Anoxic Water Column Research Articles

Impact of Electron Acceptor Availability on Methane-Influenced Microorganisms in an Enrichment Culture Obtained From a Stratified Lake.

Methanotrophs are of major importance in limiting methane emissions from lakes. They are known to preferably inhabit the oxycline of stratified water columns, often assumed due to an intolerance to atmospheric oxygen concentrations, but little is known on the response of methanotrophs to different oxygen concentrations as well as their preference for different electron acceptors. In this study, we enriched a methanotroph of the Methylobacter genus from the oxycline and the anoxic water column of a stratified lake, which was also present in the oxic water column in the winter. We tested the response of this Methylobacter-dominated enrichment culture to different electron acceptors, i.e., oxygen, nitrate, sulfate, and humic substances, and found that, in contrast to earlier results with water column incubations, oxygen was the preferred electron acceptor, leading to methane oxidation rates of 45–72 pmol cell−1 day−1. Despite the general assumption of methanotrophs preferring microaerobic conditions, methane oxidation was most efficient under high oxygen concentrations (>600 μM). Low (<30 μM) oxygen concentrations still supported methane oxidation, but no methane oxidation was observed with trace oxygen concentrations (<9 μM) or under anoxic conditions. Remarkably, the presence of nitrate stimulated methane oxidation rates under oxic conditions, raising the methane oxidation rates by 50% when compared to oxic incubations with ammonium. Under anoxic conditions, no net methane consumption was observed; however, methanotroph abundances were two to three times higher in incubations with nitrate and sulfate compared to anoxic incubations with ammonium as the nitrogen source. Metagenomic sequencing revealed the absence of a complete denitrification pathway in the dominant methanotroph Methylobacter, but the most abundant methylotroph Methylotenera seemed capable of denitrification, which can possibly play a role in the enhanced methane oxidation rates under nitrate-rich conditions.

Marine redox variability from Baltica during extinction events in the latest Ordovician–early Silurian

It is well documented that Upper Ordovician and Silurian successions record multiple marine turnover events – including the second-largest mass extinction in the Phanerozoic – widespread glaciation, and multiple global carbon cycle perturbations. Whereas causal mechanisms for the Late Ordovician major mass extinction event involving climate, paleoceanographic variation, and δ13C records have been published, similar records remain poorly constrained for subsequent extinction events in the early Silurian. Here, we present new organic matter carbon isotope (δ13Corg) chemostratigraphy and corresponding paleoredox proxies (Fe speciation, [Mn, V, Mo], and pyrite sulfur isotopes) from two organic-rich drill core sections in Sweden and Latvia that span the upper Katian through lower Wenlock stages (446–431 Ma). Pyritized Fe and bulk sedimentary Mn concentrations from Upper Ordovician strata in southern Sweden suggest a local redox shift to more reducing conditions in the late Hirnantian, possibly including euxinic (anoxic and sulfidic water column) conditions that coincide with the second mass extinction pulse. The new high-resolution δ13Corg and δ34Spyr datasets from the late Aeronian (early Silurian) interval within both drill cores show positive excursions that are broadly coincident with the associated Sandvika and sedgwickii extinction events. Independently, Fe speciation and bulk sedimentary trace metal data from this late Aeronian interval record locally euxinic conditions in both the deep basinal (Sweden) and distal shelf (Latvia) settings before and during the late Aeronian positive δ13C excursion. This multiproxy paleoredox dataset provides the first direct evidence for local to regional expansion of reducing marine conditions coincident with this early Silurian (late Aeronian) biotic event and positive δ13C excursion. Additionally, new δ34Spyr values spanning the Llandovery/Wenlock boundary interval in the Latvia core show a positive excursion coincident with Fe speciation and trace metal enrichments that imply a local redox perturbation with intermittently euxinic bottom waters during the rising limb of the Ireviken positive δ13C excursion. The combination of these geochemical data for local- to regional-scale (more data required for global interpretations) changes in marine redox conditions with paleobiological records and evidence for eustatic sea-level rise indicate that environmental stresses related to an expansion of anoxic to euxinic conditions were a probable driver for several extinction events during the latest Ordovician–early Silurian.

Redox fluctuations, trace metal enrichment and phosphogenesis in the ~2.0 Ga Zaonega Formation

The ~2.0 Ga Zaonega Formation (ZF) holds one of the oldest phosphorites in the geologic record, reaching >15% P2O5. Understanding the depositional conditions that enabled sedimentary phosphorus enrichment in this unit will thus help us to interpret the significance of the temporal distribution of phosphorites in Earth’s early history. Here we use an array of major and trace element data to constrain the redox conditions in the water column and extent of basinal restriction during deposition of the ZF. We also present new selenium (Se) abundance and isotopic data to provide firmer constraints on fluctuations across high redox potentials, which might be critical for phosphogenesis. We find that Se isotope ratios shift over a range of ~3‰ in the ZF, with the earliest stratigraphically-resolved negative Se isotope excursion in the geologic record, implying at least temporarily suboxic waters in the basin. Furthermore, we find that redox-sensitive element (RSE) enrichments coincide with episodes of P enrichment, thereby implicating a common set of environmental controls on these processes. Together, our dataset implies deposition under a predominantly anoxic water column with periodic fluctuations to more oxidizing conditions because of connections to a large oxic reservoir containing Se oxyanions (and other RSE’s, as well as sulfate) in the open ocean. This is broadly consistent with the depositional setting of many modern and recent phosphorites, thereby tying these ancient deposits to a common depositional mechanism. In light of these data, we propose that the broader prevalence of phosphogenesis in the Paleoproterozoic Era was driven by growth of the seawater oxidant reservoir (namely sulfate), thus enabling diagenetic apatite precipitation in basins with high rates of export production, particularly by facilitating the activity of sulfide-oxidizing bacteria. This suggests that the muted authigenic P burial observed in marginal, marine siliciclastic sedimentary rocks during other intervals of the Precambrian was not merely a result of low dissolved P levels in the global deep ocean, but also was influenced by sulfate scarcity and strongly reducing bottom-water conditions.

Uranium reduction and isotopic fractionation in reducing sediments: Insights from reactive transport modeling

Uranium concentrations and isotopic ratios (238U/235U, denoted as δ238U) have been used to provide quantitative information about the degree of oxygenation and de-oxygenation of past oceans. The potential to constrain changes in global redox conditions, in contrast to many other proxies that reflect local conditions, is a particular strength of the uranium isotope approach. Because uranium reduction primarily occurs in sediments underlying anoxic water columns rather than in the anoxic water column itself, the removal of uranium in organic-rich shales is the largest lever on seawater δ238U. Accordingly, accumulation and isotopic fractionation are modulated by local variations in productivity, basin connectivity, sedimentation rate, and bottom-water redox conditions. To isolate the processes at the sediment-water interface that control δ238U and uranium accumulation in reducing sediments, we constructed a reactive transport model that couples biogeochemical reactions to diffusive transport and the burial of solutes and minerals.Using the model framework, we test the sensitivity of authigenic uranium isotopic fractionation and accumulation to oxygenation, permeability, sedimentation rate, organic carbon delivery, and basin restriction. Our results demonstrate that these external forcings produce diagnostic patterns in isotopic fractionation. Specifically, the model predicts that authigenic δ238U is sensitive to productivity because of the associated organic carbon burial rate. Moreover, our results suggest that the isotopic offset does not vary significantly due to changing bottom-water O2 concentrations, but the amount of accumulation does—a result that differs from previous estimates. Water column uranium reduction adds additional complexity to the ultimate δ238U value. The predictive patterns derived from model results can offer insight into local depositional conditions, such as sedimentation patterns. Collectively, these effects—including bottom-water redox conditions and related reducing sediments—alter the isotopic signature of the overlying water column according to the authigenic δ238U value and the diffusive fluxes arising from porewater concentration gradients. More broadly, this work provides important new constraints on the major controls on the δ238U of sediments while also supporting its use as a proxy for global marine redox conditions.

Methane gas emissions of the Black Sea—mapping from the Crimean continental margin to the Kerch Peninsula slope

This study focuses on gas bubble emissions across ~ 1800 km2 of the southeastern continental slope of the Crimean Peninsula in the Eastern Black Sea basin. In total, about 3500 gas emissions were mapped as so-called flares in single- and multibeam echosounder imaginary. Flares generally emanate from the seafloor, with a few exceptions, where water depths are less than 700 m, which represents the upper limit of the gas hydrate stability zone in this region. Methane in shallow sediments below 700 m is transferred to methane hydrate, and the migration of free gas into the water column is therefore inhibited in most cases. This study illustrates further that flare occurrence is linked to morpho-structural margin characteristics. Two morphologically different margin segments are distinguished, and flare distributions were found to relate to differing morphological structures along these segments. In the western province, where the upper continental margin is steep and incised by gullies, flares occur mainly along downslope-oriented ridge crests. In the eastern province, representing a part of the Don-Kuban paleo-fan, the slope is influenced by extensive mass wasting. Gas emissions in this area were mainly detected aligned along scarps of submarine landslides and related to sediment failures. Almost all flares disappear in the acoustic records of the water column below a water depth of ~ 100 m suggesting that the gas bubbles dissolve within the water body of the Black Sea and contribute to its methane inventory and the anoxic water column.

Phosphorus-cycle disturbances during the Late Devonian anoxic events

The Late Devonian was marked by repeated faunal crises and episodes of geographically widespread marine anoxia, and featured one of the ‘Big Five’ mass extinctions of the Phanerozoic Aeon during the Frasnian–Famennian transition. However, the processes responsible for causing the numerous anoxic events remain unclear. This study highlights the occurrence of disturbances to the phosphorus cycle during several Late Devonian crises by investigating sedimentary concentrations of the element (Ptot) as a tracer of nutrient influx, as well as its ratio with total organic carbon (TOC) to infer the recycling of the element from marine sediments. Increased TOC/Ptot ratios in the Frasnian–Famennian Lower and Upper Kellwasser horizons and upper Famennian Annulata and Hangenberg levels suggest that such nutrient recycling occurred across extensive areas of the marine shelf in Laurentia and both Rheic Ocean margins at those times, helping to sustain reducing conditions in those environments. Elevated Ptot values in the Upper Kellwasser, Annulata, and Hangenberg levels are consistent with an enhanced nutrient influx as the initial trigger for the anoxia. Correlation of phosphorus trends with other geochemical indicators of weathering/detrital influx (osmium-isotope, silicon/aluminum, and titanium/aluminium ratios) support a scenario in which terrestrial runoff provided these nutrients both to marine shelves and the oceanic inventory. Upwelling of oceanic deep-water bodies may have then brought the phosphorus to areas that had not featured major direct inputs of terrigenous material. The exception is the Lower Kellwasser Event, during which there was no increase in phosphorus delivery to marine areas and no evidence for terrestrial influx at the studied sections, invoking a different mechanism for the development of water-column anoxia. Clearly, the Late Devonian marine realm was unusually susceptible to becoming anoxic through various possible triggers, including nutrient influx from land and/or deep-water upwelling, and the recycling of phosphorus from newly deposited sediments.

Geochemical characterization of the Devonian-Mississippian Woodford Shale from the McAlister Cemetery Quarry, Criner Hills Uplift, Ardmore Basin, Oklahoma

Abstract It has been estimated that technically recoverable reserves from shales in the continental U.S. are believed to be approximately 24 billion barrels of oil (BBO) and 750 trillion cubic feet (Tcf) of gas. In Oklahoma the most important hydrocarbon source rock is the Woodford Shale, proposed to be the source of some 70% of the state's liquid hydrocarbon reserves. Such a regionally widespread source rock provides potential for both academic study and industrial opportunities. In this study representative samples of the Woodford Shale from the McAlister Quarry outcrop have been characterized by a variety of geochemical techniques. TOC values range from 0.07 to 15.6 wt% and, based on Rock-Eval Pyrolysis, most of the samples plot within the Type I/II kerogen range, with several low TOC samples plotting in the Type III kerogen range. TOC and biomarker parameters, suggests that two sections of the Upper Woodford are immature paleosols, having been subaerially exposed due to abrupt episodes of sea level fall during the Late Devonian. Evidence for these zones of paleoweathering includes highly depleted TOC, increased oxygen index (OI) values, loss of n-alkanes, decreases in the aryl isoprenoid ratio (AIR), sesquiterpenoids, cheilanthanes, hopanoids, and decreases in many of the polycyclic aromatic hydrocarbons (PAHs). The values of several paleoenvironmental proxies for samples immediately following the Frasnian-Famennian (F–F) Stage extinction boundary within the Upper Woodford suggests that a large influx of weathered terrigenous material occurred at that time. The presence of pyrogenic compounds implies that paleowildfires were widespread throughout the Middle and Late Devonian in the North American midcontinent. It is possible that these influxes of weathered terrestrial organic material stimulated algal blooms that led to the anoxic water column conditions often attributed to the F–F Stage extinction event. Investigation of the stratigraphic framework of these source rocks assists in evaluating their potential as hydrocarbon producers and/or unconventional reservoirs. Integration of geochemical data adds another powerful dimension to this approach. It has been proposed that the Woodford Shale was deposited during a 2nd order depositional sequence. The lower member represented the transgressive systems tract (TST), the Upper member the highstand systems tract (HST), and the Middle member bridging the transition between the two. Numerous 3rd order parasequences were also identified as being part of the overall 2nd order sequence and could be correlated to the Devonian sea level curve. The major objectives of the study were: While this study focuses locally on the McAlister Quarry samples, it is also of regional importance. The Woodford is a prolific source rock throughout the Anadarko Basin and has been the subject of extensive exploration and production efforts, particularly in the past decade with the development of horizontal drilling and hydrofracturing techniques. Continued investigation of the heterogeneity of the shale will greatly enhance the ability to predict more productive facies within the formation throughout the basin.

Biogeochemical and physical controls on methane fluxes from two ferruginous meromictic lakes.

Meromictic lakes with anoxic bottom waters often have active methane cycles whereby methane is generally produced biogenically under anoxic conditions and oxidized in oxic surface waters prior to reaching the atmosphere. Lakes that contain dissolved ferrous iron in their deep waters (i.e., ferruginous) are rare, but valuable, as geochemical analogues of the conditions that dominated the Earth's oceans during the Precambrian when interactions between the iron and methane cycles could have shaped the greenhouse regulation of the planet's climate. Here, we explored controls on the methane fluxes from Brownie Lake and Canyon Lake, two ferruginous meromictic lakes that contain similar concentrations (max.>1mM) of dissolved methane in their bottom waters. The order Methanobacteriales was the dominant methanogen detected in both lakes. At Brownie Lake, methanogen abundance, an increase in methane concentration with respect to depths closer to the sediment, and isotopic data suggest methanogenesis is an active process in the anoxic water column. At Canyon Lake, methanogenesis occurred primarily in the sediment. The most abundant aerobic methane-oxidizing bacteria present in both water columns were associated with the Gammaproteobacteria, with little evidence of anaerobic methane oxidizing organisms being present or active. Direct measurements at the surface revealed a methane flux from Brownie Lake that was two orders of magnitude greater than the flux from Canyon Lake. Comparison of measured versus calculated turbulent diffusive fluxes indicates that most of the methane flux at Brownie Lake was non-diffusive. Although the turbulent diffusive methane flux at Canyon Lake was attenuated by methane oxidizing bacteria, dissolved methane was detected in the epilimnion, suggestive of lateral transport of methane from littoral sediments. These results highlight the importance of direct measurements in estimating the total methane flux from water columns, and that non-diffusive transport of methane may be important to consider from other ferruginous systems.

Effects of eutrophication on sedimentary organic carbon cycling in five temperate lakes

Abstract. Even though human-induced eutrophication has severely impacted temperate lake ecosystems over the last centuries, the effects on total organic carbon (TOC) burial and mineralization are not well understood. We study these effects based on sedimentary records from the last 180 years in five Swiss lakes that differ in trophic state. We compare changes in TOC content and modeled TOC accumulation rates through time to historical data on algae blooms, water column anoxia, wastewater treatment, artificial lake ventilation, and water column phosphorus (P) concentrations. We furthermore investigate the effects of eutrophication on rates of microbial TOC mineralization and vertical distributions of microbial respiration reactions in sediments. Our results indicate that the history of eutrophication is well recorded in the sedimentary record. Overall, eutrophic lakes have higher TOC burial and accumulation rates, and subsurface peaks in TOC coincide with past periods of elevated P concentrations in lake water. Sediments of eutrophic lakes, moreover, have higher rates of total respiration and higher contributions of methanogenesis to total respiration. However, we found strong overlaps in the distributions of respiration reactions involving different electron acceptors in all lakes regardless of lake trophic state. Moreover, even though water column P concentrations have been reduced by ∼ 50 %–90 % since the period of peak eutrophication in the 1970s, TOC burial and accumulation rates have only decreased significantly, by ∼ 20 % and 25 %, in two of the five lakes. Hereby there is no clear relationship between the magnitude of the P concentration decrease and the change in TOC burial and accumulation rate. Instead, data from one eutrophic lake suggest that artificial ventilation, which has been used to prevent water column anoxia in this lake for 35 years, may help sustain high rates of TOC burial and accumulation in sediments despite water column P concentrations being strongly reduced. Our study provides novel insights into the influence of human activities in lakes and lake watersheds on lake sediments as carbon sinks and habitats for diverse microbial respiration processes.

Formation Mechanism and Numerical Model of Quartz in Fine-Grained Organic-Rich Shales: A Case Study of Wufeng and Longmaxi Formations in Western Hubei Province, South China

The difference in quartz types in shales not only affects the porosity and permeability of the rocks, but also reflects the difference in the sedimentary environments. We established the formation mechanism and numerical model of quartz in shales of Wufeng and Longmaxi formations in the Wangjiawan Section, South China, based on thin-section studies using SEM (scanning electron microscope), SEM-CL (cathodoluminescence), XRD (X-ray diffraction) and geochemical analyses. There are two types of quartz in the shales: detrital quartz and authigenic quartz. Detrital quartz is mostly silt-size, typically ranging from 10 to 60 μm in size and subangular to angular monocrystal in shape, and brighter than authigenic quartz by CL intensity; authigenic quartz is present in two phases in shape: grain overgrowths and crystallite grains. Overgrowth surfaces are subhedral. Crystallite grains are typically less than 10 μm in size, euhedral or subhedral monocrystal in shape. Authigenic quartz can be subdivided into biogenic quartz and clay mineral transformed quartz according to the source of silicon. In the numerical model, the content of detrital quartz is relatively consistent (20%); the content of biogenic quartz ranges from 40% to 70%, with a sharp fall (0–30%) in the Guanyinqiao mudstone. During the Katian, a lower anoxic and dense water column make the dissolution of biogenic silica well preserved. Biogenic quartz is the major contributor to the sediment. During the early Hirnantian interval, due to the drop of sea level and the oxygenation of seafloor, the sediment is mainly composed of clay transformed quartz and detrital quartz. During the latest Hirnatian and Rhuddanian, rapid sea level rise and anoxic ocean enhance the preservation of the biogenic silica, thereby biogenic quartz re-emerges as the major contributors to the sediment. Authigenic crystallite grains and grain overgrowths have filled in primary pore space and have decreased the interparticle porosity, however, as a rigid framework, they can suppress compaction and maintain the internal pore structure. The formation of authigenic quartz results in the increase of total quartz, which fortifies the brittleness of rocks and is beneficial to the development of shale gas.

Linking the progressive expansion of reducing conditions to a stepwise mass extinction event in the late Silurian oceans

AbstractThe late Ludlow Lau Event was a severe biotic crisis in the Silurian, characterized by resurgent microbial facies and faunal turnover rates otherwise only documented during the “big five” mass extinctions. This asynchronous late Silurian marine extinction event preceded an associated positive carbon isotope excursion (CIE), the Lau CIE, although a mechanism for this temporal offset remains poorly constrained. Here, we report thallium isotope data from locally reducing late Ludlow strata within the Baltic Basin to document the earliest onset of global marine deoxygenation. The initial expansion of anoxia coincided with the onset of the extinction and therefore preceded the Lau CIE. Additionally, sulfur isotope data record a large positive excursion parallel to the Lau CIE, interpreted to indicate an increase in pyrite burial associated with the widely documented CIE. This suggests a possible global expansion of euxinia (anoxic and sulfidic water column) following deoxygenation. These data are the most direct proxy evidence of paleoredox conditions linking the known extinction to the Lau CIE through the progressive expansion of anoxia, and most likely euxinia, across portions of the late Silurian oceans.

Controls on organic matter accumulation on the early-Cambrian western Yangtze Platform, South China

Abstract The origin of widespread organic-rich shales on the early Cambrian Yangtze Platform of Nanhua Basin (South China) has been attributed to high primary productivity. To test this hypothesis, we generated multiple paleoproductivity (OCAR and PAR), paleoredox (Corg/P ratios), upwelling/restriction (CoEF × MnEF, Co (ppm) × Mn (%), Mo/TOC, and Cd/Mo ratios), and terrigenous flux proxies (Al and unreactive Fe (FeU)) for the lower Cambrian Niutitang Formation in the outer-shelf Jinsha section, which records a typical transition from the organic-rich black shales to overlying organic-lean mudstones or siltstones. These new data were integrated with published paleoredox proxies (iron speciation and redox-sensitive trace metals) for the same section. Our results suggest that the organic-rich (TOC = 4.6 ± 1.8%) lower member (LM; 0–37 m) of the Niutitang Formation records ferruginous conditions, high productivity levels, and low siliciclastic fluxes, and that the organic-poor (TOC = 0.1 ± 0.1%) upper member (UM; 37–329 m) was characterized by dominantly oxic conditions, declining productivity levels, and high siliciclastic fluxes. Our results suggest a redox shift from ferruginous to oxic conditions and enhanced terrigenous fluxes in response to falling sea level from the LM to the UM. Secular variations in primary productivity and redox conditions are strongly correlated, which is consistent with a positive feedback: high primary productivity led to increasing water-column anoxia, which enhanced organic P recycling, stimulating further productivity. Variations in primary productivity may reflect variable upwelling intensity in a semi-restricted shelf setting linked to sea-level changes. Taken together, these findings suggest that a combination of primary productivity, redox conditions, and terrigenous fluxes driven by sea-level changes played a key role in organic matter accumulation on the early-Cambrian western Yangtze Platform.

Geochemical characteristics of Early Cretaceous marine oil shale from the Changshe Mountain area in the northern Qiangtang Basin, Tibet: Implications for palaeoweathering, provenance, tectonic setting, and organic matter accumulation

The Early Cretaceous Shengli River–Changshe Mountain marine oil shale belt, located in the northern Qiangtang Basin, Tibet, is estimated to be the largest marine oil shale resource in China. However, its palaeoweathering, provenance, and tectonic setting during the depositional history have received little interest. In this paper, 19 outcrop marine oil shale samples from the ChangsheMountain (CSM) area were studied to investigate the provenance, palaeoclimate, palaeoweathering, and tectonic setting during the marine oil shale deposition. The total organic carbon and organic sulphur contents of the CSM oil shales range from 2.2% to 13.44% and 0.19% to 1.08%, respectively. The CSM oil shale samples contain abundant carbonate (e.g., calcite and dolomite), quartz, and clay minerals. The clay minerals of the CSM oil shale samples is dominated by illite and then by smectite. Other minerals, including haematite, apatite, pyrite, baryte, and celestite, were also identified by scanning electron microscope–energy‐dispersive X‐ray spectrometer. The total rare earth element (∑REE) contents of the oil shales range from 9.01 to 105.96 ppm (average 57.56 ppm), close to the average REE contents of U.S. coals. The REE contents in oil shale samples are mainly controlled by terrigenous input. The CSM oil shales show LREE‐enriched, HREE‐depleted, with the LREE/HREE ratios ranging from 5.12 to 10.18, negative Eu anomalies (0.56–0.84) and slightly negative Ce anomalies (0.87–1.05). The chemical index of alteration values of the CSM oil shales range from 67 to 76 (average 73), indicating a moderate chemical weathering condition. Sr/Cu and Rb/Sr ratios suggest the CSM oil shales were mainly deposited under a warm and humid climate regime. Sr/Ba ratios, ranging from 0.54 to 7.84, suggest a palaeoenvironment with fluctuant salinity. Major element, trace element, and REE relationships indicate that the CSM oil shales are mainly from the felsic and intermediate igneous rocks. The REE distribution patterns of the CSM oil shales are similar to the Late Triassic Nadi Kangri felsic volcanic rocks in the Qiangtang Basin, indicating that the CSM oil shale may be derived from the Late Triassic volcanic rocks and the oil shales were mainly formed in rift tectonic setting. Favourable preservation condition (e.g., warmer palaeoclimate, higher palaeosalinity, and dysoxic to anoxic water column environment) could be the main controlling factor for organic matter accumulation.

Predominantly Ferruginous Conditions in South China during the Marinoan Glaciation: Insight from REE Geochemistry of the Syn-glacial Dolostone from the Nantuo Formation in Guizhou Province, China

The Neoproterozoic Era witnessed two low-latitude glaciations, which exerted a fundamental influence on ocean–atmosphere redox conditions and biogeochemical cycling. Climate models and palaeobiological evidence support the belief that open waters provided oases for life that survived snowball Earth glaciations, yet independent geochemical evidence for marine redox conditions during the Marinoan glaciation remains scarce owing to the apparent lack of primary marine precipitates. In this study, we explore variability in rare earth elements (REEs) and trace metal concentrations in dolostone samples of the Cryogenian Nantuo Formation taken from a drill core in South China. Petrological evidence suggests that the dolostone in the Nantuo Formation was formed in near-shore waters. All the examined dolostone samples featured significant enrichment of manganese (345–10,890 ppm, average 3488 ppm) and middle rare earth elements (MREEs) (Bell Shape Index: 1.43–2.16, average 1.76) after being normalized to Post-Archean Australian Shale (PAAS). Most dolostone samples showed slight to no negative Ce anomalies (Ce*/Ce 0.53–1.30, average 0.95), as well as positive Eu anomalies (Eu*/Eu 1.77–3.28, average 1.95). This finding suggests that the dolostone samples were deposited from suboxic to iron-enriched and anoxic waters. Although total REE concentrations correlated positively with Th concentrations in dolostone samples, MREE-enriched PAAS-normalized patterns preclude the conclusion that REEs were largely introduced by terrestrial contamination. Rather, we interpret the correlation between REEs and Th as an indication that the former were transported by colloids and nanoparticles in meltwaters. Taken together, we propose that anoxic and ferruginous water columns dominated in South China during the Marinoan glaciation with a thin oxic/suboxic layer restricted to coastal waters. The extreme anoxic and ferruginous conditions prevailing in the Cryogenian would have provided a baseline for subsequent transient Ediacaran ocean oxygenation and life evolution.

Complete arsenic-based respiratory cycle in the marine microbial communities of pelagic oxygen-deficient zones

Microbial capacity to metabolize arsenic is ancient, arising in response to its pervasive presence in the environment, which was largely in the form of As(III) in the early anoxic ocean. Many biological arsenic transformations are aimed at mitigating toxicity; however, some microorganisms can respire compounds of this redox-sensitive element to reap energetic gains. In several modern anoxic marine systems concentrations of As(V) are higher relative to As(III) than what would be expected from the thermodynamic equilibrium, but the mechanism for this discrepancy has remained unknown. Here we present evidence of a complete respiratory arsenic cycle, consisting of dissimilatory As(V) reduction and chemoautotrophic As(III) oxidation, in the pelagic ocean. We identified the presence of genes encoding both subunits of the respiratory arsenite oxidase AioA and the dissimilatory arsenate reductase ArrA in the Eastern Tropical North Pacific (ETNP) oxygen-deficient zone (ODZ). The presence of the dissimilatory arsenate reductase gene arrA was enriched on large particles (>30 um), similar to the forward bacterial dsrA gene of sulfate-reducing bacteria, which is involved in the cryptic cycling of sulfur in ODZs. Arsenic respiratory genes were expressed in metatranscriptomic libraries from the ETNP and the Eastern Tropical South Pacific (ETSP) ODZ, indicating arsenotrophy is a metabolic pathway actively utilized in anoxic marine water columns. Together these results suggest arsenic-based metabolisms support organic matter production and impact nitrogen biogeochemical cycling in modern oceans. In early anoxic oceans, especially during periods of high marine arsenic concentrations, they may have played a much larger role.

High-frequency redox variations of the Eocene cyclic lacustrine sediments in the Yingxi area, western Qaidam Basin, China

The mineral assemblages of lacustrine mixed sediments have vital significance for reconstructing paleo-lake environments, and typical lacustrine mixed sediments deposited during the Eocene are distributed throughout the Yingxi area in the western Qaidam Basin. Accordingly, the framboid size distributions and sulfur isotope (δ34Spy) characteristics of pyrite in addition to the carbon isotope (δ13Ccarb) characteristics and redox-sensitive element ratios (Th/U, V/(V + Ni) and V/Cr) of authigenic carbonates were investigated to reconstruct the high-frequency redox variations in cyclic lacustrine sediments.Corresponding to different redox conditions, three types of mixed sediments developed during transgression and regression stages within the saline basin in the Yingxi area during the Eocene: mixed terrigenous clasts formed in oxic-dysoxic water column conditions during lake transgression, mixed carbonates formed in anoxic water column conditions during early-stages lake regression, and mixed evaporites formed in anoxic-sulfidic water column conditions during middle-late-stage lake regression. The redox proxies correlate well with the water salinity, exhibit little or no correlation with the water temperature, and show an incongruity with the water depth, suggesting that the redox conditions were predominantly controlled by the water salinity rather than the water depth or temperature. Therefore, based on the water redox condition variations and the salinity, three dynamic formation models of the high-frequency sedimentary cycles in a saline basin are established: a deep-water, low-salinity, oxic-dysoxic model (Model I), a medium-water, medium-salinity, anoxic model (Model II) and a shallow-water, high-salinity, anoxic-sulfidic model (Model III). Because the climate gradually turned dry and hot from lake transgression to regression, the continued closure of the basin enhanced evaporation and salinization. In addition, mixed terrigenous clasts, mixed carbonates and mixed evaporites deposited successively. Correspondingly, salinity stratification gradually developed within the lake water, increasing the extent of bacterial sulfate reduction in the bottom water.

The Sirius Passet Lagerstätte of North Greenland-A geochemical window on early Cambrian low-oxygen environments and ecosystems.

The early Cambrian Sirius Passet fauna of northernmost Greenland (Cambrian Series 2, Stage 3) contains exceptionally preserved soft tissues that provide an important window to early animal evolution, while the surrounding sediment holds critical data on the palaeodepositional water‐column chemistry. The present study combines palaeontological data with a multiproxy geochemical approach based on samples collected in situ at high stratigraphic resolution from Sirius Passet. After careful consideration of chemical alterations during burial, our results demonstrate that fossil preservation and biodiversity show significant correlation with iron enrichments (FeHR/FeT), trace metal behaviour (V/Al), and changes in nitrogen cycling (δ15N). These data, together with Mo/Al and the preservation of organic carbon (TOC), are consistent with a water column that was transiently low in oxygen concentration, or even intermittently anoxic. When compared with the biogeochemical characteristics of modern oxygen minimum zones (OMZs), geochemical and palaeontological data collectively suggest that oxygen concentrations as low as 0.2–0.4 ml/L restricted bioturbation but not the development of a largely nektobenthic community of predators and scavengers. We envisage for the Sirius Passet biota a depositional setting where anoxic water column conditions developed and passed over the depositional site, possibly in association with sea‐level change, and where this early Cambrian biota was established in conditions with very low oxygen.

Revelation of organic matter sources and sedimentary environment characteristics for shale gas formation by petrographic analysis of middle Jurassic Dameigou formation, northern Qaidam Basin, China

The 7th member of Middle Jurassic Dameigou Formation (J2d7) in northern Qaidam Basin, China was proposed to have good hydrocarbon generating potential in previous studies. Here we apply an integrated petrographic and geochemical analysis to investigate the depositional environment, real thermal maturity and shale gas potential of organic-matter (OM)-rich assemblage. The relatively high content of C29 regular sterane (56.8%–62.8%) and vitrinite predominance in maceral composition suggesting plenty of higher-plant input, combined with the high pristane/phytane ratio (Pr/Ph)(2.8–8.2) and low gammacerane index (0.2–0.4) reveals oxic water column with in-situ depositional condition of carbonaceous-mudstone when the lower J2d7 was deposited. The maceral composition of oil shale at the upper part of J2d7 is mainly amorphous OM with small proportion of reworked vitrinite and inertinite, consistent with a mainly algea and small amount of exogenous OM input. When associated with low Pr/Ph (0.8) and high gammacerane index (4.3), the oil shale was deposited in an anoxic saline water column with mainly zooplankton OM source. The geochemical and petrographic result implies a transitional environment ranging from suboxic semi-saline to oxic fresh water environment with varying proportion of higher-plant and algae input by in-situ deposition and distant transportation for the mudstone at the middle part of J2d7. By use of random reflectance (Ro) distribution, two sedimentary environment microcycles which are confirmed by maceral composition, from the depth of 1983 m to 1962 m and 1954 m to 1931.9 m, are differentiated within the homogenous mudstone section. The variation of OM input condition and alternation of depositional environment led to accumulation and deposition of various kinds of abundant OM when J2d7 was deposited. Although the OM has actually low maturity at oil window with vitrinite reflectance around 0.6% according to the petrographic results, the liptinite inherited from higher-plants especially suberinite is the main maceral to generate gaseous hydrocarbons at the low maturity, which implies that the Dameigou formation (J2d7) of Qaidam Basin is of gas potential.

Did anoxia terminate Ediacaran benthic communities? Evidence from early diagenesis

The Ediacaran oceanic redox landscape was heterogeneous, where many basins had a shallow and highly dynamic chemocline above anoxic (ferruginous or euxinic) or low oxygen (manganous) waters. Seawater mMg/Ca ratio was also high, promoting early diagenetic dolomitisation. How the benthos responded to these conditions is fundamental to understanding their ecological dynamics. Here we utilise redox sensitive elements in early marine carbonate cements to investigate possible water column redox controls on the distribution and growth of the oldest metazoan communities.Skeletal communities in the Zaris Sub-Basin of the Nama Group, Namibia (∼550–547 Ma), grew in shallow waters where fine-grained carbonate sediment often shows evidence of early dolomitisation. Mid-ramp Cloudina reefs are composed of open, highly porous structures that formed multiple, successive assemblages. Each assemblage is terminated by thin (<1 mm), layers of dolomicrite sediment and dolomite cement. All dolomitic lithologies in the Nama Group analysed via Fe speciation suggest precipitation under anoxic ferruginous water column conditions.Reef cements show a paragenetic sequence from synsedimentary to early marine cement and final burial, which we infer were precipitated under dynamic redox conditions. First, acicular pseudomorphed aragonite cement formed under oxic conditions (low Fe and Mn). Next, the presence of iron-rich dolomicrite sediment, often associated with a recrystallised ferroan dolomite crust, suggests that originally aragonitic or calcitic sediment and a high-Mg precursor cement were preferentially dolomitised. Dolomitisation may have been enhanced either via upwelling of deeper water, anoxic, ferruginous seawater, or by later fluid remobilisation from adjacent shales. A following Mn-rich calcite cement is inferred to be early marine due to its inclusion-rich, fibrous form and well-preserved CL zonation. The final blocky cement precipitated under oxic conditions, probably during shallow burial.The cements likely record a general shallow to deeper water transect, from oxic shallow waters to low oxygen manganous waters, then to oxic, shallow burial conditions. We hypothesize that Cloudina reef communities were terminated by episodic sediment incursions during short-term, transgressive cycles, possibly accompanied by upwelled, anoxic, ferruginous and dolomitising waters, although the timing for this is poorly constrained. More generally, such incursions may have terminated Ediacaran benthic communities that grew close to the chemocline.

Links between seawater paleoredox and the formation of sediment-hosted massive sulphide (SHMS) deposits — Fe speciation and Mo isotope constraints from Late Devonian mudstones

Many models of sediment hosted massive sulphide (SHMS) deposit formation invoke basin restriction events that resulted in long-term stagnation and anoxia, in which sulphidic (euxinic) conditions ultimately prevailed. Euxinic conditions are then thought to provide a chemical trap for hydrothermally exhaled base metals. Here, we present Fe speciation and Mo isotope data for organic-rich mudstones from two drill-holes intersecting Upper Devonian strata, deposited along the passive margin of ancestral North America. One drill-hole intersects a 35 m thick sequence of SHMS mineralisation, while the other intersects correlative, un-mineralised strata. All samples have high FeHR/FeT values (>0.38), indicating water-column anoxia. For the majority of samples in the un-mineralised drill-hole, the levels of pyritisation fall below the threshold typically used to define euxinic conditions (FePY/FeHR ≤ 0.70). In contrast, higher levels of pyritisation in the mineralised drill-hole (median FePY/FeHR = 0.86) likely developed via diagenetic pyrite enrichment. Whereas Pb and Zn are negatively correlated with Mo, Mo-U co-variation is consistent with Fe (oxyhydr)oxide particulate shuttling in the water-column. In addition, a weak correlation between TOC/P and Mo provides further evidence that Mo was sourced via authigenic, rather than hydrothermal, processes. The δ98Mo values (+0.66 to +1.02‰) are uniform between both drill-holes, and substantially lower than constraints for Late Devonian seawater (+1.5 to +2.0‰), consistent with Mo adsorption to Fe (oxyhydr)oxides. Collectively, the data provide evidence that local seawater was dominantly ferruginous (anoxic, non-sulphidic) at Macmillan Pass. Regional variability in the extent of ferruginous (low TOC/P) and euxinic (high TOC/P) conditions likely contributed to a balance between P regeneration and P enrichment that maintained nutrient availability and productivity in the Selwyn Basin during the Late Devonian. We argue that high primary productivity and enhanced organic carbon burial are key variables for promoting sulphate reduction in the sub-surface. Moreover, how such conditions are maintained over long periods of basin evolution is more important for producing effective metal traps in SHMS systems, rather than a specific, localised redox condition of seawater (i.e. euxinia).