Euxinic Bottom Waters Research Articles

Seasonal euxinia in a coastal basin: Impact on sedimentary molybdenum enrichments and isotope signatures

Eutrophication and global warming are leading to increased deoxygenation of coastal waters worldwide. To predict future trajectories of oxygen loss, insight into the intensity and temporal dynamics of past coastal deoxygenation is essential. Here, we assess the use of sedimentary molybdenum (Mo) enrichments and isotopic signatures (δ98Mo) as redox proxies in sediments of a seasonally euxinic coastal basin (Scharendijke, Lake Grevelingen, the Netherlands). Strong drawdown of dissolved Mo (from ∼100 to ∼60 nmol L−1) was observed in the euxinic bottom waters from July to September in 2021, coinciding with sedimentary enrichment of Mo (with peak values up to 19 ppm). A mass balance for Mo indicates that both deposition of Mo in the form of particles and diffusion of dissolved Mo into the sediment account for this Mo enrichment. The δ98Mo composition of suspended matter in the euxinic waters (0.30 to −1.95 ‰) is in line with isotopic fractionation during formation of thiomolybdates, and removal of Mo by sulfur- and/or iron-rich particles. The δ98Mo composition of the bottom water increases from 2.42 to 3.16 ‰ throughout the euxinic period, thereby further supporting preferential uptake of light Mo isotopes during sulfidation in the water column and near the sediment-water interface. The exceptionally high sedimentation rate at this site (>13 cm yr−1) allows seasonal variations in sedimentary enrichments to be preserved in the sedimentary record. Notably, sediment δ98Mo values peak during the summer euxinic period, reaching 1.28 ‰ in 2021 and as high as 2.15 ‰ in 2020. The 2020 value is close to the mean ocean value of 2.3 ‰, implying that sediments overlain by seasonally and permanently euxinic bottom waters can record the same isotopic signatures for Mo. Further work is needed to determine the potential role of diagenesis in altering δ98Mo records on time scales of months to several years.

Seasonal euxinia in a coastal basin: Impact on sedimentary molybdenum enrichments and isotope signatures

Eutrophication and global warming are leading to increased deoxygenation of coastal waters worldwide. To predict future trajectories of oxygen loss, insight into the intensity and temporal dynamics of past coastal deoxygenation is essential. Here, we assess the use of sedimentary molybdenum (Mo) enrichments and isotopic signatures (δ98Mo) as redox proxies in sediments of a seasonally euxinic coastal basin (Scharendijke, Lake Grevelingen, the Netherlands). Strong drawdown of dissolved Mo (from ~100 to ~60 nmol L−1) was observed in the euxinic bottom waters from July to September in 2021, coinciding with sedimentary enrichment of Mo (with peak values up to 19 ppm). A mass balance for Mo indicates that both deposition of Mo in the form of particles and diffusion of dissolved Mo into the sediment account for this Mo enrichment. The δ98Mo composition of suspended matter in the euxinic waters (0.30 to −1.95 ‰) is in line with isotopic fractionation during formation of thiomolybdates, and removal of Mo by sulfur- and/or iron-rich particles. The δ98Mo composition of the bottom water increases from 2.42 to 3.16 ‰ throughout the euxinic period, thereby further supporting preferential uptake of light Mo isotopes during sulfidation in the water column and near the sediment-water interface. The high sedimentation rate at this site (>13 cm yr−1) allows seasonal variations in sedimentary enrichments to be preserved in the sedimentary record. Notably, sediment δ98Mo values peak during the summer euxinic period, reaching 1.28 ‰ in 2021 and as high as 2.15 ‰ in 2020. The 2020 value is close to the mean ocean value of 2.3 ‰, implying that sediments overlain by seasonal and permanently euxinic bottom waters can record the same isotopic signatures for Mo. Further work is needed to determine the potential role of diagenesis in altering δ98Mo records on time scales of months to several years.

Links between hydrographic restriction, redox conditions, and organic matter accumulation in the Early Cambrian intrashelf basin, South China

There was a strong relationship between paleo-oceanic conditions and organic matter accumulation during the critical period of the Early Cambrian. The Yangtze Platform in South China provides an opportunity to study this relationship, but the basin architecture and paleo-hydrographic dynamics remain poorly understood, which hinders one’s understanding of the evolution in oceanic redox state and its relationship to organic matter accumulation. To fill the knowledge gap, a newly obtained data set from the Lower Cambrian Niutitang Formation shales (Late Cambrian Stage 2-Stage 3) of the intrashelf basin is used. Results show that the molybdenum–uranium covariation, along with the abnormally low Mo contents and Mo/TOC ratios in the anoxic (ferruginous and euxinic) Niutitang shales of the intrashelf basin, indicate a hydrographic circulation that is moderately to strongly restricted. The hydrographic evolution at different stages, influencing redox conditions to a certain extent, in conjunction with variations in primary productivity, controls the enrichment of organic matter. In particular, the relatively low sea level during Interval I (Late Stage 2) resulted in weak connectivity between the intrashelf basin and open ocean; this, coupled with high primary productivity and enhanced chemical weathering, formed stable stratified water (euxinic bottom-water) conditions that were favorable for organic matter enrichment. In contrast, Interval II (Early–Middle Stage 3) and Interval III (Late Stage 3) involved less organic matter enrichment due to weakened restricted hydrographic circulation (Interval II) and oxic bottom-water conditions (Interval III). This study highlights how hydrodynamic processes affected the marine environment during the Early Cambrian and reveals that sluggish oceanic circulation combined with high primary productivity led to anomalous enrichment of organic matter. This may be a common feature of basins with restricted hydrographic circulation in deep time.

The relationship between total organic carbon and bottom water redox state in North American black shales

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.

Oceanic and atmospheric oxygenation during the late Ediacaran based on multiple isotope records from South China

The Neoproterozoic–Cambrian transition was a key period in Earth's history, particularly because changes in the oceanic redox environment were crucial to the Cambrian explosion of life. However, the redox state of the ocean during this transition is unclear. In this study, the carbonate strata of the Dengying Formation in Yunnan Province, South China, were subjected to δ98/95Mo, δ13C, 87Sr/86Sr, and trace element analyses. The low δ98/95Mo results (0‰ ∼ +2‰) of most samples indicate that a shallow-marine sedimentary environment dominated by low-O2 conditions during the late Ediacaran period (Dengying Formation), but a brief period of marine oxidation existed at this time, reflected by elevated δ98/95Mo values (+2.07‰ ∼ +2.43‰). At this time, δ13C values were increasing, which possibly indicate an increase in primary productivity and photosynthesis in shallow waters, causing oxidation of the shallow seawater. However, two anomalously high δ98/95Mo values (>2.65‰) could have resulted from additional isotope fractionation due to the upwelling of euxinic bottom waters abruptly. In addition, an increase in 87Sr/86Sr ratios lagged the δ13C and δ98/95Mo changes, suggesting that atmospheric changes appear to have lagged oceanic oxidation, but more evidence are needed to prove the relationship. The dynamic changes in the redox conditions of the shallow sea during deposition of the Dengying Formation provided favorable conditions for changes in the atmosphere and the Ediacaran biota.

A volatile sulfur sink aids in reconciling the sulfur isotope mass balance of closed basin lakes

Sedimentary rocks from the early Eocene Green River Formation comprise the largest known lacustrine oil shale deposits, contain remarkably well-preserved fossils, and provide a unique record of climate evolution across the Early Eocene Climate Optimum, a period of high atmospheric CO2. The depositional environment of these intermountain lakes spanned from relatively fresh and fluvially influenced to expanded and stratified saline closed basin lakes under the influence of the Laramide orogeny and alternating humid and arid climatic conditions. As the surface area of the lakes expanded, alkalinity and salinity increased, with depositional cycles that linked to evaporative cycles and marked by an increasing abundance of organic matter-rich shales (TOC > 10 wt%). Simultaneously, an intriguing 20 ‰ positive shift in the sulfur isotope composition of sulfide minerals and organic sulfur is observed. Given that this trend cannot be simply explained by a change in the source of sulfate delivered to the basin, the evolution of biogeochemical sulfur cycling and the balance of fluxes in response to basin evolution remain unresolved. Here, we combine the sulfur isotope compositions of pyrite, organic sulfur, and carbonate-associated sulfate and molecular proxies of euxinia in samples from the Uinta basin's depocenter. We find that organic matter-rich sediments reflect deposition in a stratified water column with enhanced burial of pyrite and sulfurized organic matter, while organic-lean facies present evidence of, at least transiently, euxinic conditions reaching the photic zone during arid conditions presumably because of evaporation. As the lake became both saline-stratified and euxinic, we observe that δ34S values of all measured sulfur-bearing sedimentary proxies increase and evolve along a 1:1 line, a trend independent of facies that we interpret as reflecting a sulfate-limited system despite saline conditions. The isotopic mass balance of sulfur fluxes implies the existence of a sink of sulfur depleted in 34S that is spatially decoupled from burial in the depocenter. Modeling sulfur biogeochemical processes in a saline stratified lake system allows us to estimate that at least 50 % of the sulfur entering the lake could have been lost from the upper part of the euxinic water column where the fractionation factor imparted by microbial sulfate reduction is expressed. We propose that the overall isotopic enrichment of the system was caused by H2S degassing during arid climate intervals, presumably enhanced by transient water column mixing events. Further, episodic intrusion of euxinic bottom waters into the upper part of the water column might have triggered mass fish and plankton mortality, consequently facilitating the formation of these exceptionally fossiliferous and organic matter-rich rocks. Our study finds that volatile outgassing may be an underappreciated mechanism for the sulfur mass balance of stratified lacustrine systems.

Extremely high resolution XRF core scanning reveals the Early Triassic depositional history of the Montney Formation in northeastern British Columbia, Canada

The Montney Formation is a laterally extensive, fine-grained sedimentary unit in western Alberta and northeastern British Columbia, and a major target of hydrocarbon exploration. It also retains a complete record of the Early Triassic epoch, a time when the biosphere was recovering from the effects of the end-Permian mass extinction. An industry well provides a full-diameter core of the complete distal Montney Formation in northeastern British Columbia (over 350 m thick), with stratigraphic age control provided by conodont biostratigraphy and regional correlations. For this study, the core was scanned using an ITRAX X-ray fluorescence spectrometer, at centimeter-scale resolution. The resulting dataset (over 37,000 individual measurements) provides an extremely high level of resolution for a deep-time geochemical study. While the data generated by this instrument are semiquantitative, they can be calibrated by correlating them with more conventional ICP-MS and XRF measurements of select samples. Using this method, we assessed the reliability of each of the elemental data series, and where possible converted them to quantitative geochemical measurements. These calibrated measurements serve as the basis for our detailed reconstruction of the Montney Formation's depositional history.The distal Montney depositional basin, including the location of the c-65-F core, was euxinic immediately following the end-Permian mass extinction, and accumulated sediments from the rapidly eroding margin of western North America. Conditions stabilized somewhat in the Dienerian, with oxic bottom water and a trend toward more compositionally mature sediment, but conditions of widespread euxinia and rapid erosion of the North American craton recurred in the early Smithian, earlier than this global crisis has been recognized elsewhere. Above the middle-upper Montney sequence boundary, in the overlying Spathian succession, local effects predominate. Coastal upwelling resumed in the basal Spathian, though the Montney depositional basin was soon cut off from the global ocean by uplift of the Yukon-Tanana arc bounding the basin to the west. Restricted conditions, with euxinic bottom water, were punctuated by oxic intervals, when rising sea level allowed the basin to freely exchange water with the open ocean. Intervals of restriction became progressively less acute in the upper Spathian.

Degradation and accumulation of organic matter in euxinic surface sediments

The impact of oxygen on the preservation of organic matter in marine surface sediments is still controversial. We revisited this long-standing debate by determining the burial efficiency of sedimentary organic matter in the Black Sea, the largest anoxic and euxinic basin in the modern ocean. Surface sediments were sampled in the Danube paleodelta on the northwestern margin of the Black Sea at 420–1550 m water depth. Steady-state modeling of solid species (particulate organic carbon and nitrogen) and solutes (ammonium, sulfate, and total alkalinity) in sediments was performed to quantify rates of mass accumulation, particulate organic matter (POM) degradation, and POM burial. We develop a novel analytical model to quantify these rates applying an inverse modelling approach to down core data accounting for molecular diffusion, sediment burial and compaction. Our model results indicate that 56.7 ± 6.6 % of the particulate organic matter deposited in the study area is not degraded in surface sediments but accumulates below 10 cm sediment depth. This burial efficiency is substantially higher than those previously derived for seafloor areas underlying oxygenated bottom waters. Hence, our study confirms previous studies showing that euxinic bottom water conditions promote the preservation of particulate organic matter in marine sediments.

Nitrogen isotopes and geochemistry of the basal Datangpo Formation: Contrasting redox conditions in the upper and lower water columns during the Cryogenian interglaciation period

The late Neoproterozoic witnessed series of remarkable geological evolutions, including the Sturtian and Marinoan glaciation events during the Cryogenian. A stratified oceanic redox structure has been proposed for this period, and the dynamics of the deep water redox conditions have been well illustrated by trace metals and their isotopes. However, variations in the redox conditions of the upper water column have received much less attention. Sedimentary nitrogen isotopes (δ15N) are critical for reconstructing the redox conditions in the upper water columns of ancient oceans. Existing research on the N cycle during the Cryogenian period is scarce, and the majority of studied samples were collected from shallow and medium water depth facies. To address this paucity of studies, we conducted a high-resolution N isotope study in combination with Fe speciation and Mo concentration data from two deep-water sections of black shales in the basal Datangpo Formation in the Nanhua Basin, a typical organic-rich stratum deposited during the Cryogenian interglaciation period. While the trace metal proxies suggest a fluctuating euxinic–ferruginous bottom water column for the lower interval and a stable euxinic bottom water column for the upper interval, the redox conditions of the upper water column were relatively stable, as indicated by minimal changes in the recorded δ15N values. Furthermore, the δ15N values of black shales in the basal Datangpo Formation of the Nanhua Basin have a limited range (3.1‰ − 5.8‰, average of 4.3‰, standard deviation (SD) = 0.5‰, n = 104) and show no water-depth gradient, indicating the presence of a relatively large and stable nitrate reservoir and a deep redox chemocline in the Nanhua Basin. The characteristic of the nitrate reservoir reflected by these δ15N signals can be roughly analogized to the global interglacial ocean, although only the counterpart northeast Svalbard can be used for comparison. Therefore, the nitrate availability in the marine water column may have had little effect on animal radiation during the Cryogenian interglacial period. These findings help to clarify the N cycle in the Cryogenian Nanhua Basin and shed light on its significance on bioevolution.

Uranium and molybdenum isotope evidence for globally extensive marine euxinia on continental margins and in epicontinental seas during the Devonian-Carboniferous Hangenberg Crisis

The end-Devonian Hangenberg Crisis was one of the biggest Phanerozoic mass extinctions. However, the mechanism(s) that triggered this event is still debated. In this study, multiple geochemical paleoredox proxies (redox-sensitive trace metals [e.g., Mo, U, Re, V] and isotope systems [Mo, U, S, C]) were applied to the Exshaw Formation black shales to infer ocean redox conditions during the Hangenberg Crisis. The measured δ13Corg values generally decrease upsection in the Exshaw Formation. The Exshaw black shales have increasing maturity levels from east to west in the Western Canada Sedimentary Basin. Large sulfur isotope fractionations (–15‰ to 65‰) between original seawater sulfate and pyrite is best explained by microbial sulfate reduction during deposition and early diagenesis rather than thermochemical sulfate reduction. Precise Re-Os ages previously reported for the Exshaw Formation suggest that metal geochemical signatures in these shales, including overmature shales, were minimally affected by hydrocarbon maturation and reflected depositional conditions. Both Sr/Ba and TS/TOC ratios (the latter only from immature shales affected minimally by hydrocarbon generation) suggest predominantly brackish and marine settings with significant water exchange between the basin and open ocean. The TOC contents, redox-sensitive trace metal concentrations (Mo, U, Re), and Fe speciation indicate local bottom waters ranged from suboxic (with sulfidic pore waters) to euxinic. The authigenic δ98Mo and δ238U values for the Exshaw shales range from 0.3‰ to 1.1‰, and from –0.23‰ to 0.39‰, respectively. The δ98Mo of the Exshaw Formation may have been offset to lower values than coeval seawater because of a local particulate Fe-Mn shuttle and/or local weakly euxinic bottom waters. Two different correlation patterns (positive correlation and no correlation) of δ238U and U enrichment factors (EF) were observed for Exshaw black shales deposited from locally euxinic bottom waters. The positive correlation group samples (−0.13‰ to 0.23‰) suggest U isotope fractionations (0.4‰ to 0.8‰) between sediments and seawater like those observed in modern euxinic basins. Higher δ238U values (>0.2‰) in the no correlation group suggest even larger U isotope offsets (0.8–1.2‰) from seawater, possibly associated with removal of U into organic floccule layers during deposition. Applying the above Mo and U isotope fractionations to the Exshaw shales, global seawater δ98Mo and δ238U at the Devonian-Carboniferous boundary (DCB) may have been in the range of 1.4‰ to 1.9‰ and −0.9‰ to −0.5‰, respectively. A Mo and U isotope mass balance model suggests a large areal extent of euxinic seafloor (6–10%) at the DCB, which could be pervasive along continental margins and in epicontinental seas during transgression. Therefore, our data support expanded ocean euxinia at the DCB as an important contributor to the Hangenberg Crisis.

Organic Geochemistry of Carbonate Rocks, Silicites and Black Shales of the Vendian (Ediacaran) Khatyspyt Formation, Northeastern Siberia

Abstract —The paper presents the results of the study of organic geochemistry of carbonate rocks, silicites, and calcareous mudstones of the Vendian (Ediacaran) Khatyspyt Formation in the northeast of the Siberian Platform. The distribution of dispersed organic matter (OM) is shown to be uneven. The formation comprises carbonate-dominated intervals depleted in OM, with total organic carbon content (TOC) < 0.1%, or weakly enriched in OM (TOC up to 0.4%), interstratified with carbonate-shale, carbonate-shale-siliceous, carbonate-siliceous and siliceous intervals enriched in OM (TOC up to 1–4%). There is also a thin-layered calcareous mudstones anomalously enriched in OM (black shales with TOC at 10%) cropping out in the Khorbusuonka River valley (unit thickness 10 cm). The redox conditions in the water column varied during deposition of the Khatyspyt Formation. Certain intervals characterize a stratified water column and euxinic bottom water conditions. During the study, the assessment was conducted of the OM catagenesis and the generative potential of the Khatyspyt Formation. Based on the results of geochemical study and the synthesis of information on the geological structure of sedimentary succession in the northeastern Siberian Platform, the Khatyspyt Formation has been evaluated as one of the hydrocarbon sources for the territory.

Protracted oxygenation across the Cambrian-Ordovician transition: A key initiator of the Great Ordovician Biodiversification Event?

Fluctuations in marine oxygen concentrations have been invoked as a primary driver for changes in biodiversity throughout Earth history. Expansions in reducing marine conditions are commonly invoked as key causal mechanisms for mass extinctions, while increases in marine oxygenation are becoming an increasingly common causal mechanism invoked for biodiversification events. Here we utilize a multiproxy approach to constrain local and global marine paleoredox conditions throughout the late Cambrian-Early Ordovician from two drill core successions in Baltoscandia. Local paleoredox proxies such as manganese concentrations and iron speciation reveal that both sites in the Baltic paleobasin had persistently anoxic and predominantly euxinic (anoxic and sulfidic) bottom water conditions throughout the study interval. Corresponding trace metal datasets indicate nuanced contraction and expansion of global anoxic and euxinic conditions along continental margins during the late Cambrian-Early Ordovician. Lastly, thallium isotope data from these locally reducing sections suggest a global expansion of oxygenated shelf and deeper marine environments from the late Cambrian into the Early Ordovician. This evidence for increasingly oxic marine environments coincides with increases in burrowing depth and tiering in marine animals, as well as diversification of body fossils throughout this ~8-million-year interval. The collective geochemical datasets provide some of the first direct paleoredox evidence for an increase in marine oxygen concentrations as a key mechanism for the Ordovician radiation of marine life.

Episodic ventilation of euxinic bottom waters triggers the formation of black shale-hosted Mn carbonate deposits

Many manganese (Mn) carbonate deposits over geologic history are often closely associated with black shales. However, the mechanism(s) by which the Mn entered the sediments remains controversial because on one hand oxygenated waters are required for primary Mn(IV) oxide formation but on the other hand black shales generally form under reducing conditions. China hosts some of the world’s largest black shale-hosted Mn deposits, for example, the Carboniferous Ortokarnash and Malkantu Mn deposits in the Malkansu region, offering a good opportunity to revisit the genesis of black shale-hosted Mn carbonate deposits. Here, we present the first coupled, systematic paleoredox and hydrographic reconstruction of those deposits with the aim of elucidating the redox-state of the depositional basin at the time of their initial deposition. The Mn ore beds in this region are hosted within laminated, organic-rich mudstones (i.e., black shales) reflective of a relatively deep-water depositional environment. The Mn ores are comprised of the Mn(II) carbonate minerals (rhodochrosite and Ca-rhodochrosite), with minor alabandite, pyrite, and monazite. Multiple independent lines of evidence, including positive shale-normalized Ce anomalies (average 3.0), negative δ13CVPDB values (average −11.55 ‰), and negative δ98MoNIST+0.25 values (average −1.07 ‰), indicate that the Mn(II) carbonate ores were formed during diagenesis via the coupled oxidation of organic matter and reduction of Mn(IV) oxides originally deposited from an oxygenated water column. However, in apparent contradiction, highly reactive iron to total iron (FeHR/FeT; average 0.66) and pyrite iron to highly reactive iron (FePy/FeHR; average 0.71) ratios, combined with a high abundance of small framboidal pyrites (mean diameter ∼5 μm) with narrow size ranges (standard deviations <2 μm), suggest that the associated black shales were deposited in euxinic (H2S-bearing) bottom waters. Euxinia resulted from sluggish water mass circulation, with sedimentary Mo/TOC ratios indicating a relatively strong hydrologic restriction. During this stage, dissolved Mn(II) would have accumulated in euxinic waters but not become permanently fixed into sediments, as indicated by higher degrees of enrichment for Mo over U and lower Mo isotope values than coeval seawater recorded in the black shales. These reveal an active Mn(IV) oxide shuttle across a redox-stratified water column. Combined, the Mn ore intervals document sharp benthic oxygenation of euxinic bottom waters, a process that might be induced by the periodic incursions of oxic seawater associated with eustatic sea level rises. This model is supported by the Mo isotopic characteristics of the Mn carbonate ores, which indicate original Mn oxide precipitation from an overlying water with Mo isotopic composition close to coeval open seawater (minimum δ98MoNIST+0.25 of 1.9 ‰). In contrast to the generalized “bathtub ring” model envisaging that the black shale-hosted Mn deposits were formed at shallow basin margins, our results highlight that they were more likely formed by in-situ ventilation of anoxic (especially euxinic) deep waters of basin center settings. In this regard, we suggest that the ventilation model better explains the close association of Mn carbonate ores with black shales, and has profound implications for understanding the paleoredox framework of otherwise Mn-rich black shale successions.

Organic molecular evidence in the ∼1.40 Ga Xiamaling Formation black shales in North China Craton for biological diversity and paleoenvironment of mid-Proterozoic ocean

Indigenous hydrocarbon biomarkers in the black shales of the 1.40 billion-year-old Xiamaling Formation (XML) from the North China Craton were systematically analyzed to reveal the redox condition and biological community. These black shales are not only rich in organic matter, but also undergone an unexpectedly low thermal evolution process, both of which contribute to well-preserved indigenous hydrocarbons and promote the convincing discovery of the Precambrian biology. The combination of the absence or low concentrations of gammacerane, dibenzothiophene series and aryl isoprenoids, abundant rearranged hopanes, the occurrence of micro-ripples, and low level of redox-sensitive trace elements suggested shallow, low salinity and suboxic to anoxic conditions during the deposition period of XML. The absence of aryl isoprenoids as diagnostic biomarkers for green/purple sulfur bacteria strongly argued against the pervasively euxinic (sulphidic) bottom water in mid-Proterozoic ocean. The scenario of large hump unresolved complex mixture and abundant monomethyl alkanes as well as absent steranes may be derived from benthic microbial reworking processes for biolipids. Here the absence of saturated and aromatic steroids in the XML sediments suggested that eukaryotic algae have little ecological contribution to primitive biomass and/or are the result of heterotrophic reworking from benthic microbial mats. Abundant presence of hopanoid, tricyclic terpane and n-alkane in these samples supported the predominant contribution of (cyano) bacteria.

Multi‐elemental chemostratigraphy of Triassic mudstones in eastern Svalbard: Implications for source rock formation in front of the World’s largest delta plain

AbstractThe Triassic Boreal Ocean was a shallow epicontinental basin and the sink of the World's largest delta plain known to date. Nutrient and freshwater supply from this delta have been regarded as important causes for high productivity and water mass stratification, forming Middle Triassic oil‐prone source rocks. Recent studies attribute upwelling and a productivity‐induced oxygen minimum zone as important factors. A multi‐elemental chemostratigraphic study of a Spathian–Carnian mudstone succession exposed in eastern Svalbard was performed to investigate their formation. This includes 89 samples from three localities, from which 34 elements were acquired using combustion and X‐ray fluorescence analyses. The goal is to provide a correlation framework and infer the role of productivity, redox and water mass restriction on organic matter accumulation and source rock formation. These processes had major impact on the source potential. The Spathian Vendomdalen Member suggests deposition during intermittent benthic euxinia and low productivity, corresponding with a reported deep thermocline that obstructed upwelling. The lower Anisian lower–middle Muen Member shows negligible enrichment in redox‐sensitive elements but in situ phosphate nodules, consistent with developing upwelling and moderate productivity. The middle Anisian upper Muen Member formed during high productivity and phosphogenesis and is linked with basin‐wide upwelling. Productivity, phosphate and redox proxies are all strongly enriched in the upper Anisian–Ladinian Blanknuten Member. In the south‐western Barents Sea, the pro‐deltaic environment of the emerging Triassic Boreal Ocean delta system had terminated these conditions. The upper Ladinian upper Blanknuten Member formed within intermittent euxinic bottom waters due to the shallowing sea level. The Carnian Tschermakfjellet Formation marks the dominance of the prograding delta system and the end of Triassic oil‐prone source rock formation in Svalbard.

Molybdenum isotope-based redox deviation driven by continental margin euxinia during the early Cambrian

Oceanic redox changes may be a key environmental trigger for the “Cambrian explosion”. However, a hypothesized predominantly oxygenated early Cambrian ocean, inferred from high sedimentary molybdenum (Mo) isotope ratios, conflicts with other evidence for euxinic continental margins. Here, we demonstrate that seawater Mo isotope ratios like those of today’s predominantly well-oxygenated oceans can also occur in less oxygenated early Cambrian oceans. New and existing Mo isotope data from early Cambrian black shales in South China span a range of greater than 3‰, which can only be explained by multi-stage fractionation of Mo isotopes. The lowest Mo isotopes ratios likely reflect a Fe-Mn (oxyhydr)oxide shuttle that preferentially transferred the lighter Mo isotopes into weakly euxinic bottom waters where Fe-Mn (oxyhydr)oxide dissolution released isotopically light Mo that was then scavenged by organic matters and sulfide minerals. We use a novel isotope mass balance model to show that Fe-Mn (oxyhydr)oxide shuttle operating on euxinic continental margins would preferentially bury lighter-mass Mo isotopes to such an extent that early Cambrian seawater can become enriched in heavier Mo isotopes at levels comparable to modern seawater. Hence, widespread ocean oxygenation may not have occurred during the early Cambrian as previously thought. Based on this paradigm shift, reconsideration of sedimentary Mo isotope temporal trends suggests a stepwise and protracted oxidation of the oceans until the Late Devonian. Sporadic intervals with Mo isotope ratios spanning over 3‰ and often accompanied by dramatic change in biodiversity (e.g., Ediacaran-Cambrian and Permian-Triassic transitions) probably had euxinic continental margins. Links between fossil records and marine redox structures disclose the importance of spatiotemporal fluctuations in continental margin euxinia on biodiversity changes.

Mechanism and geological significance of anomalous negative δ13Ckerogen in the Lower Cambrian, NW Tarim Basin, China

The Lower Cambrian black strata with an anomalous negative excursion of carbon isotope in organic carbon are widely developed in many continents, contracting few attentions from scholars around the world. Based on the detailed investigations for the strata from the Xiaoerbulake and Shiairike outcrop sections located in the Aksu area, northwest Tarim Basin, multiple test and analysis methods including the total organic carbon (TOC), carbon isotope of kerogen (δ13Ckerogen), aryl isoprenoids and major/trace elements were systematically performed to reveal the mechanism and developmental model for the anomalous negative δ13Ckerogen. This anomalous negative excursion was caused by the coupling of paleoweathering and hydrothermal activities. Euxinic bottom water created by hydrothermal activities made the organic carbon (CO2 or HCO3-) from the decomposing organisms as the additional carbon source of phytoplankton photosynthesis, resulting in the development of 13C-depleted original organisms. Insufficient availability of essential nutrient (particularly Fe) caused by paleoweathering enhanced the low growth rate, resulting in the development of more 13C-depleted original organisms during the deposition of the organic-poor siliceous shales compared to that of the organic-rich shales. Besides, TOC was mainly affected by the dilution of high concentrations of hydrothermal SiO2, resulting in the organic-rich shales under weak hydrothermal conditions, while the organic-poor siliceous shales under strongly hydrothermal condition. Importantly, the production of anomalous negative δ13CKerogen triggered the occurrence of diagnostic biomarkers, aryl isoprenoids, indicating the photic zone euxinia. These contributes allow for potential application for deep petroleum exploration in the Lower Paleozoic in the Tarim Basin and insights for biological evolution.

Decoupled Cr, Mo, and U records of the Hongshuizhuang Formation, North China: Constraints on the Mesoproterozoic ocean redox

Multiple lines of evidence have suggested a mix of oxic, ferruginous, and euxinic conditions in the Mesoproterozoic oceans. It is important to constrain the relative proportions of these different redox environments because they might have governed the availability of some bio-essential elements and influenced the evolution of early eukaryotes. Here, we present a suite of geochemical data from the Mesoproterozoic Hongshuizhuang Formation, North China. Sampled shales were deposited under ferruginous to intermittently euxinic bottom waters, with heavy organic matter loading. Such environments are often characterized by co-enrichments of redox-sensitive trace elements. However, contrary to expectations, Cr contents of the Hongshuizhuang shales show almost no discernible authigenic enrichment relative to the upper continental crust, while the enrichments of U are muted as well. Molybdenum, in contrast to Cr and U, is moderately enriched. Since these elements respond differently to anoxia with or without sulfide, the global redox landscape can therefore be estimated. By integrating the budgets of Cr, Mo, and U, we infer that during the deposition of the Hongshuizhuang Formation, at least ~8% (up to ~46%) of seafloor was covered by anoxic waters, but euxinia accounted for only ~1–3% of the total seafloor area.

Deoxygenation dynamics on the western Nile deep-sea fan during sapropel S1 from seasonal to millennial timescales

Abstract. Ocean deoxygenation is a rising threat to marine ecosystems and food resources under present climate warming conditions. Organic-rich sapropel layers deposited in the Mediterranean Sea provide a natural laboratory to study the processes that have controlled changes in seawater oxygen levels in the recent geological past. Our study is based on three sediment cores spanning the last 10 000 years and located on a bathymetric transect offshore from the western distributaries of the Nile delta. These cores are partly to continuously laminated in the sections recording sapropel S1, which is indicative of bottom-water anoxia above the western Nile deep-sea fan. We used a combination of microfacies analyses and inorganic and organic geochemical measurements to reconstruct changes in oxygenation conditions at seasonal to millennial timescales. Millimetre-thick laminations are composed of detrital, biogenic and chemogenic sublayers reflecting seasonal successions of sedimentation. Dark layers reflect the deposition of summer floods and two types of light layers correspond to autumn plankton blooms and authigenic carbonates formed in the water column during spring–early summer, respectively. The isotopic signature of the authigenic carbonates suggests permanent anoxic to euxinic bottom waters resulting in high levels of anaerobic remineralization of organic matter and highlights their potential to reconstruct seawater chemistry at times when benthic fauna was absent. Ratios of major elements combined with biomarkers of terrestrial and marine organic matter and redox-sensitive compounds allow changes in terrigenous input, primary productivity and past deoxygenation dynamics on millennial timescales to be tracked. Rapid fluctuations of oxygenation conditions in the upper 700 m water depth occurred above the Nile deep-sea fan between 10 and 6.5 ka BP, while deeper cores recorded more stable anoxic conditions. Synchronous changes in terrigenous input, primary productivity and past oxygenation dynamics after 6.5 ka BP show that runoff-driven eutrophication played a central role in rapid oxygenation changes in the south-eastern Levantine Basin. These findings are further supported by other regional records and reveal time-transgressive changes in oxygenation state driven by rapid changes in primary productivity during a period of long-term deep-water stagnation.

Anatomy of the Major Baltic Inflow in 2014: Impact of manganese and iron shuttling on phosphorus and trace metals in the Gotland Basin, Baltic Sea

The deep basins of the Baltic Sea experienced dramatic climate- and eutrophication-induced redox changes between oxic and euxinic water column conditions. Irregularly appearing Major Baltic Inflows (MBI) carrying North Sea waters to the Baltic Sea are partly able to oxygenate euxinic bottom waters within several weeks. After an absence of ~10 years, an exceptional strong inflow event in December 2014 reached the Gotland Basin in early March 2015 providing the opportunity of detailed studies on the impact of fast redox shifts on elemental cycles. Here we report on P and trace metal (Co, Mo, U, V and W) dynamics in the water column, pore water, and sediment of the central Gotland Basin over a 4.5 year-long observation period. These time series record the entire redox development including the primary MBI-related oxygenation, the transitional development to anoxia before a second inflow pulse, and the final re-establishment of euxinia. Samples obtained in August 2012 represent the previous euxinic stagnation period not affected by MBI's since nearly a decade. Concentration measurements and a budget calculation suggest only a limited impact of the MBI on the water column P inventory and the corresponding eutrophication level of the Gotland Basin. This is due to insufficient Fe availability preventing efficient trapping of phosphate during water column oxygenation. In addition, the fast recovery of reducing conditions allowed only a short-term storage of deposited Mn–Fe–P mineral phases in the surface sediment. Due to pronounced scavenging by Mn oxides, substantial water column depletion occurred intermittently for V and W, but again, re-establishing reducing conditions favored Mn oxide dissolution and the release especially of W back into the water column. Mo and U were less affected by Mn and Fe shuttling and Mo even showed an increasing water column inventory due to replenishment by intruding North Sea waters. In contrast, the water column inventory of Co remained on an approx. 50% level about 4.5 years after the inflow suggesting a significant sedimentary burial of Co within the course of the inflow event. Although sedimentary Mn carbonate layers, which were commonly formed in concert with the frequent inflows between ~1960 and 1980, were missing or only weakly developed after the single inflow events in 1994, 2003, and 2014, dated short cores from the study area reveal clear Co and less pronounced V enrichments during the latter inflows. Because Mo, U and W are synchronously depleted compared with their normal sapropel levels, the combination of these trace metals and Co may help to identify past MBIs not reflected by Mn carbonate presence.