Lithium-isotope evidence for enhanced silicate weathering during OAE 1a (Early Aptian Selli event)

An abrupt rise in temperature, forced by a massive input of CO2 into the atmosphere, is commonly invoked as the main trigger for Oceanic Anoxic Events (OAEs). Global warming initiated a cascade of palaeoenvironmental perturbations starting with increased continental weathering and an accelerated hydrological cycle that delivered higher loads of nutrients to coastal areas, stimulating biological productivity. The end-result was widespread anoxia and deposition of black shales: the hallmarks of OAEs. In order to assess the role of weathering as both an OAE initiator and terminator (via CO2 sequestration) during the Early Aptian OAE 1a (Selli Event, ∼120 Ma) the isotopic ratio of lithium isotopes was analysed in three sections of shallow-marine carbonates from the Pacific and Tethyan realms and one basinal pelagic section from the Tethyan domain. Because the isotopic composition of lithium in seawater is largely controlled by continental silicate weathering and high- and low-temperature alteration of basaltic material, a shift to lighter δ7Li values is expected to characterize OAEs. The studied sections illustrate this phenomenon: δ7Li values decrease to a minimum coincident with the negative carbon-isotope excursion that effectively records the onset of OAE 1a. A second negative δ7Li excursion occurs coeval with the minimum in strontium isotopes after the event. The striking similarity to the strontium-isotope record argues for a common driver. The formation and destruction (weathering) of an oceanic LIP could account for the parallel trend in both isotope systems. The double-spike in lithium isotopes is probably related to a change in weathering congruencies. Such a chemostratigraphy is consistent with the hypothesis that an increase in silicate weathering, in conjunction with organic-carbon burial, led to drawdown of atmospheric CO2 during the early Aptian OAE 1a

Stratigraphic completeness and resolution in an ancient mudrock succession

Funded by NERC Fellowship. Grant Number: NE/I02089X/1 Santander student project scholarship grantPeer reviewedPublisher PD

A Field Guide to Finding Fossils on Mars

The Martian surface is cold, dry, exposed to biologically harmful radiation and apparently barren today. Nevertheless, there is clear geological evidence for warmer, wetter intervals in the past that could have supported life at or near the surface. This evidence has motivated National Aeronautics and Space Administration and European Space Agency to prioritize the search for any remains or traces of organisms from early Mars in forthcoming missions. Informed by (1) stratigraphic, mineralogical and geochemical data collected by previous and current missions, (2) Earth's fossil record, and (3) experimental studies of organic decay and preservation, we here consider whether, how, and where fossils and isotopic biosignatures could have been preserved in the depositional environments and mineralizing media thought to have been present in habitable settings on early Mars. We conclude that Noachian‐Hesperian Fe‐bearing clay‐rich fluvio‐lacustrine siliciclastic deposits, especially where enriched in silica, currently represent the most promising and best understood astropaleontological targets. Siliceous sinters would also be an excellent target, but their presence on Mars awaits confirmation. More work is needed to improve our understanding of fossil preservation in the context of other environments specific to Mars, particularly within evaporative salts and pore/fracture‐filling subsurface minerals

Magmatism, serpentinization and life: Insights through drilling the Atlantis Massif (IODP Expedition 357)

IODP Expedition 357 used two seabed drills to core 17 shallow holes at 9 sites across Atlantis Massif ocean core complex (Mid-Atlantic Ridge 30°N). The goals of this expedition were to investigate serpentinization processes and microbial activity in the shallow subsurface of highly altered ultramafic and mafic sequences that have been uplifted to the seafloor along a major detachment fault zone. More than 57 m of core were recovered, with borehole penetration ranging from 1.3 to 16.4 meters below seafloor, and core recovery as high as 75% of total penetration in one borehole. The cores show highly heterogeneous rock types and alteration associated with changes in bulk rock chemistry that reflect multiple phases of magmatism, fluid-rock interaction and mass transfer within the detachment fault zone. Recovered ultramafic rocks are dominated by pervasively serpentinized harzburgite with intervals of serpentinized dunite and minor pyroxenite veins; gabbroic rocks occur as melt impregnations and veins. Dolerite intrusions and basaltic rocks represent the latest magmatic activity. The proportion of mafic rocks is volumetrically less than the amount of mafic rocks recovered previously by drilling the central dome of Atlantis Massif at IODP Site U1309. This suggests a different mode of melt accumulation in the mantle peridotites at the ridge-transform intersection and/or a tectonic transposition of rock types within a complex detachment fault zone. The cores revealed a high degree of serpentinization and metasomatic alteration dominated by talc-amphibole-chlorite overprinting. Metasomatism is most prevalent at contacts between ultramafic and mafic domains (gabbroic and/or doleritic intrusions) and points to channeled fluid flow and silica mobility during exhumation along the detachment fault. The presence of the mafic lenses within the serpentinites and their alteration to mechanically weak talc, serpentine and chlorite may also be critical in the development of the detachment fault zone and may aid in continued unroofing of the upper mantle peridotite/gabbro sequences. New technologies were also developed for the seabed drills to enable biogeochemical and microbiological characterization of the environment. An in situ sensor package and water sampling system recorded real-time variations in dissolved methane, oxygen, pH, oxidation reduction potential (Eh), and temperature and during drilling and sampled bottom water after drilling. Systematic excursions in these parameters together with elevated hydrogen and methane concentrations in post-drilling fluids provide evidence for active serpentinization at all sites. In addition, chemical tracers were delivered into the drilling fluids for contamination testing, and a borehole plug system was successfully deployed at some sites for future fluid sampling. A major achievement of IODP Expedition 357 was to obtain microbiological samples along a west–east profile, which will provide a better understanding of how microbial communities evolve as ultramafic and mafic rocks are altered and emplaced on the seafloor. Strict sampling handling protocols allowed for very low limits of microbial cell detection, and our results show that the Atlantis Massif subsurface contains a relatively low density of microbial life

A study of biodegraded petroleum,The sulfur isotopic composition as correlation tool and indicator of alteration processes

Dans le cadre de cette thèse, nous nous sommes intéressés à la biodégradation dans les réservoirs pétroliers par l'étude moléculaire et isotopique du soufr de trois séries naturelles de pétrole et de carottes, provenant de l'Alberta (Canada), du bassin de Potiguar (Brésil) et de la vallée de San Joaquin (Californie, USA). L'étude moléculaire des échantillons a permis de leur attribuer un niveau de biodégradation sur l'échelle de Peters et Moldowan (1993) et a également mis en évidence des variations dans les degrés de maturité atteints et l'origine de la matière organique des échantillons, au sein de chaque série. Les corrélations entre les échantillons ainsi que l'identification de leurs roches-mères se sont révélées, par contre, complexes, du fait de l'altération des biomarqueurs. L'étude isotopique du soufr des pétroles étudiés a montré que le 34S constitue un outil de corrélation adapté. En effet, celui-ci ne semble pas affecté par la biodégradation des composés organo-soufrés. Cependant, dans les réservoirs susceptibles de contenir de l'H2S, notamment formé par la réduction bactérienne des sulfates, des réactions secondaires de sulfuration et d'échange de soufr pourraient se produire au cours de la biodégradation, et entraîner des variations de 34S du pétrole. A cet égard, des expériences de simulation au laboratoire ont mis en évidence que de telles réactions pouvaient effectivement se produire dans les conditions des réservoirs biodégradés. Enfin, des essais de couplage irm-GC/MS ont été réalisés pour mesurer la composition isotopique du soufr de composés individuels et ainsi approfondir l'étude des processus de sulfuration et d'échange de soufr.In the present study, the biodegradation of petroleum in reservoirs has been investigated by the molecular and isotopic study of three series of petroleum and core extracts, coming from Alberta (Canada), from the Potiguar Basin (Brazil) and from the San Joaquim Valley (California, USA). The molecular study allowed us to rank them according to the biodegradation scale of Peters and Moldowan (1993). This study also showed variations in the level of maturity reached by the samples and in the origin of the organic matter, within each series. However, correlations between oil samples as well as the identification of their source rocks appeared difficult to establish, due to the biodegradation of biomarkers. The sulfur isotopic study of oil samples showed that the 34S constitutes a good correlation tool because it does not seem to be affected by the biodegradation of sulfur organic compounds. However, this work suggested that secondary reactions of sulfur exchange and/or incorporation could happen with increasing biodegradation, and lead to variations in the sulfur isotopic composition of oil, in reservoirs containing H2S, generated notably by bacterial sulphate reduction. This was further corroborated by laboratory experiments of simulation. Finally, tests for the development of irm-GC/MS to measure the sulfur isotopic composition of individual compounds were performed in order to progress in the study of the sulfurization processes of organic matter

A volcanic CO2 pulse triggered the Cretaceous Oceanic Anoxic Event 1a and a biocalcification crisis

The Aptian Oceanic Anoxic Event 1a (OAE1a, ca.120 Ma ago) is one of the most prominent of a series of geologically brief intervals in the Cretaceous characterized by the deposition of organic carbon–rich sediments. OAEs reflect major perturbations in the global carbon cycle evidenced by sedimentary carbon isotope records. However, the triggering mechanisms for OAEs remain controversial. Here we present a bulk-rock and molecular (marine and terrestrial bio-markers) C isotope record at unprecedented time resolution, from the Cismon section of northern Italy, that shows that OAE1a conditions were reached over a period of several thousands of years through a stepwise perturbation of the carbon cycle. The documented sequence of events is most compatible with a trigger associated with increased CO2 emissions, possibly leading to a doubling of pCO2, which in turn caused larger C isotope fractionation in marine and terrestrial organisms and a major biotic crisis in the calcareous nannoplankton. Our data also show that a release of isotopically light carbon from partial methane hydrate dissociation probably played a minor role in the OAE1a carbon cycle perturbation

Orbital control on carbon cycle and oceanography in the mid-Cretaceous greenhouse

We established a new high-resolution carbonate carbon isotope record of the Albian interval of the Marne a Fucoidi Formation (Central Apennines, Italy), which was deposited on the southern margin of the western Tethys Ocean. Bulk carbonate sampled with 10–15 cm spacing was used for the construction of a continuous carbon isotope curve through the Albian stage. Spectral analyses reveal prominent 400 kyr cyclicity in the δ13C curve, which correlates with Milankovitch long eccentricity changes. Cycles occurring in our record resemble those observed in several Cenozoic δ13C records, suggesting that a link between orbital forcing and carbon cycling existed also under mid-Cretaceous greenhouse conditions. Based on comparisons with Cenozoic eccentricity-carbon cycle links we hypothesize that 400 kyr cycles in the mid-Cretaceous were related to a fluctuating monsoonal regime, coupled with an unstable oceanic structure, which made the oceanic carbon reservoir sensitive to orbital variations. In the Tethys these oceanographic conditions lasted until the Late Albian, and then were replaced by a more stable circulation mode, less sensitive to orbital forcing