Euxinic Research Articles

Reconstruction of the Eukaryotic Communities in Beppu Bay Over the Past 50 Years Based on Sedimentary DNA Barcoding

AbstractComprehensive reconstruction of changes in eukaryotic communities in the recent past is useful for determining the response of the local ecosystems to global changes during the Anthropocene. We used DNA barcoding technology to reconstruct the marine eukaryotic communities of Beppu Bay, the Seto Inland Sea, Japan, over the past 50 years based on a short sediment core. Highly vulnerable DNA fragments were preserved in the sediments, possibly due to seasonally euxinic conditions. Analysis of the 18S rRNA V9 gene region indicated the temporal variability in eukaryotic communities, which consisted mainly of dinoflagellates and diatoms, in response to changes in the nutrient regime. The dominant species in the dinoflagellate genus Alexandrium changed as the water temperature increased. In addition, enhanced contributions by terrestrial plants and mosses were detected in flood sediments. Our results suggest that DNA fragments can be used as a proxy for the paleoenvironmental and paleoecological conditions in Beppu Bay.

Nitrogen isotope evidence for oxygenated upper ocean during the Cryogenian interglacial period

The Cryogenian interglacial period have witnessed dramatic changes in climate, oceanic environment and biological evolution. The nitrogen isotopic composition, as an important biogeochemical proxy, has the potential to track both the nutrient cycling and redox conditions in the past. However, nitrogen isotopic data during this interglacial time is rather limited. Here, we present integrated data for nitrogen isotopes (δ15N), as well as organic carbon isotopes (δ13Corg), iron (Fe) speciation, pyrite morphology and trace elements from the Cryogenian interglacial Datangpo Formation derived from a drill core from South China to figure out the nitrogen cycling and coeval redox states. The results reveal a gradual oxygenation bottom waters along with deepening O2-H2S chemocline from euxinic black shale in the lower unit (LU), to oxic siltstone in the upper unit (UU), which is consistent with the redox variation inferred in previous studies. Sedimentary δ15N values constantly remain positive (mean value> + 4‰) throughout the Datangpo Formation and display an increase from the LU to the UU. We interpreted the positive δ15N values in the LU as a result of denitrification related to the development of euxinic conditions. The further increase towards the UU associated with limited nutrient supply may indicate the existence of a stable nitrate reservoir in the upper water column, which was consistent with an increased oxygenation during the interglacial time. The elevated O2 levels and bioavailable nitrogen in seawater may have further contributed to the appearance of the earliest metazoan. In addition, our data lay good foundation for further global δ15N correlations among other interglacial successions.

Deep-ocean anoxia across the Pliensbachian-Toarcian boundary and the Toarcian Oceanic Anoxic Event in the Panthalassic Ocean

The early Toarcian Oceanic Anoxic Event (T-OAE, or Jenkyns Event, ~183 million years ago) was a major hyperthermal and global carbon-cycle perturbation, likely associated with the release of a substantial volume of 12 C-enriched carbon to the Earth's surface. Seawater deoxygenation and the associated deposition of organic-rich facies during this event have been noted in many locations around the world, but evidence for pervasive and extreme oceanic anoxia has thus far been described mainly from European sections deposited in hydrographically restricted basins. Here we present new geochemical data on redox changes during the T-OAE, as well as the preceding Pliensbachian-Toarcian boundary (Pl/To) event, from a deep Panthalassic Ocean site at Inuyama, Japan. Redox-sensitive trace element data reveal an extended interval of seawater deoxygenation that began prior to the Pl/To and continued to the end of the T-OAE. A marked expansion of anoxic and possibly euxinic conditions to the seafloor occurred during both the Pl/To and T-OAE, accompanied by increased organic carbon burial. During these intervals of severe deep-ocean deoxygenation, our data suggest a global drawdown of trace elements such as Mo, U and As. Our findings highlight that: (1) the Panthalassic Ocean was likely an important locus of deoxygenation and organic carbon burial during the early Toarcian, and (2) the spread of anoxia during the T-OAE was a globally distributed phenomenon. • Anoxia in deep water Panthalassa from late Pliensbachian to early Toarcian. • A putative Oceanic Anoxic Event at the Pliensbachian-Toarcian boundary. • Global drawdown of redox-sensitive trace elements during Toarcian OAE. • Deep sea organic carbon burial at Pliensbachian-Toarcian and Toarcian OAE.

Geochemistry of oils and condensates from the lower Eagle Ford Formation, south Texas. Part 2: Molecular characterization

Fifty-five petroleum samples from unconventional wells in the self-sourced lower Eagle Ford Shale were analyzed using routine geochemical methods. The samples are broadly distributed, geographically and vertically, and range in maturity from mid-oil to wet gas. Their physical and chemical properties span most of the range observed in the entire play. Two source facies are identified: west of San Marcos Arch is a marine marl facies deposited under anoxic to euxinic conditions containing abundant type II/IIS kerogen and east of the Arch is a marine shale to marl facies deposited under mostly oxic to anoxic conditions that received an additional input of terrigenous organic matter. The unconventional oils are too mature to detect any subtle differences that could distinguish a marl from a pure carbonate source facies. Saturated and aromatic biomarkers rapidly decrease with depth and are at or near the limits of detection below ∼9,000 feet. Condensates >13,500 ft show evidence of advanced hydrocarbon cracking. All properties and molecular parameters that are dependent on thermal maturity for oils/condensates west of the San Marcos Arch exhibit two trends with true vertical depth (TVD). One is defined by samples between the Karnes Trough area and the Maverick Basin; the other trend defined by samples near the Karnes Trough is offset with equivalent maturity occurring at deeper depths. This ∼2,000 ft offset is likely due to differences in the amount of uplift and erosion experienced in the two regions after the source rocks achieved their maximum maturity.

Palaeoenvironments and elemental geochemistry across the Permian–Triassic boundary at Ursula Creek, British Columbia, Canada, and a comparison with some other deep‐water Permian–Triassic boundary shelf/slope sections in western North America

The Permian–Triassic boundary sediments at Ursula Creek accumulated in a continental shelf basin, or on the continental slope of the western Canadian passive margin, at 30°N palaeolatitude along the eastern Panthalassic Ocean margin. The area lay within the cold northerly ocean currents at the junction of westerly and north-easterly trade wind belts, the latter causing summer coastal upwelling. The shift from uppermost Permian grey radiolarian cherts and grey shales to lowermost Triassic grey and black shales and fine-grained dolomites is typical of deep-water Panthalassic sediments. The palaeogeographical situation and palaeoenvironments are comparable to those of the present Canadian north-western Pacific margin. The Ursula Creek section reveals the progressive decline of seafloor oxygen values in the Changhsingian Stage), followed by the persistent development of euxinic conditions in the latest Changhsingian and throughout the Early Triassic; a transition that coincides with the disappearance of a siliceous sponge fauna and the loss of diverse radiolarian populations. Much of the detrital sediment was supplied by summer north-east Trade winds from the deserts of western North America, although variable amounts may have come across the Panthalassic Ocean as dust from contemporary volcanic eruptions. Relative palaeoproductivity changes show no consistent change in productivity across the Permian–Triassic boundary producing results that are comparable with those from the similar Opal Creek section to the south-east. The Ni/Co, Cu/Zn, U/Al and Th/U ratios indicate variable redox conditions in all sections, but with a tendency for oxic conditions to change to dysoxic across the Permian–Triassic boundary. The lack of consistent element geochemical changes across the boundary accompanied by significant isotopic changes, here and elsewhere, suggests that atmospheric and oceanic chemistry rather than physical changes, like provenance and sea-level changes, drove Permian–Triassic environmental changes and extinctions.

Co-variation systematics of uranium and molybdenum isotopes reveal pathways for descent into euxinia in Mediterranean sapropels

The elemental concentrations and isotope compositions of molybdenum (Mo) and uranium (U) are commonly used for the reconstruction of past global and local redox conditions, and recent studies using both elements have revealed the potential of their paired application. However, such studies have generally focused either on modern marine sediments or on relatively low-resolution reconstructions of deep-time paleo-redox conditions. Here, we present high-resolution profiles (every 0.2-0.3 kyr) of Mo and U elemental and isotope compositions for anoxic organic-rich sediments of Eastern Mediterranean sapropels S5 and S7. The new Mo-U data reveal the processes leading to descent into basinal euxinia in more precise and systematic detail than lower resolution datasets focused on either Mo or U only.During the intensification from anoxic non-sulfidic to persistently euxinic conditions, δ98Mo and δ238U covariation systematics exhibit two stages. We identify the Mo-U isotope signature of the early transition from anoxic non-sulfidic to mildly euxinic conditions in the first stage, characterized by a rise in U isotope ratios (from −0.3‰ to +0.2‰ ±0.05‰) controlled by the depth within the sediment of the uranium reduction-accumulation front. As the water column turns persistently euxinic, δ98Mo values approach the seawater value for both sapropels, but δ238U evolves to different final values in the two sapropels. We interpret these differences as reflecting different redox potentials and/or different degrees of restriction of these two sapropel events, and the more gradual response of U sequestration to redox variation in comparison with threshold behavior of Mo. The findings presented here show temporal patterns in δ98Mo and δ238U on relatively short timescales that suggest the combined use of these proxies at high resolution allows detailed reconstruction of local redox and hydrographic conditions.

Mechanism of Organic Matter Accumulation in Black Shales of the Yuertusi Formation in the Tarim Basin: Insights From Paleoenvironmental Variation During the Early Cambrian

The paleoenvironment during the Early Cambrian is closely related to the accumulation mechanism of organic matter (OM) from the Lower Cambrian black shales. However, paleoenvironment remains a controversial issue. Here, we reported a lot of detailed data of sedimentary stratigraphy and geochemistry of the Lower Cambrian Yuertusi Formation in the Aksu area, Tarim Basin. The Yuertusi Formation from the Yutixi outcrop consists mainly of silicalite at the base, two sets of black shales, and crystalline dolostone. Based on the redox conditions traced by U/Th, V/Cr, Ni/Co, and V/Sc, the hydrothermal activity traced by Ce/Ce*, Cr/Zr, U/Th, Fe/Ti, and (Fe + Mn)/Ti ratios, as well as paleo-productivity traced by Ba, Cu, Rb/Sr, and other parameters, variations were observed in the depositional environments of the Yuertusi Formation: 1) the silicalite at the base was deposited under an euxinic condition and intense hydrothermal activity. Mo-U co-variation analysis revealed that the north margin of Tarim Basin belonged to the unrestricted marine during the Early Cambrian, 2) the lower black shales were deposited under an oxygen-poor condition and weak hydrothermal activity, and 3) the upper black shales were deposited under oxygen-poor, sub-oxic conditions and almost no hydrothermal activity. Although the hydrothermal activity improved paleo-productivity, the TOC values were low on the whole, which may be due to the intense hydrothermal activity that damaged the formation of source rocks. Comprehensive studies showed a gradually oxidizing environment and weakening paleo-productivity during the Yuertusi Formation deposited. The anoxic conditions were conducive to the preservation of OM, and the high-quality source rocks represented by the black shales of the Yuertusi Formation were formed, especially the first set of black shales. However, the enrichment of OM may be affected by the intense hydrothermal activity.

Marine anoxia as a trigger for the largest Phanerozoic positive carbon isotope excursion: Evidence from carbonate barium isotope record

The mid-Ludfordian Lau carbon isotope excursion (Lau CIE) represents the largest positive carbon isotope excursion in the Phanerozoic (∼9‰), coincident with the biodiversity loss of many marine animal clades. Two main explanations for the Lau CIE are enhanced organic carbon burial via increased marine productivity and preservation-driven expansion of anoxia. While these two explanations are not mutually exclusive, the main driver of Lau CIE is yet to be constrained. Here, we resolve this longstanding debate using barium isotopes (δ138Ba) of marine carbonates deposited across the Lau CIE. Our δ138Ba data from the Kosov section (Czech Republic) record a large negative excursion in correlation to the positive shift in δ13Ccarb. We suggest that the observed negative shift in δ138Ba to values as low as −0.33‰ can be best interpreted as upwelling of isotopically light Ba from deeper waters due to pelagic barite dissolution under euxinic conditions. This hypothesis is consistent with results from barium concentration data as well as the results from the sulfate mass balance modeling that indicates a contraction in the seawater sulfate reservoir, with seawater sulfate concentrations decreasing from several mM ranges before the Lau CIE to less than 100 μM during Lau CIE. Taken together, evidence for a strong negative correlation between δ138Ba and δ13Ccarb suggests that shallow water anoxia, rather than enhanced marine productivity, was a primary driver of the Lau CIE that resulted in a notable decrease in the size of seawater sulfate reservoir.

Extensive marine anoxia in the European epicontinental sea during the end-Triassic mass extinction

Warming-induced marine anoxia has been hypothesized as an environmental stressor for the end-Triassic mass extinction (ETME), but links between the spread of marine anoxia and the two phases of extinction are poorly constrained. Here, we report iron speciation and trace metal data from the Bristol Channel Basin and Larne Basin of the NW European epicontinental sea (EES), spanning the Triassic–Jurassic (T–J) transition (~ 202–200 Ma). Results show frequent development of anoxic-ferruginous conditions, interspersed with ephemeral euxinic episodes in the Bristol Channel Basin during the latest Rhaetian, whereas the contemporaneous Larne Basin remained largely oxygenated, suggesting heterogeneous redox conditions between basins. Subsequently, more persistent euxinic conditions prevailed across the T–J boundary in both basins, coinciding precisely with the second phase of the ETME. We propose that this later phase of benthic faunal loss in the NW EES was directly driven by the bottom-water oxygen crisis. Conversely, although anoxic conditions persisted into the early Hettangian, the benthos diversified at this time in nearshore areas. Post-extinction conditions were poised at a fluctuating redox state, but anoxia did not extend into the shallowest areas where benthic marine ecosystem recovery was occurring. • Water column anoxia was common in the European epicontinental sea through the Triassic–Jurassic transition. • Intensified marine euxinia developed at the second phase of the end-Triassic mass extinction. • A low oxygen ocean persisted post-extinction, but with a fluctuating redox state and limited ecological influence.

Geochemical and carbon isotopic studies of carbonaceous phyllites from Dharwar craton, India – Reconstruction of Precambrian depositional environment

Carbonaceous shales formed in anoxic, deep marine environment are depocenters of prolific microbial life and rich sources of organic matter. In the present study, geochemical and organic carbon isotopic (δ13Corg) signatures of carbonaceous phyllites from Archean Chitradurga, Gadag, Sandur, Shimoga greenstone belts and Proterozoic Cuddapah basin of Dharwar Craton were studied to understand the Precambrian depositional environment by delineating the similarities and differences in the Archean and Proterozoic samples. Both Archean and Proterozoic carbonaceous phyllites are fine grained siliceous in nature with depleted CaO, MgO and alkalies. The REE concentrations in most of the Archean samples are characterized by conspicuous positive Europium anomalies while the Proterozoic counterparts display feebly positive ratios indicating hydrothermal source. The Archean samples possess elevated Chemical Index of Alteration (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Weathering (PIA) values reflecting extreme weathering conditions while the Proterozoic carbonaceous phyllites are confined to moderate weathering conditions. Cr/Th, La/Sc, Th/Sc and Co/Th indicate mafic provenance and the Cr-Zr relationship suggests deep sea depositional setting for both Archean and Proterozoic carbonaceous phyllites. The Archean carbonaceous phyllites indicate humid to semi-humid paleoclimate conditions while the Proterozoic samples are restricted to humid palaeoclimatic conditions which is evident from Sr/Cu ratios. V/(V + Ni) ratios indicate fluctuating dysoxic to euxinic redox conditions for the Archean samples while the Proterozoic samples display euxinic conditions. The predominantly negative δ13Corg values of Chitradurga (−38.5‰ to −14.2‰ VPDB), Gadag (−24.3‰ to −8.06‰ VPDB), Sandur (−24.8‰ to −29.2‰ VPDB), Shimoga (−24.6‰ to −11.8‰ VPDB) and Cuddapah (−30.19 to −13.98‰ VPDB) suggest the role of primitive life forms through biological processes during the deposition of organic matter.

Reconstructing the paleoceanographic and redox conditions responsible for variations in uranium content in North American Devonian black shales

The uranium (U) content, and more recently, the ratio between 238 U and 235 U in black shales are commonly applied as a proxy to determine redox conditions and infer organic-richness. Uranium contents typically display a linear relationship with total organic carbon (TOC) in shales. This relationship is due to the processes and mechanisms responsible for the incorporation of U into the sediment during the deposition and remineralization of organic matter. This U/TOC relationship can vary, however, and some shales display uncharacteristically low U content despite having high TOC content, while others show large enrichments of U relative to TOC. Here we examine the U to TOC ratios and U-isotope compositions of three Upper Devonian-Lower Mississippian shales: the Woodford Shale, the Cleveland Shale, and the Bakken Shale, with two study sites in Oklahoma, one site in eastern Kentucky, and three sites in eastern Montana and western North Dakota, respectively. The U/TOC ratios of each shale are distinct from one another exhibiting average ratios ranging from 3 in the Cleveland Shale, to over 10 in the Bakken Shale. The distinct geochemical composition of the three shales suggests that, although lithologically similar, each study site represents a markedly different and dynamic depositional environment. The low average U/TOC (~3) along with the relatively high δ 238 U values (~0.03‰) of the Cleveland Shale core suggests deposition along the basin margin under normal marine conditions with periods of reduced bottom water oxygenation, likely due to fluctuations in the location of the pycnocline. The Woodford Shale on the other hand, shows higher U/TOC ratios (~4, George core, ~9, Poe core) and δ 238 U (~0.02‰ average, George core, ~0.06‰ average, Poe core), which suggests an unrestricted setting with intermittent euxinic conditions. In contrast, high U/TOC ratios (2–15), and very high δ 238 U values (up to 0.55‰) in the Bakken Shale cores indicate intense metal draw-down into sediments under sulfidic waters. The results show that when the U/TOC ratios and U-isotopic compositions of each studied shale are compared to modern anoxic basins and upwelling areas, it allows for an enhanced understanding of the paleoenvironmental conditions such as basin restriction and redox state of waters within the Late Devonian epicontinental seas of North America. • U/TOC ratios of Late Devonian shales vary due to basin restriction. • Bottom water euxinia does not require strong basin restriction. • δ 238 U values provide new insight into the paleogeography of N. American basins.

Geochemical Records Reveal Protracted and Differential Marine Redox Change Associated With Late Ordovician Climate and Mass Extinctions

AbstractThe Ordovician (Hirnantian; 445 Ma) hosts the second most severe mass extinction in Earth history, coinciding with Gondwanan glaciation and increased geochemical evidence for marine anoxia. It remains unclear whether cooling, expanded oxygen deficiency, or a combination drove the Late Ordovician Mass Extinction (LOME). Here, we present combined iodine and sulfur isotope geochemical data from three globally distributed carbonate successions to constrain changes in local and global marine redox conditions. Iodine records suggest locally anoxic conditions were potentially pervasive on shallow carbonate shelves, while sulfur isotopes suggest a reduction in global euxinic (anoxic and sulfidic) conditions. Late Katian sulfate‐sulfur isotope data show a large negative excursion that initiated during elevated sea level and continued through peak Hirnantian glaciation. Geochemical box modeling suggests a combination of decreasing pyrite burial and increasing weathering are required to drive the observed negative excursion suggesting a ∼3% decrease of global seafloor euxinia during the Late Ordovician. The sulfur datasets provide further evidence that this trend was followed by increases in euxinia which coincided with eustatic sea‐level rise during subsequent deglaciation in the late Hirnantian. A persistence of shelf anoxia against a backdrop of waning then waxing global euxinia was linked to the two LOME pulses. These results place important constraints on local and global marine redox conditions throughout the Late Ordovician and suggest that non‐sulfidic shelfal anoxia—along with glacioeustatic sea level and climatic cooling—were important environmental stressors that worsened conditions for marine fauna, resulting in the second‐largest mass extinction in Earth history and the only example during an icehouse climate.

Archean Biogeochemical Cognizance from Dharwar Craton, India – A Review

Abstract The Banded iron formations (BIFs) and manganese formations of Chitradurga, Shimoga and Sandur greenstone belts of Dharwar craton, associated with the stromatolitic carbonates, carbonaceous phyllites and shales along with gold mineralization, are best geological entities to evaluate the Archean biogeochemical processes and transformation of a habitable Earth. The geochemical anomalies along with C, O and S isotopic signatures of stromatolitic carbonates, carbonaceous phyllites and sulphidic BIFs reflect on biogenic signatures, fluctuating Archean ocean temperatures from 25-75°C and anoxic to euxinic redox conditions. The U-Pb detrital zircon ages of these stromatolitic carbonates indicate 3.5 to 2.6 Ga whereas the carbonaceous shales indicate 3.2 – 2.2 Ga reflecting the transportation of organic matter to the ocean basin during the growth of stromatolitic carbonates. The gold content of carbonaceous phyllites and sulphidic BIFs indicates hydrothermal source. The O2 produced due to stromatolitic activity has deposited Mn and Fe of the Archean oceans as BIFs and Mn formations. The biogenic matter of the stromatolites along with other siliciclastic material, gold and sulphides derived from the volcanic activity mixed and formed as carbonaceous shales in the ocean basin under euxinic conditions. The comprehensive geological, geochemical including isotopic studies on these rock types collectively indicate the interaction of lithosphere-hydrosphere-atmosphere-biosphere in the Archean oceans which paved the way for the advanced forms of life.

Uranium isotope cycling on the highly productive Peruvian margin

Uranium isotopes (δ238U values) in ancient sedimentary rocks (shales, carbonate rocks) are widely used as a tool to reconstruct paleo-redox conditions, but the behaviour of U isotopes under modern non-sulfidic anoxic vs. oxic conditions remains poorly constrained. We present U concentration and isotope data for modern sediments from the Peruvian margin, a highly productive open ocean environment with a range of redox conditions. To investigate U in different host fractions of the sediment (reactive, silicate, and HNO3-soluble fraction), we conducted a series of sequential extractions. Detrital-corrected authigenic U isotope compositions (δ238Uauth) in sediments deposited beneath an oxic water column show little deviation from the dissolved seawater U source, while anoxically deposited sediments have δ238Uauth values that are up to 0.4‰ heavier compared to seawater δ238U. Under anoxic, non-euxinic conditions, the U isotope offset between sediment and seawater is larger compared with oxic, but significantly smaller when compared with euxinic conditions from the literature. The results from sequential extractions show that the reactive sediment fraction records more pronounced differences in δ238Ureactive than δ238Uauth values depending on the oxidation state of the overlying water column. Furthermore, we found a strong correlation between total organic carbon (TOC) and both U concentrations (Uauth) and δ238Uauth values (R2 = 0.70 and 0.94, respectively) at the persistently anoxic site that we examined. These correlations can be caused by several processes including U isotope fractionation during microbially-mediated U reduction at the sediment-water interface (diffusive U input), during sorption onto and/or incorporation into organic matter in the water column (particulate U input) and diagenetic redistribution of U, or a combination of these processes. Our data show that several factors can influence δ238U values including oxidation state of U, the presence or absence of hydrogen sulfide and organic matter. These findings add new constraints to the degree of U isotope fractionation associated with U incorporation into sediments in different low-oxygen environments, thus aiding in interpretation of ancient paleo-redox conditions from U isotope data.

Using whole rock and in situ pyrite chemistry to evaluate authigenic and hydrothermal controls on trace element variability in a Zn mineralized Proterozoic subbasin

The mid-Proterozoic stratigraphy of the McArthur Basin (Australia) contains some of the most well-preserved sedimentary rocks of Precambrian age, which are also host to giant, clastic dominant (CD-type) massive sulfide Zn deposits. The most recently discovered CD-type deposit (the Teena deposit) is located in the Teena subbasin and hosted by the 1.64 Ga Barney Creek Formation. The Teena subbasin, therefore, provides the perfect natural laboratory for evaluating authigenic and hydrothermal controls on trace element (TE) variability, both of which contribute to paleoenvironmental reconstructions and ore deposit models. As the Teena deposit formed beneath the paleoseafloor, this also provides the opportunity to evaluate TE zonation around a fossilized subseafloor replacement hydrothermal system. In situ laser ablation inductively coupled mass spectrometry (LA-ICP-MS) has been used to define compositional end members in diagenetic and hydrothermal pyrite. The overgrowth of hydrothermal sulfides on diagenetic pyrite is associated with TE anomalism (Tl, Pb, As, Zn) that extends > 100 meters above the main high grade sulfide mineralization the Teena subbasin. The vertical zonation in TEs is consistent with the infiltration of hydrothermal fluids into overlying hangingwall sediments that were undergoing diagenesis. Bulk rock lithogeochemical data record covariation between total organic carbon (TOC) and a suite of TEs (Mo, Co, Ni, V). We suggest this was caused by local hydrographic factors during deposition of the Barney Creek Formation. High TOC/P molar ratios, resulting from regeneration of P in a euxinic water column, are associated with an interval overlying the main maximum flooding surface in the subbasin. The relationships between TOC, P and TEs resemble the redox architecture of a silled basin rather than an open marine margin. Sulfidic conditions developed during periods of high productivity, which were linked to nutrient supply that was enhanced by connectivity with surrounding water masses. The evidence of redox bistability, involving a delicate balance between ferruginous (anoxic, non-sulfidic) and euxinic (sulfidic) conditions, is consistent with recent models for other mid-Proterozoic sedimentary units. Nevertheless, there was a strong localised (101 km2) control on the authigenic and hydrothermal TE chemistry of the Barney Creek Formation in the Teena subbasin, which highlights a key challenge when extrapolating from data collected in partially restricted intracontinental marine settings.

Depositional sequence interpretation using seismic and well data of offshore Central Sumatra Basin

Offshore Central Sumatra Basin is an integral part of Central Sumatra Basin known for producing hydrocarbon basins. The derivation of stratigraphic study of seismic and well data is intended to improve accuracy of geological interpretation. Sequence stratigraphy studies have a significant role in exploratory studies to determine which depositional sequence can be inferred as hydrocarbon reservoir and its correlation in petroleum system. This study aims to identify biogenic gas sequential interpretation using seismic and well data of offshore Central Sumatra Basin. The procedure to analyze sequence stratigraphy is to identify stratigraphy surface markers using GR log, then map these markers to the seismic section that has been tied with good data to determine the distribution of each stratigraphy sequence. This study area has five depositional sequences, which are predominantly formed in marine depositional environments. Potential source rock in this area is at DS-1 which has a lacustrine depositional environment with euxinic conditions. The euxinic shale at the upper TST-1 deposit could be a source rock with hydrocarbon migration through faults. Biogenic gas reservoir potential is in Petani Formation (DS-5). Shale in MFS-5 and HST-5 could be a hydrocarbon trap, whereas LST-5 and TST-5 sandstone deposits can be a reservoir.

Progressive development of ocean anoxia in the end-Permian pelagic Panthalassa

The end-Permian mass extinction (EPME) has been linked with the widespread development of oxygen-poor oceanic conditions. However, information on the spatial extent of anoxia in the Panthalassa super-ocean has been limited. This study reports oceanic redox records from a deep-sea chert succession (the Waiheke 1 section, WHK 1, New Zealand) that was located in southern mid-latitudes of Panthalassa. High-resolution carbon isotope (δ13C) correlation between Waiheke and the Permian-Triassic boundary (PTB) type section indicates that the EPME is recorded in a thin black claystone interbedded between siliceous mudstone beds at WHK 1. Pyrite-dominated enrichment in highly reactive iron, coupled with elevated U/Al and Mo/Al ratios, are prevalent through this black claystone bed and the overlying Permo-Triassic transition strata, suggesting the development of euxinic water column conditions. Similar redox variations across the EPME horizon have been reported from other Panthalassic deep-sea PTB sections. Comparison with these PTB sections indicates that euxinic conditions were widespread in low-latitude regions of the Panthalassan ocean, and such conditions developed earlier than in mid-latitude settings, up to 100,000 years before the EPME. This suggests there was a gradual expansion of ocean anoxia from low to middle-high latitude regions during the Permo-Triassic transition. The extent of ocean anoxia resulted in a decrease in the seawater inventory of redox sensitive trace metals (e.g., Mo), which is evident in the earliest Triassic strata of the studied section and other PTB sections. Panthalassic anoxia during the EPME coincides with extreme climate warming and the associated effects (e.g., changes in ocean circulation, marine eutrophication intensified by terrestrial weathering) were likely critical triggers for ocean deoxygenation.

Origin and Geochemical Implications of Hopanoids in Saline Lacustrine Crude Oils from Huanghekou East Sag and Laizhouwan Northeastern Sag, Bohai Bay Basin.

A suite of low-mature crude oils (five high-sulfur oils and six low-sulfur oils) from the Huanghekou and the Laizhouwan Sags, Bohai Bay Basin, are analyzed to investigate the fate of the hopanoids. Abundant hopanes, such as secohopanes, 25-norhopanes, benzohopanes, aromatized secohopanes, and sulfide hopanes, are identified, and their carbon isotope compositions are determined. Varying 13C isotope values of C31 hopane (−38.7–34.0‰) and C29-30 hopanes (−38.5–31.5‰) suggest different bacterial sources of these compounds. The presence of 25-norhopanes with enriched heavy carbon isotopes in severely biodegraded oils suggests that they are microbially mediated products. The detection of the isotopically depleted C29 and C30 D-ring-8,14-secohopanes (−45.6–41.2‰) indicates that secohopanes are from methane-oxidizing bacteria (methanotrophs). The presence of isorenieratane, lower aryl isoprenoid ratios, and a good correlation between the sulfur content and the gammacerane index indicate the presence of green sulfur bacteria (Chlorobiaceae) under photic zone euxinic conditions. Water column stratification results in good preservation of the organic matter, and it is in favor of diversity of aquatic microorganisms. The ratios of C35/C34 sulfide hopane, C35 sulfide hopane-2/C35 sulfide hopane-1, and C35/C34 benzohopane are influenced by the reducing environments in this region. In addition, the D-ring monoaromatized 8,14-secohopanoid/(D-ring monoaromatized 8,14-secohopanoid + benzohopanes) and C31–C35 secomoretanes/secohopanes are affected by the maturity. We hypothesize that the reducing environments and thermal effects are important markers for the hopanoid transformation, including the incorporation of inorganic sulfur in substituting functional groups, cyclizing, aromatizing, and opening ring C of the hopanoids.

A re-assessment and calibration of redox thresholds in the Permian Lucaogou Formation of the Malang Sag, Santanghu Basin, Northwest China

Analysis of redox conditions of lake water is of great significance to the reconstruction of sedimentary environments. However, previously established threshold values of redox-sensitive element proxies may not be directly applicable to various study areas even with some degree of calibration. The present study of the Permian Lucaogou Formation (P2l), Santanghu Basin, re-evaluates and calibrates commonly used redox proxies, including bimetal ratios, the C–S–Fe–P system, and proxies based on U abundances. Specifically, we rely on the compound covariation theory of proxies proposed by previous researchers within the redox framework according to three key redox thresholds (T1: suboxidized/subreduced boundary, T2: middle of subreduced zone, and T3: suboxic/euxinic boundary) and organic/inorganic geochemical data. The results show that the fixed thresholds of widely used redox proxies, including bimetal ratios, are not fully applicable to the studied succession. Reassessment of the use of bimetal ratios based on covariation theory suggests that the V/Cr, V/(V + Ni), TOC/P, and Fe/Al ratios are especially useful to redox analysis of the P2l succession whereas the Ni/Co, Ni/V, (Cu + Mo)/Zn, U/Th, and Uauth proxies yield spurious results. It is important to point out, however, that the threshold values of those proxies that have yielded useful results cannot be used without calibration. Therefore, those redox proxies used in our investigation of the P2l succession have been re-calibrated based on the proxy covariation theory. For example, V/(V + Ni) values of T1, T2, and T3 thresholds of approximately 0.78 differ from the fixed threshold values established by previous investigations, suggesting that avoiding erroneous redox interpretations will require calibration of the thresholds. Other redox proxies display a similar need for calibration. Deposits of the P2l, by virtue of small variations among the three thresholds, record a complex history of rapid transitions from suboxic to euxinic conditions.

Insights into hydrothermal controls and processes leading to the formation of the Late Ediacaran Gaoyan stratiform manganese-carbonate deposit, Southwest China

The stratiform Mn-carbonate ore from the Gaoyan deposit occurs within terrigenous-sedimentary rocks of the upper part of the Ediacaran Doushantuo Formation and is characterized by rhodochrosite spherulites. Here we examine the effect of depositional environment and hydrothermal contribution based on new petrographical, mineralogical and geochemical data to shed light on major controls on formation of sedimentary Mn mineralization. The significant geochemical characteristics such as high Mn/Fe ratios (average 32.07), high Ba content (average 1940.9 ppm), positive Eu anomalies (average 1.38) and low REE contents (average 51 ppm) reveal a hydrothermal source. Meanwhile, 87Sr/86Sr ratios of Mn ores are substantially higher than those of carbonate wall rocks and contemporaneous seawater, indicating mixing of radiogenic Sr from the Mn-rich hydrothermal extraction from underlying sediments. This explanation is supported by a positive linear correlation between 87Sr/86Sr ratios and Eu anomalies. The slightly positive Ce anomaly of most Mn carbonate ore samples is mirrored in the negative Ce anomaly of black shale, while different Ce anomalies provide evidence that Mn redox cycling took place across a sub-oxic to anoxic/euxinic water interface. The euxinic conditions, as evidenced by the co-occurrence of fine-grained disseminated pyrite to framboidal aggregates (average diameters <5 μm) with rhodochrosite, can account for the high Mn/Fe ratios via ongoing Fe-sulfide precipitation. Calcite introduction to metal-rich hydrothermal waters with a lower pH relative to surface waters, together with Mn-oxide reduction and sulfate reduction, triggers substantial increases in rhodochrosite saturation and precipitation near the water–sediment interface. Subsequently, increasing Ca2+ in early diagenesis resulted in the precipitation of kutnohorite rims. Altogether, we develop a hydrothermal sedimentary model of the Gaoyan Mn mineralization with rhodochrosite spherulites as the hydrothermal sedimentary mineral phases, and kutnohorite forming during early diagenesis. Slightly light carbon isotope compositions (∼–6.1‰) of the manganese carbonate ores than those of normal dolostones (∼–4.8‰) suggest a limited carbon source from oxidation of organic material by methanogenesis processes during burial diagenesis. This model supports the model for direct Mn-carbonate precipitation from redox-stratified water columns and means that sedimentary Mn mineralization may be mainly controlled by hydrothermal contribution, rather than seawater redox conditions. This means exploration strategies that focus on oxic zone alone as an indication of prospectivity may be ineffective.