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A newly located exposure of the Niveau Thomel, an organic-rich level at the Cenomanian-Tur-onian boundary, provides a highly expanded record of Oceanic Anoxic Event (OAE) 2, except for the lower relatively condensed glauconite-rich part of the section. The new locality, close to Barreme in the Vocontian Basin, SE France, is developed in deep-water hemi-pelagic facies (shales, marls, marly limestones, variably enriched in organic matter) and provides an improved understanding of palaeoceanographic events associated with OAE 2. Investigation of the biostratigraphy (nannofossils and planktonic foraminifera), organic and inorganic geochemistry (bulk carbonate δ 18 O, total organic carbon (TOC), bulk organic, biomarker-specific and carbonate δ13C, major and trace elements, and Rock-Eval data) has allowed characterization of the sediments in great detail. The combined study further constrains the detailed relationship between bio-and chemostratigraphy (particularly with respect to the details of the well-displayed positive carbon-isotope excursion) for this interval. The section also provides new evidence, in the form of a positive oxygen-isotope excursion and an offset between carbonate and organic-carbon carbon-isotope records, which confirms the importance of cooling accompanied by a drop in dissolved CO 2 in near-surface waters during the Plenus Cold Event that characterized the early part of OAE 2. Evidence for increased oxygenation of bottom waters, together with elevated concentrations of redox-sensitive and chalcophilic elements registered elsewhere through the level of the Plenus Cold Event, may be reflected in enhanced concentrations of iron (in glauconite) and nickel in coeval strata from the Clot Chevalier section. © 2018 Gebrüder Borntraeger, Stuttgart, Germany.

The Campanian-Maastrichtian (83-66 Ma) was a period of global climate cooling, featuring significant negative carbon-isotope (d13C) 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 d13C 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 palaeotemperature 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 d13C 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 pCO2, and was likely associated with decreased pCO2.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (d13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ~0.40 to ~0.53, in addition to new data that show elevated 187Os/188Os (from ~0.42 to ~0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.

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The Early Jurassic was characterized by a global disturbance of the carbon cycle known as the Toarcian Oceanic Anoxic Event (T-OAE). This event is recorded worldwide by a negative excursion in marine and terrestrial carbon-isotope ratios, typically interrupting an overarching positive trend attributed to large-scale burial of marine organic matter under oxygen-depleted conditions. The negative excursion is attributed to introduction of isotopically light carbon into the ocean-atmosphere system. Three sections from the Ionian Zone in Greece have been analysed in terms of biostratigraphy, Total Organic Carbon (TOC), CaCO3, δ13Ccarb, δ18Ocarb and δ13Corg. On the basis of bio- and chemostratigraphy, the age of Pliensbachian-Toarcian formations from the Ionian Zone in Greece has been refined and the geochemical signature of the T-OAE recognized. All sections illustrate the characteristic negative excursion in carbon isotopes from both carbonates and organic matter and, in only one locality, a positive excursion has also been recorded. The recognition of the T-OAE in this part of the Tethyan continental margin offers additional information on the global impact and amplitude of this important Jurassic palaeoceanographic event. © 2013.

Oceanic Anoxic Event 2 (OAE2), spanning the Cenomanian-Turonian boundary (CTB), represents one of the largest perturbations in the global carbon cycle in the last 100 Myr. The δ 13C carb, δ 13C org, and δ 18O chemostratigraphy of a black shale-bearing CTB succession in the Vocontian Basin of France is described and correlated at high resolution to the European CTB reference section at Eastbourne, England, and to successions in Germany, the equatorial and midlatitude proto-North Atlantic, and the U.S. Western Interior Seaway (WIS). 13C (offset between δ 13C carb and δ 13C org) is shown to be a good pCO 2 proxy that is consistent with pCO 2 records obtained using biomarker δ 13C data from Atlantic black shales and leaf stomata data from WIS sections. Boreal chalk δ 18O records show sea surface temperature (SST) changes that closely follow the 13C pCO 2 proxy and confirm TEX 86 results from deep ocean sites. Rising pCO 2 and SST during the Late Cenomanian is attributed to volcanic degassing; pCO 2 and SST maxima occurred at the onset of black shale deposition, followed by falling pCO 2 and cooling due to carbon sequestration by marine organic productivity and preservation, and increased silicate weathering. A marked pCO 2 minimum (∼25% fall) occurred with a SST minimum (Plenus Cold Event) showing >4C of cooling in ∼40 kyr. Renewed increases in pCO 2, SST, and δ 13C during latest Cenomanian black shale deposition suggest that a continuing volcanogenic CO 2 flux overrode further drawdown effects. Maximum pCO 2 and SST followed the end of OAE2, associated with a falling nutrient supply during the Early Turonian eustatic highstand. Copyright 2011 by the American Geophysical Union.

The Early Toarcian (Early Jurassic, c. 183 Ma) was characterized by an Oceanic Anoxic Event (T-OAE), primarily identified by the presence of globally distributed approximately coeval black organic-rich shales. This event corresponded with relatively high marine temperatures, mass extinction, and both positive and negative carbon-isotope excursions. Because most studies of the T-OAE have taken place in northern European and Tethyan palaeogeographic domains, there is considerable controversy as to the regional or global character of this event. Here, we present the first high-resolution integrated chemostratigraphic (carbonate, organic carbon, δ13 C carb, δ13Corg) and biostratigraphic (calcareous nannofossil) records from the Kastelli Pelites cropping out in the Pindos Zone, western Greece. During the Mesozoic, the Pindos Zone was a deep-sea oceanmargin basin, which formed in mid-Triassic times along the northeast passive margin of Apulia. In two sections through the Kastelli Pelites, the chemostratigraphic and biostratigraphic (nannofossil) signatures of the most organic-rich facies are identified as correlative with the Lower Toarcian, tenuicostatum/polymorphum-falciferum/serpentinum/levisoni ammonite zones, indicating that these sediments record the T-OAE. Both sections also display the characteristic negative carbon-isotope excursion in organic matter and carbonate. This occurrence reinforces the global significance of the Early Toarcian Oceanic Anoxic Event. © 2010 Cambridge University Press.

Integrated biostratigraphic (planktonic foraminifera, calcareous nannofossils), chemostratigraphic (bulk C and O isotopes) and compound-specific organic geochemical studies of a mid-Cretaceous pelagic carbonate - black shale succession of the Ionian Zone (western Greece), provide the first evidence for the Cenomanian-Turonian oceanic anoxic event (OAE2, 'Bonarelli' event) in mainland Greece. The event is manifested by the occurrence of a relatively thin (35 cm), yet exceptionally organic carbon-rich (44.5 wt% TOC), carbonate-free black shale, near the Cenomanian-Turonian boundary within the Vigla limestone formation (Berriasian-Turonian). Compared to the 'Bonarelli' black-shale interval from the type locality of OAE2 in Marche-Umbria, Italy, this black shale exhibits greatly reduced stratigraphic thickness, coupled with a considerable relative enrichment in TOC. Isotopically, enriched δ13C values for both bulk organic matter (-22.2‰) and specific organic compounds are up to 5‰ higher than those of underlying organic-rich strata of the Aptian-lower Albian Vigla Shale member, and thus compare very well with similar values of Cenomanian-Turonian black shale occurrences elsewhere. The relative predominance of bacterial hopanoids in the saturated, apolar lipid fraction of the OAE2 black shale of the Ionian Zone supports recent findings suggesting the abundance of N2-fixing cyanobacteria in Cretaceous oceans during the Cenomanian-Turonian and early Aptian oceanic anoxic events. © Springer-Verlag 2006.

Carbon stable-isotope variation through the Cenomanian–Santonian stages is characterized using data for 1769 bulk pelagic carbonate samples collected from seven Chalk successions in England. The sections show consistent stratigraphic trends and δ13C values that provide a basis for highresolution correlation. Positive and negative δ13Cexcursions and inflection points on the isotope profiles are used to define 72 isotope events. Key markers are provided by positive δ13C excursions of up to + 2‰: the Albian/CenomanianBoundary Event; Mid-Cenomanian Event I; theCenomanian/Turonian Boundary Event; the Bridgewick, Hitch Wood and Navigation events of Late Turonian age; and the Santonian/Campanian Boundary Event. Isotope events are isochronous within a framework provided by macrofossil datum levels and bentonite horizons. An age-calibrated composite δ13C reference curve and an isotope event stratigraphy are constructed using data from the English Chalk. The isotope stratigraphy is applied to successions in Germany, France, Spain and Italy. Correlation with pelagic sections at Gubbio, central Italy, demonstrates general agreement between biostratigraphic and chemostratigraphic criteria in the Cenomanian–Turonian stages, confirming established relationships between Tethyan planktonic foraminiferal and Boreal macrofossil biozonations. Correlation of the Coniacian–Santonian stages is less clear cut: magnetostratigraphic evidence for placing the base of Chron 33r near the base of the Upper Santonian is in good agreement with the carbon-isotope correlation, but generates significant anomalies regarding the placement of the Santonian and Campanian stage boundaries with respect to Tethyan planktonic foraminiferal and nannofossil zones. Isotope stratigraphy offers a more reliable criterion for detailed correlation of Cenomanian–Santonian strata than biostratigraphy.With the addition of Campanian δ13C data from one of the English sections, a composite Cenomanian–Campanian age-calibrated reference curve is presented that can be utilized in future chemostratigraphic studies. \ud The Cenomanian–Campanian carbon-isotope curve is remarkably similar in shape to supposedly eustatic sea-level curves: increasing δ13C values accompanying sea-level rise associated with transgression, and falling δ13C values characterizing sea-level fall and regression. The correlation between carbon isotopes and sea-level is explained by variations in epicontinental sea area affecting organic-matter burial fluxes: increasing shallow sea-floor area and increased accommodation space accompanying sea-level rise allowedmore efficient burial ofmarine organic matter, with the preferential removal of 12C from the marine carbon reservoir. During sea-level fall, reduced seafloor area, marine erosion of previously deposited sediments, and exposure of basin margins led to reduced organiccarbon burial fluxes and oxidation of previously deposited organic matter, causing falling δ13C values. Additionally, drowning of carbonate platforms during periods of rapid sea-level rise may have reduced the global inorganic relative to the organic carbon flux, further enhancing δ13C values, while renewed platform growth during late transgressions and highstands prompted increased carbonate deposition. Variations in nutrient supply, changing rates of oceanic turnover, and the sequestration or liberation of methane from gas hydrates may also have played a role in controlling carbon-isotope ratios.

We present new, detailed carbon-isotope records for bulk carbonate, total organic carbon (TOC) and phytane from three key sections spanning the Cenomanian-Turonian boundary interval (Eastbourne, England; Gubbio, Italy; Tarfaya, Morocco), with the purpose of establishing a common chemostratigraphic framework for Oceanic Anoxic Event (OAE) 2. Isotope curves from all localities are characterized by a positive carbon-isotope excursion of c. 4‰ for TOC and phytane and c. 2.5‰ for carbonate, although diagenetic overprinting appears to have obliterated the primary carbonate carbon-isotope signal in at least part of the Tarfaya section. Stratigraphically, peak ä13C values for all components are followed by intervals of high, near-constant ä13C in the form of an isotopic plateau. Recognition of an unambiguous return to background ä13C values above the plateau is, however, contentious in all sections, hence no firm chemostratigraphic marker for the end-point of the positive isotopic excursion can be established. The stratigraphically consistent first appearance of the calcareous nannofossil Quadrum gartneri at or near the Cenomanian-Turonian boundary as established by ammonite stratigraphy, in conjunction with the end of the ä13C maximum characteristic of the isotopic plateau, provides a potentially powerful tool for delimiting the stratigraphic extent and duration of OAE 2. This Oceanic Anoxic Event is demonstrated to be largely, if not wholly, confined to the latest part of the Cenomanian stage

We present new stable (C, O) isotopic, biostratigraphic and organic geochemical data for the Vigla Shale Member of the Ionian Zone in NW Greece, in order to characterize organic carbon-rich strata that potentially record the impact of Cretaceous Oceanic Anoxic Events (OAEs). In a section exposed near Gotzikas (NW Epirus), we sampled a number of decimetre-thick, organic carbon-rich units enclosed within marly, locally silicified, Vigla Limestone (Berriasian-Turonian). All these units are characterized by largely comparable bulk geochemical characteristics, indicating a common marine origin and low thermal maturity. However, the stratigraphically highest of these black shales is further distinguished by its much higher total organic-carbon (TOC) content (28.9 wt%) and Hydrogen Index (HI) (529), and much enriched δ13Corg value (-22.1‰). Planktonic foraminiferal and calcareous nannofossil biostratigraphy indicate a lower to middle Albian age for the strata immediately above, and a lower Aptian age for the strata below, the uppermost black shale. In terms of molecular organic geochemistry, the latter black shale is also relatively enriched in specific isoprenoidal compounds (especially monocyclic isoprenoids), whose isotopic values are as high as - 15‰, indicating a substantial archaeal contribution to the organic matter. The striking similarities between the molecular signatures of the uppermost Vigla black shale and coeval organic-rich strata from SE France and the North Atlantic (ODP Site 1049C) indicate that this level constitutes a record of the Paquier Event (OAE 1b). © 2004 Cambridge University Press.

The Mesozoic Era featured emplacement of a number of Large Igneous Provinces (LIPs), formed by the outpouring of millions of cubic kilometres of basaltic magma. The radiometric ages of several Mesozoic LIPs coincide with the dates of Oceanic Anoxic Events (OAEs). As a result of these coincidences, a causal link has been suggested, but never conclusively proven. This study explores the use of mercury as a possible direct link between the Karoo–Ferrar LIP and the coeval Toarcian OAE (T-OAE). Mercury is emitted to the atmosphere as a trace constituent of volcanic gas, and may be distributed globally before being deposited in sediments. Modern marine deposits show a strong linear correlation between mercury and organic-matter content. Results presented here indicate departures from such a simple linear relationship in sediments deposited during the T-OAE, and also during the Pliensbachian–Toarcian transition (an event that saw elevated benthic extinctions and carbon-cycle perturbations prior to the T-OAE). A number of depositional settings illustrate an increased mercury concentration in sediments that record one or both events, suggesting a rise in the depositional flux of this element. Complications to this relationship may arise from very organic-rich sediments potentially overprinting any Hg/TOC signal, whereas environments preserving negligible organic matter may leave no record of mercury deposition. However, the global distribution of coevally elevated Hg-rich levels suggests enhanced atmospheric mercury availability during the Early Toarcian, potentially aided by the apparent affinity of Hg for terrestrial organic matter, although the relative importance of aquatic vs terrestrial fixation of Hg in governing these enrichments remains uncertain. A perturbation in atmospheric Hg is most easily explained by enhanced volcanic output. It is suggested that extrusive igneous activity caused increased mercury flux to the Early Toarcian sedimentary realm, supporting the potential of this element as a proxy for ancient volcanism. This interpretation is consistent with a relationship between LIP formation and a perturbed carbon cycle during the Pliensbachian–Toarcian transition and T-OAE. The recording of these two distinct Hg excursions may also indicate that the Karoo–Ferrar LIP released volatiles in temporally distinct episodes, due either to multiple phases of magmatic emplacement or sporadic release of thermogenic gaseous products from intrusion of igneous material into volatile-rich lithologies.