Global perturbations to the Early Jurassic environment (∼201 to ∼174 Ma), notably during the Triassic–Jurassic transition and Toarcian Oceanic Anoxic Event, are well studied and largely associated with volcanogenic greenhouse gas emissions released by large igneous provinces. The long-term secular evolution, timing, and pacing of changes in the Early Jurassic carbon cycle that provide context for these events are thus far poorly understood due to a lack of continuous high-resolution δ13C data. Here we present a δ13CTOC record for the uppermost Rhaetian (Triassic) to Pliensbachian (Lower Jurassic), derived from a calcareous mudstone succession of the exceptionally expanded Llanbedr (Mochras Farm) borehole, Cardigan Bay Basin, Wales, United Kingdom. Combined with existing δ13CTOC data from the Toarcian, the compilation covers the entire Lower Jurassic. The dataset reproduces large-amplitude δ13CTOC excursions (>3‰) recognized elsewhere, at the Sinemurian–Pliensbachian transition and in the lower Toarcian serpentinum zone, as well as several previously identified medium-amplitude (∼0.5 to 2‰) shifts in the Hettangian to Pliensbachian interval. In addition, multiple hitherto undiscovered isotope shifts of comparable amplitude and stratigraphic extent are recorded, demonstrating that those similar features described earlier from stratigraphically more limited sections are nonunique in a long-term context. These shifts are identified as long-eccentricity (∼405-ky) orbital cycles. Orbital tuning of the δ13CTOC record provides the basis for an astrochronological duration estimate for the Pliensbachian and Sinemurian, giving implications for the duration of the Hettangian Stage. Overall the chemostratigraphy illustrates particular sensitivity of the marine carbon cycle to long-eccentricity orbital forcing.

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Little is known about the fractionation of Li isotopes during formation of biogenic carbonates, which form the most promising geological archives of past seawater composition.Here we investigated the Li isotope composition (δ 7 Li) and Li/Ca ratios of organisms that are abundant in the Phanerozoic record, mollusks (mostly bivalves), echinoderms, and brachiopods. The measured samples include (i) modern calcite and aragonite shells from variable species and natural environments (13 mollusk samples, 5 brachiopods and 3 echinoderms), and (ii) shells from organisms grown under controlled conditions at various temperatures. When possible, the mollusk shell ultrastructure was micro-sampled in order to assess intra-shell heterogeneity. In this paper, we systematically characterize the respective influence of mineralogy, temperature, and biological processes on the δ 7 Li and Li/Ca of these shells and compare with published data for other taxa (foraminifera and corals).Aragonitic mollusks have the lowest δ 7 Li, ranging from +16 to +22‰, echinoderms have constant δ 7 Li of about +24‰, brachiopods have δ 7 Li of +25 to +28‰, and finally calcitic mollusks have the largest range and highest δ 7 Li values, ranging from +25‰ to +40‰. Measured brachiopods have similar δ 7 Li compared to inorganic calcite precipitated from seawater (δ 7 Li of +27 to +29‰), indicating minimum influence of vital effects, as also observed for other isotope systems and making them a potentially viable proxy of past seawater composition. Calcitic mollusks, on the contrary, are not a good archive for seawater paleo-δ 7 Li because many samples have significantly higher δ 7 Li values than inorganic calcite and display large inter-species variability, which suggest large vital effects. In addition, we observe very large intra-shell variability, in particular for mixed calcitearagonite shells (over 20‰ variability), but also in mono-mineralic shells (up to 12‰ variability). Aragonitic bivalves have less variable δ 7 Li (7‰ variability) compared to calcitic mollusks, but with significantly lower δ 7 Li compared to inorganic aragonite, indicating the existence of vital effects. Bivalves grown at various temperatures show that temperature has only a minor influence on fractionation of Li isotopes during shell precipitation. Interestingly, we observe a strong correlation (R 2 =0.83) between the Li/Mg ratio in bivalve Mytilus edulis and temperature with potential implications for paleo-temperature reconstructions.Finally, we observe a negative correlation between the δ 7 Li and both the Li/Ca and Mg/Ca ratio of calcite mollusks, which we relate to biomineralization processes.

Abstract:The biostratigraphy of Sinemurian to lower Toarcian calcareous nannofossils has been investigated in the Sancerre-Couy core (Paris Basin), which contains a mixed assemblage of species with affinities to the northern and southern areas of the peritethyan realm, thus allowing for the use and calibration of the Mediterranean Province (Italy/S France) and NW Europe (UK) biozonation schemes. This study is based on semi-quantitative analyses of the calcareous nannofossil assemblage performed on 145 samples and the recorded bioevents are calibrated to the NW European Ammonite Zonation and to a new organic carbon isotope curve based on 385 data points. The main bioevents, i.e. the first occurrences of Parhabdolithus liasicus, Crepidolithus pliensbachensis, Crepidolithus crassus, Mitrolithus lenticularis, Similiscutum cruciulus sensu lato, Lotharingius hauffii, Crepidolithus cavus and Lotharingius sigillatus as well as the last occurrence of Parhabdolithus robustus, have been identified. However, we show that a large number of standard biostratigraphic markers show inconsistent occurrences at the base and top of their range, possibly accounting for some of the significant discrepancies observed between the different domains. In addition to the nine main bioevents used for the biozonation of the core, we document an additional 50 distinct bioevents, evaluate their reliability and discuss their potential significance by comparison to previous studies. A total of five significant negative organic carbon isotope excursions are identified and defined in the Paris Basin including the well-documented Sinemurian-Pliensbachian boundary event. One positive excursion is further defined in the Pliensbachian interval. Our calibration of high-resolution calcareous nannofossil biostratigraphy to ammonite biostratigraphy and organic carbon isotopes represents a new stratigraphic reference for the Lower Jurassic series.

Many aspects of the supposed hyperthermal Toarcian Oceanic Anoxic Event (T-OAE, Early Jurassic, c. 182 Ma) are well understood but a lack of robust palaeotemperature data severely limits reconstruction of the processes that drove the t-oAe and associated environmental and biotic changes. new oxygen isotope data from calcite shells of the benthic fauna suggest that bottom water temperatures in the western Tethys were elevated by c. 3.5 °C through the entire T-OAE. Modelling supports the idea that widespread marine anoxia was induced by a greenhouse-driven weathering pulse, and is compatible with the OAE duration being extended by limitation of the global silicate weathering flux. In the western Tethys Ocean, the later part of the T-OAE is characterized by abundant occurrences of the brachiopod Soaresirhynchia, which exhibits characteristics of slow-growing, deep sea brachiopods. The unlikely success of Soaresirhynchia in a hyperthermal event is attributed here to low metabolic rate, which put it at an advantage over other species from shallow epicontinental environments with higher metabolic demand.

Citation for published item:hiultD xiols nd uhlD wih nd llmnnD glemens F nd uorteD ghristoph nd uempD hvid fF nd qr¤ okeD hrren F nd resseloD tephen F @PHIVA 9he wider ontext of the vower turssi orin oeni noxi event in orkshire ostl outropsD uF9D roeedings of the qeologists9 essoitionFD IPW @QAF ppF QUPEQWIF Further information on publisher's website: httpsXGGdoiForgGIHFIHITGjFpgeolFPHIUFIHFHHU Publisher's copyright statement: c 2017 This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe Toarcian Oceanic Anoxic Event (T-OAE, ~183 Ma) was characterized by enhanced carbon burial, a prominent negative carbon-isotope excursion (CIE) in marine carbonate and organic matter, and numerous geochemical anomalies. A precursor excursion has also been documented at the Pliensbachian/Toarcian boundary, but its possible causes are less constrained. The T-OAE is intensively studied in the Cleveland Basin, Yorkshire, UK, whose sedimentary deposits have been litho-, bio-and chemostratigraphically characterized. Here, we present new elemental data produced by hand-held X-ray fluorescence analysis to test the expression of redox-sensitive trace metals and detrital elements across the upper Pliensbachian to mid-Toarcian of the Cleveland Basin. Detrital elemental concentrations (Al, Si, Ti, Zr) are used as proxies for siliciclastic grain content and thus, sea-level change, which match previous sequence stratigraphic interpretations from the Cleveland Basin. The timescale of the event is debated, though our new elemental proxies of relative sea level change show evidence for a cyclicity of 360 cm that may be indicative of ~405 kyr eccentricity cycles in Yorkshire. Trends in total organic carbon and redox-sensitive elements (S, Fe, Mo, As) confirm scenarios of widespread ocean deoxygenation across the T-OAE. The correlation of comparable trends in Mo across the T-OAE in Yorkshire and the Paris Basin suggests a similar oceanic drawdown of this element accompanying widespread anoxia in the two basins. Data from Yorkshire point to a transgressive trend at the time of the Mo drawdown, which contradicts the "basin restriction" model for the euxinic conditions that characterise the CIE interval.

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