Understanding oxygenation throughout Earth history, particularly intervals where marine deoxygenation occurred, are crucial to investigating the changes in habitability on Earth. Marine deoxygenation events, in particular, can result in changes in the carbon, sulfur, and iron cycles on our planet. Changes in these elemental cycles lead to distinctive variation in the chemical composition of seawater that is recorded in marine sediments that are preserved into the sedimentary record. Our modern ocean is experiencing rapid deoxygenation, thus understanding the duration and extent of ancient deoxygenation events is vital to predicting future climate scenarios. Here I investigated the record of environmental change during the Early Jurassic Toarcian Oceanic Anoxic Event or T-OAE (~183 Ma). The first chapter of this dissertation investigates the record of marine anoxia across the Pliensbachian to Toarcian transition. Specifically, I investigate the temporal and geographic development of anoxia across three basins from the European Epicontinental Seaway. Through utilization of iron speciation, a local redox proxy, I identify anoxia developing before and persisting well after the negative carbon isotope excursion (NCIE) conventionally used to define the T-OAE. These data indicate an increase in the occurrence of anoxia at the Pliensbachian – Toarcian boundary, coincident with the initial phase of volcanism associated with the Karoo-Ferrar Large Igneous Province and an interval of heightened marine invertebrate extinction. Ultimately, our data support a greater temporal extent of anoxic conditions around the T-OAE, which support the greater sensitivity of marine oxygen levels to climatic change outside of the NCIE interval. The second chapter of this dissertation assesses the occurrence and extent of organic matter sulfurization (OMS), a biogeochemical feedback known to enhance the preservation and burial of OM. Because this process is accelerated when euxinic conditions develop in the water column, I investigated it as a mechanism promoting OM burial across two oceanic anoxic events of the Mesozoic. Importantly, I find that sulfurization does not occur uniformly across both events and propose a conceptual model of the depositional settings most favorable for sulfurization to occur and when throughout geologic time OMS is most likely to influence the global cycles of carbon and sulfur. / Doctor of Philosophy / Understanding past time intervals where there was widespread loss of oxygen in the oceans is crucial to understanding habitability on Earth. Since our modern oceans are experiencing a rapid loss of oxygen, understanding the duration and extent of ancient marine oxygen loss events is vital to predicting future habitability of the oceans. These ancient events can result in distinctive changes in the carbon, sulfur, and iron cycles on our planet. Variation in these elemental cycles lead to distinctive shifts in the chemical composition of seawater that is recorded in marine sediments that get preserved as rocks in the geologic record. Here, I investigated the record of environmental change during the Early Jurassic Toarcian Oceanic Anoxic Event or T-OAE (~183 Ma). The first chapter of this dissertation investigates the record of marine oxygen loss across the T-OAE. Specifically, I investigate the temporal and geographic development of oxygen loss across three ancient marine basins. Through utilization of a local tracer of water column oxygen loss (e.g. iron speciation) I identify oxygen loss developing before and persisting well after the conventional timeframe associated with the event. These data indicate oxygen loss first occurred before the T-OAE, coincident with the initial phase of volcanic eruptions from the Karoo-Ferrar Large Igneous Province and an interval of heightened marine extinction. Ultimately, these data support a longer time interval of oxygen loss around the T-OAE and the greater sensitivity of marine oxygen levels to climatic change. The second chapter of this dissertation assesses the occurrence and extent of organic matter sulfurization (OMS), a feedback known to enhance the preservation and burial of organic matter (OM). Because this process is accelerated when oxygen is lost and free sulfur builds up in the water column, I investigated its occurrence across two oceanic oxygen loss events of the Mesozoic Era. Importantly, I find that sulfurization does not occur uniformly across both events and propose a conceptual model of the settings most favorable for sulfurization to occur and also when in geologic time it is most likely to influence the global cycling of carbon and sulfur.

The Toarcian Oceanic Anoxic Event (T-OAE; ~183 million years ago) represents an interval during the Mesozoic when the emplacement of the Karoo-Ferrar Large Igneous Province (LIP) is thought to have resulted in significant environmental change. Associated with this interval was the widespread deposition of organic-rich sediments, carbon cycle and seawater chemistry changes, global warming, the development of marine anoxia, and major extinction events. The majority of studies of this event that have documented these responses have come from the Boreal and Tethyan regions of Europe, thus casting some doubt to the regional versus global significance of the event. Thus my dissertation has sought to reconstruct biogeochemical and paleoenvironmental changes across the T-OAE from a sedimentary succession that was deposited on the margins of a different ocean basin away from the well-studied European successions. Specifically, I have studied the chemostratigraphy of the Fernie Formation of the Western Canada Sedimentary Basin (WCSB), which was deposited on the eastern margin of the Panthalassa Ocean. The Toarcian carbon isotope excursions (CIEs) in the WCSB confirm that these features are global phenomena. I have suggested a new driver for small-scale CIEs observed during the event: the release of wetland-derived methane during progressive global warming. The osmium isotope record and numerical modeling of the osmium cycle suggests that continental weathering rates increased during the T-OAE by 230 – 540%. Rhenium abundance data also suggests that the increased geographic extent of marine anoxia during the T-OAE caused a global drawdown in the seawater rhenium inventory. Iron speciation data are used to reconstruct redox conditions within the WCSB, which suggest ferruginous conditions developed in the more distal locations at the onset of the T-OAE before returning to euxinic (anoxic and sulfidic) conditions. This is likely related to enhanced pyrite burial on a global scale, which caused the drawdown of the seawater sulfate inventory, thus limiting pyrite formation in the distal locations. The proximal setting remained euxinic across the T-OAE, and in all locations the iron speciation data suggest anoxic conditions persistent well after the interval that has been traditionally called the end of the T-OAE. / Ph. D.

Globaler Temperaturanstieg, Ozeanversauerung und Sauerstoffmangel (temperaturbedingte Stressoren), spielen eine wichtige Rolle während Klimawandel. Die kombinierten Auswirkungen wirken sich negativ auf marine Lebensgemeinschaften und Ökosystemen aus und verschärfen die Effekte anderer Stressoren. Es gibt für den aktuellen und vergangenen Erwärmungsphasen Belege für veränderte Artenverteilung, Lebensraumverlust, Artensterben und verminderte physiologische Leistungen von Organismen. Die spezifischen Mechanismen werden diskutiert. Umweltveränderungen in der Erdvergangenheit bieten die Gelegenheit, die Dynamik von Ökosystemkrisen vor, zu untersuchen. Diese Arbeit integriert verschiedenen Disziplinen um unser Verständnis der Rolle temperaturbedingter Stressoren für marine benthische Ökosysteme zu verbessern. Das Toarcian Event (Unterjura) wurde aufgrund seiner geologischen, geochemischen und paläontologischen Überlieferung ausgewählt. Hochaufgelöste quantitative taxonomische, paläoökologische und geochemische Daten von benthischen Makroinvertebraten wurden analysiert. Ziel ist es, die Mechanismen ökologischer Veränderungen unter Temperaturstress zu bewerten, mit Schwerpunkt auf Körpergrößenmuster sowie Veränderungen in der Zusammensetzung und Struktur von Lebensgemeinschaften, und die Rolle von Umweltstressoren als Ursachen der biotischen Krise abzuschätzen. Der Temperaturanstieg führte zu dem Verlust an biologischer Vielfalt und zu der Verringerung der Körpergröße der Organismen vor und während der biotischen Krise. Die Struktur der Gemeinschaften wurde in Bezug auf die taxonomische und ökologische Zusammensetzung neu organisiert. Die Reaktion auf Umweltstress war innerhalb und zwischen den taxonomischen Gruppen unterschiedlich, wobei Brachiopoden stark betroffen waren. Diese Ergebnisse verbessern unser Verständnis der biotischen Reaktionen auf temperaturbedingte Stressoren und können zur Vorhersage Veränderungen Ökosysteme bei den aktuellen Erwärmungstrends beitragen. / Global warming, oceanic acidification and deoxygenation (temperature-related stressors) play an important role during climate change. The combined impact of these stressors is known to negatively affect marine biota and ecosystems, often exacerbating the impact of other stressors. Under the current and past climate change, there is record of altered species distribution, habitat loss, extinctions and decreased physiological performance of organisms. Despite the increasing evidence, the specific mechanisms through which climate change influences ecological patterns are debated. Past environmental perturbations represent an opportunity to investigate the dynamics of ecosystem and biotic crises across Earth history. This work integrates different disciplines to increase our understanding on the role played by temperature-related stressors on marine benthic biota and ecosystems. The Toarcian Event (Early Jurassic) was chosen for its well-preserved geological, geochemical and palaeontological record. High-resolution quantitative faunal and geochemical data from benthic marine macroinvertebrates were investigated. The aims are to identify and evaluate the mechanisms of faunal and ecological shifts under a temperature-related stressor scenario, with focus on body size patterns and ecosystem change and recovery, and to estimate the role of environmental stressors as proximate causes of the biotic crisis. Temperature increase led to biodiversity loss and reduced body size of organisms during and possibly before the event. Moreover, the structure of marine communities was reorganized in terms of taxonomic and ecological composition. The response to environmental stress was variable within and between taxonomical groups, with brachiopods severely affected. These findings increase our understanding of biotic responses and ecosystem and biodiversity shifts under temperature stress, hopefully contributing to the prediction of ecosystem changes under the current warming scenario.

Le géothermomètre Δ47 est basé sur la relation entre l’abondance des liaisons 13C–18O des carbonates et la température de calcification. Ce proxy contourne potentiellement les limites des autres thermomètres (δ18O, Mg/Ca) pour reconstruire les paléo-températures des océans, expliquant son développement exponentiel depuis dix ans. Cette thèse teste pour la première fois le potentiel et les limites de la thermométrie Δ47 sur les coccolithes, des nannofossiles calcaires produits par des organismes calcifiants dans la zone photique. Ces biominéraux calcitiques et ubiquistes constituent une part importante de l’archive sédimentaire. Des cultures in vitro nous ont permis d’établir que trois espèces de coccolithes actuelles enregistrent la même relation Δ47 – T que la calcite inorganique, alors qu'elles présentent de très larges effets vitaux en δ18O (±5‰). Nous concluons que ces espèces de coccolithes d'importance géologique ne présentent pas d’effets vitaux en Δ47. Nous avons ensuite appliqué le Δ47 à l’étude des sédiments enregistrant l’événement d’anoxie océanique du Toarcien (–183 Ma) au cours duquel les reconstructions de températures restent encore ambigües, notamment du fait de la méconnaissance de la composition isotopique en oxygène de l’eau de mer. Sur la base des données Δ47 acquises, nous proposons des températures élevées (de l’ordre de 36°C), mais restant relativement stables sur l'intervalle d'étude. En couplant ces températures aux données de δ18O des carbonates, nous suggérons une variation importante du δ18O de l'eau de mer dans le Bassin de Paris lors de la mise en place des faciès black shales. Enfin, sur des sédiments pélagiques subactuels, l’une des espèces étudiées présente des déséquilibres isotopiques en Δ47 non observés en culture et explicables par d’autres paramètres environnementaux comme l’intensité lumineuse. Cette thèse illustre le potentiel du thermomètre Δ47 des coccolithes en différents contextes, ouvrant un vaste champ d’application de reconstruction des paléo-environnements sur le Méso-Cénozoïque / The Δ47 geothermometer relies on the relationship between the 13C–18O abundance in carbonateand temperature of calcification. This proxy has the potential to overcome limitations of other thermometers(δ18O, Mg/Ca) to reconstruct oceanic paleotemperatures. This thesis evaluates for the first time the potentialand the limitations of the Δ47 thermometry of the coccoliths, the calcareous nannofossils produced byorganisms calcifying in the photic zone. These calcitic and ubiquitous biominerals represent an importantpart of the sedimentary archive. In vitro cultures allow us to establish that three modern coccoliths speciesrecord the same Δ47–T relation than inorganic calcite, although exhibiting substantial δ18O vital effects(±5‰). We conclude that these coccoliths species do not present any Δ47 vital effect. We subsequentlyapplied the Δ47 proxy to sediments from the Toarcian oceanic anoxic events (–183 Ma) during which thetemperatures reconstructions are still elusive, mainly due to the unknown oxygen isotopic composition ofseawater. On the basis of our Δ47 data, we infer relatively high, yet steady temperatures (around 36°C) duringthe examined interval. By combining these Δ47-derived temperatures to carbonate δ18O data, we can suggestdrastic change in the seawater δ18O composition in the Paris Basin at the onset of black shale deposition. Acore top calibration of Δ47 of coccoliths revealed that one of the studied cultured species exhibits Δ47disequilibrium that is accountable by other environmental parameters, such as light irradiance in the naturalenvironment. Thus, this thesis illustrates the potential of the coccolith Δ47 thermometer in different settings,opening a wide range of application to reconstruct the palaeoenvironments over the Meso-Cenozoic Eras