra interval) are characterized by pronounced and abrupt compositional changes that suggest repeated erosion and re-deposition of material. Regarding redox conditions, euxinic bottom waters prevailed at the Eocene Lomonosov Ridge, and became even more severe directly before the hiatus. With detrital sedimentation rates decreasing, authigenic trace metals were highly enriched in the sediment. This continuous authigenic trace metal enrichment under persistent euxinia implies that the Arctic trace metal pool was renewed continuously by water mass exchange with the world ocean, so the Eocene Arctic Ocean was not fully restricted. Above the hiatus, extreme positive Ce anomalies are clear signs of a periodically well-oxygenated water column, but redox conditions were highly variable during deposition of the Zebra interval. Significant Mn enrichments only occur above the Zebra interval, documenting the Miocene establishment of stable oxic conditions in the Arctic Ocean. In summary, extreme and abrupt changes in geochemistry and mineralogy across the studied sediment section do not suggest continuous sedimentation at the Lomonosov Ridge around the Eocene–Miocene transition, but imply repeated periods of very low sedimentation rates and/or erosion.

Reconstruction of paleo-redox conditions and early sulfur cycling during deposition of the Cryogenian Datangpo Formation in South China

In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (Fe HR/Fe T, Fe P/Fe HR and Fe T/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (Fe HR/Fe T > 0.38 and Fe P/Fe HR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (Fe HR/Fe T > 0.38 and Fe P/Fe HR ≈ 0.80) and oxic (Fe HR/Fe T < 0.38) intervals could have occurred. Furthermore, Fe T/Al ratios (Fe T/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ 34S Py values in the Mesoproterozoic deep ocean, more positive δ 34S Py values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.

A critical look at iron paleoredox proxies: New insights from modern euxinic marine basins

Enrichments in reactive iron occur under euxinic marine conditions, that is, where dissolved sulfide is present in the water column. These enrichments result primarily from the export of remobilized iron from the oxic shelf, which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments. Strongly elevated ratios of highly reactive iron to total iron (Fe HR/Fe T) and total iron to aluminum (Fe T/Al) and high degrees of pyritization (DOP) are each products of this enrichment process. These paleoredox proxies are among the most faithful recorders of ancient euxinia. Contrary to previous arguments, iron enrichment is decoupled from biogenic sediment inputs, but it does appear to be a uniquely euxinic phenomenon. In other words, we can rule out a major contribution from preferential physical transport of Fe HR-rich detrital sediment to the deep basin, which could also operate under oxic conditions. Furthermore, enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins. Elevated Fe T/Al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net Fe HR addition. These conclusions are supported by observations in the modern Black Sea, Orca Basin, and Effingham Inlet. Fe T/Al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration. However, this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism, resulting in only intermediate DOP values for euxinic sediments and Fe T/Al ratios that mimic the oxic shelf. Such dilution effects are well expressed in Black Sea basinal turbidites and rapidly accumulating muds on euxinic basin margins. Under conditions of persistent euxinia, varying extents of Fe HR enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation. The magnitude of enrichment is a function of the source (shelf) to sink (ocean basin) areal ratio, suggesting that iron proxies can also record ocean-scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia. For the first time, manganese data are interpreted in light of the redox shuttle model. As for the iron data, the Black Sea, Orca Basin, and Effingham Inlet show enrichments in total manganese in the deep euxinic basin, suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin. The Black Sea data reveal iron and manganese enrichment across the broad, deep euxinic basin, suggesting efficient lateral transport and deep-water mixing tied to the physical properties of the water column.