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

Shale anisotropy and natural hydraulic fracture propagation: An example from the Jurassic (Toarcian) Posidonienschiefer, Germany

This is the author accepted manuscript. The final version is available from the publisher via the DOI in this recordData for this study are available at https://doi.org/10.26208/xny8-4t47.Cores recovered from the Jurassic (Toarcian) Posidonienschiefer (Posidonia Shale) in the Lower Saxony Basin, Germany, contain calcite filled fractures (veins) at low angle to bedding. The veins preferentially form where the shale is both organic rich and thermally mature, supporting previous interpretations that the veins formed as hydraulic fractures in response to volumetric expansion of organic material during catagenesis. Despite the presence of hydrocarbons during fracturing, the calcite fill is fibrous and so the veins appear to have contained a mineral-saturated aqueous solution as they formed. The veins also contain myriad host-rock inclusions having sub-millimetric spacing. These inclusions are strands of host rock that were entrained as the veins grew by separating the host rock along bedding planes, rather than cutting across planes. The veins therefore produce significantly more surface area—by a factor of roughly five, for the size of veins observed—compared to an inclusion-free fracture of the same size. Analysis of vein geometry indicates that, with propagation, fracture surface area increases with fracture length raised to a power between 1 and 2, assuming linear aperture-length scaling. As such, this type of fracture efficiently dissipates elastic strain energy as it lengthens, stabilizing propagation and precluding dynamic crack growth. The apparent separation of the host rock along bedding planes suggests that the mechanical weakness of bedding planes is the cause of this inherently stable style of propagationUniversity of Oxfor

Two-pronged kill mechanism at the end-Triassic mass extinction

High-resolution biomarker and compound-specific isotope distributions coupled with the degradation of calcareous fossil remnants reveal that intensive euxinia and decalcification (acidification) driven by Central Atlantic magmatic province (CAMP) activity formed a twopronged kill mechanism at the end-Triassic mass extinction. In a newly proposed extinction interval for the basal Blue Lias Formation (Bristol Channel Basin, UK), biomarker distributions reveal an episode of persistent photic zone euxinia (PZE) that extended further upward into the surface waters. In the same interval, shelly taxa almost completely disappear. Beginning in the basal paper shales of the Blue Lias Formation, a Lilliput assemblage is preserved consisting of only rare calcitic oysters (Liostrea) and ghost fossils of decalcified aragonitic bivalves. The stressors of PZE and decalcification parsimoniously explain the extinction event and inform possible combined causes of other biotic crises linked to emplacement of large igneous provinces, notably the end-Permian mass extinction, when PZE occurred on a broad and perhaps global scal

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

No effect of thermal maturity on the Mo-, U-, Cd- and Zn-isotope compositions of Lower Jurassic organic-rich sediments

The isotope ratios of redox-sensitive metals in organic-rich rocks are critical tools for quantifying the timing and severity of deoxygenation and nutrient cycling in Earth’s past. The resilience of isotopic data to thermal alteration of the host sediments over millions of years of burial is, however, largely unknown. We present molybdenum, uranium, cadmium, and zinc stable-isotope data from two stratigraphic successions of the same Lower Jurassic Posidonienschiefer unit in the Lower Saxony Basin of northern Germany that were affected by different burial histories. We show that thermal maturity had no effect on the isotopic compositions of these elements but does appear to have increased their concentrations in the rock. The data corroborate the results of laboratory-based maturation studies and provide constraints on the Mo, U, Cd, and Zn isotopic compositions of ca. 182 Ma seawater in the Lower Saxony Basin

No effect of thermal maturity on the Mo, U, Cd, and Zn isotope compositions of Lower Jurassic organic-rich sediments

This is the final version. Available on open access from the Geological Society of America via the DOI in this recordThe isotope ratios of redox-sensitive metals in organic-rich rocks are critical tools for quantifying the timing and severity of deoxygenation and nutrient cycling in Earth's past. The resilience of isotopic data to thermal alteration of the host sediments over millions of years of burial is, however, largely unknown. We present molybdenum, uranium, cadmium, and zinc stable-isotope data from two stratigraphic successions of the same Lower Jurassic Posidonienschiefer unit in the Lower Saxony Basin of northern Germany that were affected by different burial histories. We show that thermal maturity had no effect on the isotopic compositions of these elements but does appear to have increased their concentrations in the rock. The data corroborate the results of laboratory-based maturation studies and provide constraints on the Mo, U, Cd, and Zn isotopic compositions of ca. 182 Ma seawater in the Lower Saxony Basin.Shell Global Solutions International B.

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

This is the final version. Available on open access from Copernicus Publications via the DOI in this recordData availability: Full core scan data (https://doi.org/10.5285/91392f09-25d4-454c-aece-56bde0dbf3ba, BGS Core Scanning Facility, 2022) will be available after 1 November 2024 via the Natural Environment Research Council (NERC) National Geoscience Data Centre (https://webapps.bgs.ac.uk/services/ngdc/accessions/index.html#, last access: 12 October 2023). Downhole logging data (https://doi.org/10.5880/ICDP.5065.001​​​​​​​, Wonik, 2023) will be made available via the ICDP (https://www.icdp-online.org/projects/by-continent/europe/jet-uk/, last access: 12 October 2023). The JET Operational Report is published as Hesselbo et al. (2023); full information about the operational dataset, the logging dataset, data availability and the explanatory remarks is available on the ICPD-JET project website: https://www.icdp-online.org/projects/by-continent/europe/jet-uk/ (last access: 12 October 2023). A subset of data, additional biostratigraphic tables, and vector graphics files for Figs. 3–5 are included as the Supplement. Supplementary Data File 1 tabulates the corrected depth scale for Prees 2C. Supplementary Data File 2 summarizes the ammonite-based chronostratigraphy of the Prees 2 cores (ammonite identifications by Kevin N. Page). Supplementary Data File 3 summarizes the ammonite-based chronostratigraphy for the Hettangian to Early Pliensbachian of the Llanbedr (Mochras Farm) borehole (updated by Kevin N. Page). Supplementary Data File 4 tabulates the organic carbon-isotope ratios, TOC, and carbonate content of low-resolution samples taken at the Prees drill site; TOC and carbonate data are calculated using calibration based on portable XRF (Supplementary Data File 5) and a gas source isotope ratio mass spectrometer (Supplementary Data File 6). Supplementary Data File 5 tabulates portable XRF results for bulk rock powders of low-resolution samples taken at the Prees drill site; uncertainties stated in the table are given for the fit to the raw data and do not reflect the true reproducibility of the data. Empty fields indicate values under the detection limit. Sample SSK116001 acted as a repeat sample which was measured 70 times over the course of the data acquisition to determine the repeatability and drift of the instrument. LE stands for “light elements”. Supplementary Data File 6 tabulates gas source isotope ratio mass spectrometry (GS-IRMS) data (oxygen- and carbon-isotope ratios of carbonate as well as carbonate content calculated as calcite) for a set of 24 samples covering the entire core length and reflecting a representative spread of carbonate content. Comparison of GS-IRMS data with p-XRF data was used to create a calibration curve to calculate the carbonate (and TOC) content of all low-resolution samples. Supplementary Data File 7 tabulates pyrolysis data (Rock-Eval 6) for Prees 1 well cuttings and Wilkesley borehole samples. Supplementary Data File 8 contains vector graphics files (.svg) for Figs. 3–5.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 32.2 m below surface (m b.s.) and Prees 2B to 37.0 m b.s.) together with Early Jurassic and Late Triassic mudstone from the principal hole, Prees 2C, which was cored from 32.92 to 651.32 m (corrected core depth scale). Core recovery was 99.7 % 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 4 % total organic carbon (TOC) is recorded. Other parts of the succession are generally organic-lean, containing less than 1 % TOC. Carbon-isotope values from bulk organic matter have also been determined, initially at a resolution of ∼ 1 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.ICDPNatural Environment Research Council (NERC)German Research FoundationHungarian Scientific Research FundNational Science Centre, PolandPolish Geological Institut

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