Zinc- and cadmium-isotope evidence for redox-driven perturbations to global micronutrient cycles during Oceanic Anoxic Event 2 (Late Cretaceous)

This study uses organic-rich sediments from the Tarfaya Basin, Morocco, to assess the Cd- and Zn-isotope response to dramatic global palaeoenvironmental change during the Cenomanian–Turonian interval (Late Cretaceous). These organic-rich continental-margin deposits include an expression of Oceanic Anoxic Event 2 (OAE 2, ∼94 Ma), an interval associated with the spread of low-oxygen marine environments and widespread burial of organic-rich sediments. Due to placement of the Tarfaya Basin in a region of upwelling and relatively constant local environmental conditions, the stratigraphic variations in δ114Cd and δ66Zn values largely reflect changes in the seawater isotopic composition of the sub-surface proto-North Atlantic Ocean. Positive shifts of ∼0.2–0.3‰ away from background values in δ114Cd and δ66Zn are observed during the main phase of the positive carbon-isotope excursion associated with OAE 2. These isotopic shifts are coeval with decreases in Cd/TOC and Zn/TOC ratios and thus imply that drawdown of isotopically light Cd and Zn from seawater inventories was a result of extensive burial of these metals in organic-rich marine sediments globally. Low δ66Zn values during the Plenus Cold Event, a cooler episode during OAE 2, are similar in timing and magnitude to variations found in the English Chalk (Eastbourne, UK) and support the inference of a global control on these isotopic excursions. The δ66Zn values during the Plenus Cold Event are taken to record global oxygenation, possibly including the remobilization of isotopically light Zn from continental-margin sediments. A considerably smaller change in δ114Cd values for this interval implies that the Cd- and Zn-isotope systems can provide information about slightly different environmental processes, with global seawater composition with respect to Zn also being influenced by the magnitude of oxic removal sinks and isotopically light Zn input fluxes from sediments and hydrothermal fluids

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

Integrated stratigraphy of the Kimmeridge Clay Formation (Upper Jurassic) based on exposures and boreholes in south Dorset, UK

For the purposes of a high-resolution multi-disciplinary study of the Upper Jurassic Kimmeridge Clay Formation, two boreholes were drilled at Swanworth Quarry and one at Metherhills, south Dorset, UK. Together, the cores represent the first complete section through the entire formation close to the type section. We present graphic logs that record the stratigraphy of the cores, and outline the complementary geophysical and analytical data sets (gamma ray, magnetic susceptibility, total organic carbon, carbonate, [delta]13Corg). Of particular note are the new borehole data from the lowermost part of the formation which does not crop out in the type area. Detailed logs are available for download from the Kimmeridge Drilling Project web-site at http://kimmeridge.earth.ox.ac.uk/. Of further interest is a mid-eudoxus Zone positive shift in the [delta]13Corg record, a feature that is also registered in Tethyan carbonate successions, suggesting that it is a regional event and may therefore be useful for correlation. The lithostratigraphy of the cores has been precisely correlated with the nearby cliff section, which has also been examined and re-described. Magnetic-susceptibility and spectral gamma-ray measurements were made at a regular spacing through the succession, and facilitate core-to-exposure correlation. The strata of the exposure and core have been subdivided into four main mudrock lithological types: (a) medium-dark–dark-grey marl; (b) medium-dark–dark grey–greenish black shale; (c) dark-grey–olive-black laminated shale; (d) greyish-black–brownish-black mudstone. The sections also contain subordinate amounts of siltstone, limestone and dolostone. Comparison of the type section with the cores reveals slight lithological variation and notable thickness differences between the coeval strata. The proximity of the boreholes and different parts of the type section to the Purbeck–Isle of Wight Disturbance is proposed as a likely control on the thickness changes

Did Late Cretaceous cooling trigger the Campanian–Maastrichtian Boundary Event?

The Campanian-Maastrichtian (83-66 Ma) was a period of global climate cooling, featuring significant negative carbon-isotope (delta C-13) anomalies, such as the Late Campanian Event (LCE) and the Campanian-Maastrichtian Boundary Event (CMBE). A variety of factors, including changes in temperature, oceanic circulation and gateway opening, have been invoked to explain these delta C-13 perturbations, but no precise mechanism has yet been well constrained. In order to improve our understanding of these events, we measured stable carbon and oxygen isotopes of hemipelagic sediments from the Shuqualak-Evans cored borehole (Mississippi, USA) and compared the data with previously published sea-surface temperature (SST) estimates from the same core. We found that the CMBE can be recognised, unambiguously, in the Shuqualak-Evans core, and that it is associated with an interval of cooler SSTs suggesting a possible mechanistic link between palaeotemperat ure change and this event. Determining the precise position of the LCE in the Shuqualak-Evans core is more problematic, but it may also be associated with cooler SSTs. Our combined records of carbon cycling and SSTs compare well with other studies and provide evidence that cooling during the CMBE (and possibly LCE) was global in nature and affected surface waters, in addition to the deep-ocean. We suggest that short-term cooling drove intensification of high-latitude deep-water formation, which in turn led to changes in the ratio of carbonate to organic carbon burial that led to a negative delta C-13 excursion. Critically, the absence of warming during these intervals implies that the Late Cretaceous events must not have been associated with an appreciable increase in atmospheric pCO(2), and was likely associated with decreased pCO(2)

Helium-isotope constraints on palaeoceanographic change and sedimentation rates during precession cycles (Cenomanian Scaglia Bianca Formation, central Italy)

For much of the pelagic sedimentary record, time control is limited to the resolution of precession cycles (ca 20 kyr): the Milankovitch parameter that forms the most detailed metronome for the Cenozoic and Mesozoic Eras. The influence of precession is often detected in lithological alternations, where the duration represented by individual lithologies is not well constrained. Here the novel technique of extraterrestrial helium abundance (3HeET) is used to investigate the sedimentation dynamics and palaeoceanography within individual precessional cycles. High-resolution 3HeET timescales were produced for four precession cycles from the rhythmically bedded Scaglia Bianca Formation, a sequence of Upper Cretaceous (Cenomanian) deep-marine pelagic limestones from central Italy that are well characterized by cyclostratigraphy. Using 3HeET concentrations as a proxy for sedimentation rate allows instantaneous sedimentation rates and organic-carbon mass accumulation rates to be calculated for each bed within a precession cycle. Eccentricity is known to modulate the amplitude of precession forcing, and precession cycles deposited under eccentricity maxima and minima were selected for comparison. Lithological changes through these chert–(black shale)–limestone cycles are explained using the concept of ‘palaeoenvironmental thresholds’; these timescale calculations indicate that when the amplitude of precessional insolation forcing was greatest (at eccentricity maxima) the palaeoenvironmental system spent longer in the more nutrient-rich environment under which siliceous and organic-rich sediments were deposited, reflecting increased time spent above a ‘threshold’ insolation level. Estimates of primary productivity are relatively elevated for organic-rich beds. An increase in the flux of terrestrial helium (4Heterr) during the deposition of cherts may have been coincident with an increase in terrestrially derived nutrients. The presented results indicate great potential for the use of 3HeET to understand past oceanographic, climatic and sedimentological processes at high temporal resolution

A re‐evaluation of the Plenus Cold Event, and the links between CO2, temperature, and seawater chemistry during OAE 2

International audienceThe greenhouse world of the mid‐Cretaceous (~94 Ma) was punctuated by an episode of abrupt climatic upheaval: Oceanic Anoxic Event 2 (OAE 2). High‐resolution climate records reveal considerable changes in temperature, carbon cycling, and ocean chemistry during this climatic perturbation. In particular, an interval of cooling has been detected in the English Chalk on the basis of an invasive boreal fauna and bulk oxygen‐isotope excursions registered during the early stages of OAE 2—a phenomenon known as the Plenus Cold Event (PCE), which has tentatively been correlated with climatic shifts worldwide.Here we present new high‐resolution neodymium‐, carbon‐, and oxygen‐isotope data, as well as elemental chromium concentrations and cerium anomalies, from the English Chalk exposed at Dover, UK, which we evaluate in the context of >400 records from across the globe. A negative carbon‐isotope excursion that correlates with the original ‘PCE’ is consistently expressed worldwide, and CO2 proxy records, where available, indicate a rise and subsequent fall in CO2 over the Plenus interval. However, variability in the timing and expression of cooling at different sites suggests that, although sea‐surface paleo‐temperatures may reflect a response to global CO2 change, local processes likely played a dominant role at many sites. Variability in the timing and expression of changes in water‐mass character, and problems in determining the driver of observed proxy changes, suggest that no single simple mechanism can link the carbon cycle to oceanography during the Plenus interval and other factors including upwelling and circulation patterns were locally important. As such, it is proposed that the Plenus carbon‐isotope event is a more reliable stratigraphic marker to identify the Plenus interval, rather than any climatic shifts that may have been overprinted by local effects

No evidence for a volcanic trigger for late Cambrian carbon-cycle perturbations

The early Paleozoic was marked by several carbon-cycle perturbations and associated carbon-isotope excursions (CIEs). Whether these CIEs are connected to significant (external) triggers, as is commonly considered to be the case for CIEs in the Mesozoic and Cenozoic, or result from small carbon-cycle imbalances that became amplified through lack of efficient silicate weathering or other feedbacks remains unclear. We present concentration and isotope data for sedimentary mercury (Hg) and osmium (Os) to assess the impact of subaerial and submarine volcanism and weathering during the late Cambrian and early Ordovician. Data from the Alum Shale Formation (Sweden) cover the Steptoean positive carbon-isotope excursion (SPICE; ca. 497–494 Ma), a period marked by marine anoxia and biotic overturning, and several smaller CIEs extending into the early Ordovician. Our Hg and Os data offer no strong evidence that the CIEs present in our record were driven by (globally) elevated volcanism or continental weathering. Organic-carbon and Hg concentrations covary cyclically, providing further evidence of an unperturbed Hg cycle. Mesozoic and Cenozoic CIEs are commonly linked to enhanced volcanic activity and weathering, but similar late Cambrian–early Ordovician events cannot easily be connected to such external triggers. Our results are more consistent with reduced early Paleozoic carbon-cycle resilience that allowed small imbalances to develop into large CIEs

The toarcian oceanic anoxic event (Early Jurassic) in the Neuquén Basin, Argentina: A reassessment of age and carbon isotope stratigraphy

The Toarcian oceanic anoxic event (T-OAE) is recorded by the presence of globally distributed marine organic carbon– rich black shales and a negative carbon isotope shift, with δ13Corg values as low as -33‰, interrupting an overarching positive excursion. Here we present new biostratigraphic data and high-resolution δ13Corg data from two Southern Hemisphere localities: Arroyo Serrucho in the north and Arroyo Lapa in the south of the Neuquén Basin, Argentina. Previous studies at these localities aimed to provide an accurate numerical age for the T-OAE and characterization of its carbon isotope stratigraphy. The new carbon isotope data and ammonite biostratigraphy presented here from Arroyo Serrucho show the T-OAE to be recorded lower in the section than supposed by previous authors, thus calling into question the published age of the T-OAE in this section. A newly investigated exposure at Arroyo Lapa North shows a complex carbon isotope record with at least three high-amplitude fluctuations in the hoelderi zone (equivalent to the serpentinum zone in northwestern Europe), with δ13Corg values of <-28‰, and two intervening positive isotope excursions, with δ13Corg values around -24‰. At Arroyo Lapa South, the characteristic major stepped negative carbon isotope excursion is recorded, with δ13Corg values of <-30‰ and total organic-carbon contents increasing to 11%; above this level an erosional surface of a submarine channel truncates the section. These new data are globally correlative and unambiguously illustrate the global reach of the T-OAE.Fil: Al Suwaidi, Aisha H.. Petroleum Institute University; Emiratos Árabes UnidosFil: Hesselbo, Stephen P.. University of Exeter; Reino UnidoFil: Damborenea, Susana Ester. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Paleozoología Invertebrados; ArgentinaFil: Manceñido, Miguel Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo. División Paleozoología Invertebrados; ArgentinaFil: Jenkyns, Hugh C.. University of Oxford; Reino UnidoFil: Riccardi, Alberto Carlos. Universidad Nacional de La Plata. Facultad de Ciencias Naturales y Museo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata; ArgentinaFil: Angelozzi, Gladys Noemí. YPF - Tecnología; ArgentinaFil: Baudin, François. Université Pierre et Marie Curie; Franci

Orbital pacing and secular evolution of the Early Jurassic carbon cycle

Cyclic variations in Earth’s orbit drive periodic changes in the ocean–atmosphere system at a time scale of tens to hundreds of thousands of years. The Mochras δ13CTOC record illustrates the continued impact of long-eccentricity (405-ky) orbital forcing on the carbon cycle over at least ∼18 My of Early Jurassic time and emphasizes orbital forcing as a driving mechanism behind medium-amplitude δ13C fluctuations superimposed on larger-scale trends that are driven by other variables such as tectonically determined paleogeography and eruption of large igneous provinces. The dataset provides a framework for distinguishing between internal Earth processes and solar-system dynamics as the driving mechanism for Early Jurassic δ13C fluctuations and provides an astronomical time scale for the Sinemurian Stage

Astronomical constraints on the duration of the Early Jurassic Pliensbachian Stage and global climatic fluctuations

The Early Jurassic was marked by multiple periods of major global climatic and palaeoceanographic change, biotic turnover and perturbed global geochemical cycles, commonly linked to large igneous province volcanism. This epoch was also characterised by the initial break-up of the super-continent Pangaea and the opening and formation of shallow-marine basins and ocean gateways, the timing of which are poorly constrained. Here, we show that the Pliensbachian Stage and the Sinemurian–Pliensbachian global carbon-cycle perturbation (marked by a negative shift in δ13Cδ13C of 2–4‰2–4‰), have respective durations of ∼8.7 and ∼2 Myr. We astronomically tune the floating Pliensbachian time scale to the 405 Kyr eccentricity solution (La2010d), and propose a revised Early Jurassic time scale with a significantly shortened Sinemurian Stage duration of 6.9±0.4 Myr6.9±0.4 Myr. When calibrated against the new time scale, the existing Pliensbachian seawater 87Sr/86Sr record shows relatively stable values during the first ∼2 Myr of the Pliensbachian, superimposed on the long-term Early Jurassic decline in 87Sr/86Sr. This plateau in 87Sr/86Sr values coincides with the Sinemurian–Pliensbachian boundary carbon-cycle perturbation. It is possibly linked to a late phase of Central Atlantic Magmatic Province (CAMP) volcanism that induced enhanced global weathering of continental crustal materials, leading to an elevated radiogenic strontium flux to the global ocean