Microbial vs thermogenic gas hydrates in the South Falkland Basin: BSR distribution and fluid origin

The South Falkland Basin hosts a working petroleum system, as well as one of the most recently discovered gas hydrate provinces of the South Atlantic Ocean. Using three-dimensional reflection seismic data, a series of bottom-simulating reflections (BSRs) are interpreted within two contrasting settings, (1) the thrust-cored anticlines, developed by the oblique convergence of the Scotia and the South American plates, and (2) the foreland basin, formed to the north of this plate boundary. These BSRs are interpreted as the base of the gas hydrate stability zone, and are associated with seismic indicators of underlying free-gas accumulations and overlying hydrate-bearing sediments. In the foreland basin, the BSR is laterally continuous for tens of kilometres, whereas in the fold belt, BSR occurrences are restricted to limited portions of the thrust-cored anticline crests. These observations, calibrated with sedimentological analyses and gas geochemistry, argue that the gas source for the gas hydrates within the thrust-cored anticlines is unrelated to in-situ microbial generation of methane, but instead is associated with the vertical seepage of thermogenic fluids from deeper cores of the anticlines. In contrast, the nature of the sediments in the foreland basin appears more favourable for the generation of shallow microbial methane. This study highlights that, in specific tectonic and depositional environments, the character of the BSR observed on reflection seismic data with the limited support of in-situ data, can be used to predict the most likely source of natural gas hydrate systems

A Southern Hemisphere record of global trace-metal drawdown and orbital modulation of organic-matter burial across the Cenomanian–Turonian boundary (Ocean Drilling Program Site 1138, Kerguelen Plateau)

Despite its assumed global nature, there are very few detailed stratigraphic records of the late Cenomanian to the early Turonian Oceanic Anoxic Event 2 from the Southern Hemisphere. A highly resolved record of environmental changes across the Cenomanian\u2013Turonian boundary interval is presented from Ocean Drilling Program Site 1138 on the central Kerguelen Plateau (southern Indian Ocean). The new data lead to three key observations. Firstly, detailed biostratigraphy and chemostratigraphy indicate that the record of Oceanic Anoxic Event 2 is not complete, with a hiatus spanning the onset of the event. A decrease in glauconite and highly weathered clays after the onset of Oceanic Anoxic Event 2 marks the end of the hiatus interval, which can be explained by a relative sea-level rise that increased sediment accommodation space on the Kerguelen Plateau margin. This change in depositional environment controlled the timing of the delayed peak in organic-matter burial during Oceanic Anoxic Event 2 at Site 1138 compared with other Oceanic Anoxic Event 2 locations worldwide. A second key observation is the presence of cyclic fluctuations in the quantity and composition of organic matter being buried on the central Kerguelen Plateau throughout the latter stages of Oceanic Anoxic Event 2 and the early Turonian. A close correspondence between organic matter, sedimentary elemental compositions and sediments recording sea-floor oxygenation suggests that the cycles were mainly productivity-driven phenomena. Available age-control points constrain the periodicity of the coupled changes in sedimentary parameters to ca 20 to 70 ka, suggesting a link between carbon burial and astronomically forced climatic variations (precession or obliquity) in the Southern Hemisphere mid-latitudes both during, and after, Oceanic Anoxic Event 2: fluctuations that were superimposed on the impact of global-scale processes. Finally, trace-metal data from the black-shale unit at Site 1138 provide the first evidence from outside of the proto-North Atlantic region for a global drawdown of seawater trace-metal (Mo) inventories during Oceanic Anoxic Event 2

Investigating the behavior of sedimentary mercury (Hg) during burial-related thermal maturation

Understanding the behavior of mercury (Hg) in organic-rich sediments as they undergo thermal maturation is important, for example, because enrichment of Hg in sedimentary deposits has become a widely used proxy for volcanism from Large Igneous Provinces (LIPs). In this study, we evaluate the effects of such processes on sedimentary Hg concentrations by investigating a common stratigraphic interval in three drill cores with different levels of thermal maturity (immature, mature and post-mature) in Toarcian sediments (Posidonienschiefer Formation) from the Lower Saxony Basin, Germany. We present Hg concentrations, bulk organic geochemistry, and total sulfur data. Mercury concentrations in the mature and post-mature sediments are increased >2-fold relative to the immature material, which is greater than any potential differences in original Hg concentrations in the studied successions prior to burial. Organic-carbon and host-rock mass loss during thermal maturation may have concentrated Hg in the mature sediments to some extent, provided Hg is considered effectively immobile. The increased Hg, TOC-normalized Hg, and TS-normalized Hg are most likely linked to the “closed system” behavior of Hg in sedimentary basins and the relatively low temperatures (70–260°C) during maturation that resulted in limited Hg mobility. More speculatively, a certain degree of redistribution of Hg within the mature sediments is suggested by its enrichment in distinct stratigraphic levels. Regardless of the exact mechanisms at play, the elevated Hg concentrations in mature sediments amplify both Hg/TOC and Hg/TS, implying that thermal effects must be considered when using normalized Hg as a proxy for far-field volcanic activity

Investigating the behavior of sedimentary mercury (Hg) during burial-related thermal maturation

Understanding the behavior of mercury (Hg) in organic-rich sediments as they undergo thermal maturation is important, for example, because enrichment of Hg in sedimentary deposits has become a widely used proxy for volcanism from Large Igneous Provinces (LIPs). In this study, we evaluate the effects of such processes on sedimentary Hg concentrations by investigating a common stratigraphic interval in three drill cores with different levels of thermal maturity (immature, mature and post-mature) in Toarcian sediments (Posidonienschiefer Formation) from the Lower Saxony Basin, Germany. We present Hg concentrations, bulk organic geochemistry, and total sulfur data. Mercury concentrations in the mature and post-mature sediments are increased >2-fold relative to the immature material, which is greater than any potential differences in original Hg concentrations in the studied successions prior to burial. Organic-carbon and host-rock mass loss during thermal maturation may have concentrated Hg in the mature sediments to some extent, provided Hg is considered effectively immobile. The increased Hg, TOC-normalized Hg, and TS-normalized Hg are most likely linked to the “closed system” behavior of Hg in sedimentary basins and the relatively low temperatures (70–260°C) during maturation that resulted in limited Hg mobility. More speculatively, a certain degree of redistribution of Hg within the mature sediments is suggested by its enrichment in distinct stratigraphic levels. Regardless of the exact mechanisms at play, the elevated Hg concentrations in mature sediments amplify both Hg/TOC and Hg/TS, implying that thermal effects must be considered when using normalized Hg as a proxy for far-field volcanic activity

Molybdenum-isotope chemostratigraphy and paleoceanography of the Toarcian Oceanic Anoxic Event (Early Jurassic)

Molybdenum (Mo)-isotope chemostratigraphy of organic-rich mudrocks has been a valuable tool for testing the hypothesis that the Toarcian Oceanic Anoxic Event (T-OAE, Early Jurassic, ~183 Ma) was characterized by the spread of marine euxinia (and organic-matter burial) at a global scale. However, the interpretation of existing Mo-isotope data for the T-OAE (from Yorkshire, Cleveland Basin, U.K.) is equivocal. In this study, three new Mo-isotope profiles are presented: from Dotternhausen Quarry (South German Basin, Germany), the Rijswijk core (West Netherlands Basin, Netherlands) and the Dogna core (Belluno Basin, northern Italy). Precise bio- and chemo34 stratigraphic correlation between the three sites allows a direct comparison of the data, enabling some key conclusions to be reached: (i) The Mo-isotope composition of seawater during the peak of the T-OAE was probably close to ~1.45 ‰, implicating a greater removal flux of sulphides from seawater, and a larger extent of global seafloor euxinia compared to the present day; (ii) Moisotope cycles previously identified in the Yorkshire sedimentary succession are attributed to changes in the degree of local 39 Mo drawdown from overlying Cleveland Basin seawater; (iii) The consistency of the new multi-site Mo-isotope dataset indicates a secular reduction in the burial of sulphides globally in the late stages of the T-OAE, implying a contraction in the extent of global marine euxinia; (iv) Subtle differences in the Mo-isotope composition of deposits formed in different euxinic sub-basins of the European epicontinental shelf were probably governed by local variations in basin hydrography and rates of water renewa

Nearshore euxinia in the photic zone of an ancient sea:Part II – The bigger picture and implications for understanding ocean anoxia

Biomarker, palaeontological and isotopic evidence suggests that the Late Permian carbonate seas, i.e. the Northern (NPB) and Southern (SPB) Permian basins of northern Pangea, were characterized by significant spatial and temporal variations in the palaeowater-column redox state. This is particularly the case with regard to the deposition of the Lopingian Zechstein cycle 2 carbonate rocks. A shelf to basin reconstruction of environmental conditions was achieved by analysing nearly 400 core samples from 49 wells. This allowed an evaluation of the spatial variations in facies and broad oceanographic conditions at the basin scale. Specifically, in the lower slope and shallow-basin facies of the northern margin of the SPB (present-day northern Poland and eastern Germany), highly variable concentrations of the green sulphur bacterial biomarkers chlorobactane and isorenieratane (and their likely degradation products, C15 to C31 2,3,6-aryl isoprenoids, indicative of photic zone euxinia) and homohopane indices (indicative of anoxia), combined with the presence of a benthic fauna and bioturbation, indicate a variable but occasionally anoxic/euxinic water column. Locally in lagoonal facies in the northern and southern margin of the SPB, euxinic conditions also developed but these were likely associated with localised conditions or benthic production in association with microbialites. The presence of gammacerane in the eastern SPB (south-eastern Germany and eastern Poland) suggests elevated salinities there, compatible with the restricted configuration of the basin. However, a lack of these signatures in basinal settings of the eastern SPB indicates that strongly reducing conditions were restricted to the lower slope and shallow-basin locations and restricted lagoons, and were not developed in the basin centre. Moreover, this anoxia/euxinia in marginal settings is restricted to the north-eastern part of the SPB. The south-eastern part of the SPB (SE Poland), in contrast, is devoid of evidence for PZE. The southern margin of the SPB is also characterized by generally oxic-suboxic conditions, with local anoxia limited to more restricted embayments, and elevated salinities limited to restricted oxic-anoxic lagoons. In the western SPB (NE England and adjacent offshore) and the NPB (Outer Moray Firth, offshore Scotland) the water columns were oxic-suboxic. Overall, it appears that high but episodic primary bioproductivity of organic matter was concentrated on (or even limited to) the lower slopes of the SPB's north-eastern margin and the restricted lagoons and shallow basin of its southern margin, leading to the formation of source rocks for petroleum in these areas. In addition, the temporal and geographical restriction of anoxia appears to have prevented the accumulation of large and more widespread quantities of organic matter; in fact TOC contents exhibit a poor correlation with ecological and anoxia indicators. Crucially, this work confirms that the strong evidence for PZE observed in shelf and lower slope/shallow-basin facies of the north-eastern SPB need not be associated with widespread, basin-scale anoxia; this conclusion has implications for organic matter burial, carbon cycling and biotic crises during other times in Earth history

Molecular and petrographical evidence for lacustrine environmental and biotic change in the palaeo-Sichuan mega-lake (China) during the Toarcian Oceanic Anoxic Event

The organic-rich upper Lower Jurassic Da'anzhai Member (Ziliujing Formation) of the Sichuan Basin, China is the first stratigraphically well-constrained lacustrine succession associated with the Toarcian Oceanic Anoxic Event (T-OAE; c. 183 Ma). The expansion of the palaeo-Sichuan mega-lake, probably one of the most extensive freshwater systems to have existed on the planet, is marked by large-scale lacustrine organic productivity and carbon burial during the T-OAE, possibly owing to intensified hydrological cycling and nutrient supply. New molecular biomarker and organic petrographical analyses, combined with bulk organic and inorganic geochemical and palynological data, are presented here, providing insight into aquatic productivity, land-plant biodiversity and terrestrial ecosystem evolution in continental interiors during the T-OAE. We show that lacustrine algal growth during the T-OAE accounted for a significant organic-matter flux to the lakebed in the palaeo-Sichuan mega-lake. Lacustrine water-column stratification during the T-OAE facilitated the formation of dysoxic–anoxic conditions at the lake bottom, favouring organic-matter preservation and carbon sequestration into organic-rich black shales in the Sichuan Basin. We attribute the palaeo-Sichuan mega-lake expansion to enhanced hydrological cycling in a more vigorous monsoonal climate in the hinterland during the T-OAE greenhouse

Zechstein Main Dolomite oil characteristics in the Southern Permian Basin:I. Polish and German sectors

Geochemical analyses were used to classify 39 Zechstein (Late Permian, Lopingian) Main Dolomite (Ca2) crude oil samples from fields in the eastern and southern sector of the Southern Permian Basin (SPB) of Europe and to provide new insights into the origin of the oil. Geochemical data indicate that Ca2 oils were generated in the early-to-late oil window and are mostly non-waxy oils. Various biomarker and stable carbon isotopic ratios were used to identify source and depositional settings for source rocks of Ca2 oils arranged within 10 distinct oil groups. Specifically, the geochemical analyses and oil-oil correlations revealed a set of characteristic biomarkers including an even-over-odd predominance (EOP) for the C20-30n-alkanes, C40 carotenoid occurrence (isorenieratane, chlorobactane, β-isorenieratane), bisnorhopane/hopane (BNH/H) ratios >0.1, high abundances of C35 homohopanes and elevated concentrations of C32 and C34 homohopanes, a predominance of C29 homologues among 4-desmethyl steranes in the majority of oil samples, and a high abundance of diasteranes. Stable carbon isotopes and biomarkers provided ample evidence that Ca2 oils were generated from predominantly algal-rich marly carbonate/evaporite source rocks located in the lower slope/shallow-basin and lagoonal facies of the Ca2 basin, all deposited under suboxic-anoxic (euxinic) conditions. In the case of all higher maturity oils, the source rocks could not be reliably identified but high (>2) C24Tet/C23 values suggest a carbonate-evaporite depositional setting

Initial results of coring at Prees, Cheshire Basin, UK (ICDP JET project): Towards an integrated stratigraphy, timescale, and Earth system understanding for the Early Jurassic

Drilling for the International Continental Scientific Drilling Program (ICDP) Early Jurassic Earth System and Timescale project (JET) was undertaken between October 2020 and January 2021. The drill site is situated in a small-scale synformal basin of the latest Triassic to Early Jurassic age that formed above the major Permian-Triassic half-graben system of the Cheshire Basin. The borehole is located to recover an expanded and complete succession to complement the legacy core from the Llanbedr (Mochras Farm) borehole drilled through 1967-1969 on the edge of the Cardigan Bay Basin, North Wales. The overall aim of the project is to construct an astronomically calibrated integrated timescale for the Early Jurassic and to provide insights into the operation of the Early Jurassic Earth system. Core of Quaternary age cover and Early Jurassic mudstone was obtained from two shallow partially cored geotechnical holes (Prees 2A to 32.2g¯m below surface (mg¯b.s.) and Prees 2B to 37.0g¯mg¯b.s.) together with Early Jurassic and Late Triassic mudstone from the principal hole, Prees 2C, which was cored from 32.92 to 651.32g¯m (corrected core depth scale). Core recovery was 99.7g¯% for Prees 2C. The ages of the recovered stratigraphy range from the Late Triassic (probably Rhaetian) to the Early Jurassic, Early Pliensbachian (Ibex Ammonoid Chronozone). All ammonoid chronozones have been identified for the drilled Early Jurassic strata. The full lithological succession comprises the Branscombe Mudstone and Blue Anchor formations of the Mercia Mudstone Group, the Westbury and Lilstock formations of the Penarth Group, and the Redcar Mudstone Formation of the Lias Group. A distinct interval of siltstone is recognized within the Late Sinemurian of the Redcar Mudstone Formation, and the name "Prees Siltstone Member"is proposed. Depositional environments range from playa lake in the Late Triassic to distal offshore marine in the Early Jurassic. Initial datasets compiled from the core include radiography, natural gamma ray, density, magnetic susceptibility, and X-ray fluorescence (XRF). A full suite of downhole logs was also run. Intervals of organic carbon enrichment occur in the Rhaetian (Late Triassic) Westbury Formation and in the earliest Hettangian and earliest Pliensbachian strata of the Redcar Mudstone Formation, where up to 4g¯% total organic carbon (TOC) is recorded. Other parts of the succession are generally organic-lean, containing less than 1g¯% TOC. Carbon-isotope values from bulk organic matter have also been determined, initially at a resolution of g1/4g¯1g¯m, and these provide the basis for detailed correlation between the Prees 2 succession and adjacent boreholes and Global Stratotype Section and Point (GSSP) outcrops. Multiple complementary studies are currently underway and preliminary results promise an astronomically calibrated biostratigraphy, magnetostratigraphy, and chemostratigraphy for the combined Prees and Mochras successions as well as insights into the dynamics of background processes and major palaeo-environmental changes