Clumped isotope paleothermometry defines carbonate formation temperature based upon the relative abundance of the 13C18O16O isotopologue within CO2 (Δ47) formed through phosphoric acid digestion of carbonates. When precipitated in equilibrium, resultant Δ47 values are inversely-proportional to growth temperature, where 13C18O16O is more abundant at lower temperatures. To precisely define Δ47 values, a rigorous analytical protocol is required to: (1) minimize CO2-H2O isotope exchange during acid digestion; (2) purify CO2 to remove contaminants; (3) quantify the raw Δ47 value using a mass spectrometer configured for m/z 44 – 49; and (4) normalize the raw Δ47 value to account for machine-specific isotopic scrambling and Δ47 vs. δ47 non-linearity. Amongst laboratories with well-established analytical protocols, substantial disagreement still exists between proposed clumped isotope calibrations at low temperatures. To investigate the source of this discrepancy, calcite was precipitated between 15 – 40 °C from a HCO3-(aq)-dominated solution using an upgraded constant addition technique. This technique is the first to provide simultaneous control of δ18OH2O and δ13CDIC values of parent solution. Observed oxygen isotope fractionation between calcite and water is in agreement with Kim and O’Neil (1997), providing robust evidence of calcite precipitation in oxygen isotope equilibrium. Δ47 values were determined using McMaster’s clumped isotope facility, yielding the following calibration: Δ47-RF = 0.0351 (± 0.0021) × 106/T2 + 0.2982 (± 0.0233) This calibration observes a similar temperature dependency to theoretical models as well as ‘shallow’ slope experimental studies. To provide context to experimental calibrations with ‘steep’ slopes, we consider the non-equilibrium isotope effects of CO2 hydration/hydroxylation and HCO3- dehydration/dehydroxylation reactions on precipitating calcite. We propose that low temperature calcites primarily responsible for the ‘steep’ slopes of certain calibrations have partially inherited the disequilibrium isotope composition of DIC due to significant non-equilibrium isotope effects associated with the aforementioned CO2 hydration/hydroxylation and HCO3- dehydration/dehydroxylation reactions. / Thesis / Master of Science (MSc)

Studying the mean state and variability of past climate provides important insight into the dynamically coupled climate system, directly aiding projections of future climate. Reconstruction of past climate conditions can be achieved using geochemical proxies including the novel clumped isotope paleothermometer. In this thesis I use multiple proxies to study climate variability during the last glacial period and at the onset of Antarctic glaciation. Greenland ice cores record repeated millennial-scale fluctuations in climate during the last glacial period known as Dansgaard-Oeschger (DO) cycles. We measure 18O of bulk sediment and planktonic foraminifera (Neogloboquadrina Pachyderma) in sediment cores from the North Atlantic to investigate fluctuations in sediment properties on the timescale of DO cycles. We find evidence of episodic deposition of carbonate ice-rafted debris near Iceland. Integrating these observations with published data and modeling studies, we propose a new hypothesis to explain DO cycles. We suggest that a large ice shelf in the Nordic Seas acted in concert with sea ice to set the slow and fast timescales of DO cycles. The ice shelf was periodically removed by subsurface warming with the timescale of shelf regrowth setting the duration of each interstadial. We utilize the clumped isotope proxy to reconstruct the climate history during a key period of the Cenozoic - the onset of Antarctic glaciation. To facilitate this work, a new inlet is developed to streamline sample preparation and reduce sample size requirements. We decrease the required sample size from 5-8mg to 1-2mg per replicate, while still achieving external precision of 0.005-0.010o/oo, equivalent to previous methods. This new capability increases the range of possible applications for the clumped isotope paleothermometer, specifically in the field of paleoceanography. We apply the clumped isotope paleothermometer to thermocline-dwelling foraminifera (Subbotina angiporoides and Subbotina utilisindex) from the Southern Ocean core ODP689 across the Eocene-Oligocene transition. With the clumped isotope paleothermometer we separate the contributions of near- surface temperature change and ice sheet growth on the ~1o/oo increase in 18O observed in planktonic foraminifera from this site. We measure no change in temperature, and 0.8±0.2o/oo change in 18Osw, equivalent to 124-140% of the modern Antarctic ice sheet volume. / Earth and Planetary Sciences

Speleothems (cave carbonate deposits) have been recognized as a multi-proxy paleoclimate archive. Variations in carbon and oxygen isotopes in speleothems can record past climate changes (e.g., temperature, rainfall and vegetation) under isotopic equilibrium conditions. However, non-climatic noises caused by in-cave processes may affect these stable isotope records under non-equilibrium isotopic conditions. The identification of equilibrium and non-equilibrium isotopic conditions in speleothems is still disputed in the speleothem research community; however, this is a prerequisite for the interpretation of carbon and oxygen isotope records in speleothems as paleoclimate proxies. In this Ph.D. thesis, a series of laboratory experiments under cave-analogue conditions were performed to simulate the formation of speleothems in natural caves. The results of these experiments demonstrate that stable isotope equilibrium in speleothems is achieved under slow carbonate precipitation in pool-like settings (pool carbonates). On the basis of these pool carbonates, equilibrium carbon and oxygen isotope fractionation factors between calcite and water (or DIC for carbon) were determined. Our experiments show larger carbon and oxygen isotope non-equilibrium fractionations between calcite and water (or DIC for carbon) in stalagmite-like settings (fast carbonate precipitate) than those determined in pool-like settings. The flow rate of drip water above the surface of stalagmite appears to control the magnitude of these non-equilibrium isotope effects which increase with decreasing the flow rate. Furthermore, a natural speleothem sample was examined as a paleoclimate archive in this thesis. The growth of a double stalagmite (WS-5d) in Wadi Sannur Cave from the Northeastern Sahara was used to infer the greening of the Sahara (intensive rainfall and vegetation). The U/Th dating in the WS-5d stalagmite suggests that greening conditions extended widely in the Sahara during the interglacial Marine Isotope Stages MIS 5.5, MIS 7.3, and the early MIS 9. Based upon oxygen isotope compositions from the WS-5d, we attributed the source of these greening periods to long-traveling rains from the Atlantic Ocean that were delivered via the West African monsoon system. Our study suggests that the two youngest greening periods were concurrent with the arrival of Homo sapiens in the Levant and an earlier possible change in human population at 244 ka, indicating a key role of the Sahara route in early human dispersal out of Africa. Finally, clumped isotope measurements (Δ47) on carbonate-derived CO2 have been shown to reflect the formation temperature of the carbonate minerals. The absolute Δ47 values of these isotopic measurements seem to be sensitive to the standardization methods (heated CO2 gases and water-equilibrated CO2 gases) that are used to normalize the raw Δ47 measurements. Neither the hypothetical base for the heated CO2 gas standardization method nor the theoretical base for the water-equilibrated CO2 gas standardization method has been experimentally tested. A series of CO2 gases were heated in pre-dehumidified quartz tubes to obtain equilibrium Δ47 values of these CO2 gases at temperature range of 50 – 1100 °C. Consequently, the first experimentally derived Δ47 – T calibration in a CO2 gas phase was proposed. This experimental calibration provides a validated base for the standardization of the raw Δ47 data. Moreover, heating CO2 in a pre-humidified quartz tube enables us to easily prepare a CO2 standard gas of a similar Δ47 value to the CO2 sample (i.e., similar Δ47 correction matrix). This will lead to an improvement in the correction scheme of the carbonate clumped isotope thermometry and reliably adjust the absolute Δ47 scale. / Thesis / Doctor of Philosophy (PhD)

Quantifier les variations de température océanique du passé est nécessaire pour comprendre les mécanismes qui régissent l’évolution climatique. Les méthodes de paléo-thermométrie classiques peuvent souffrir de limitation inhérente à l’écologie des organismes et/ou à cause de l’influence d'effets physico-chimiques (salinité, acidité de l’eau de mer…). Ce travail se focalise sur la technique de paléothermométrie Δ47, qui repose sur la mesure du « clumping isotopique » dans les carbonates. Il vise d’abord à établir une calibration appliquée aux foraminifères et ensuite à mettre en œuvre cette calibration pour l’étude des variations climatiques au cours de la transition du Pléistocène moyen (MPT). Notre calibration Δ47-température des foraminifères planctoniques et benthiques, prélevés dans des sédiments modernes, couvre une gamme de température de -2 à 25°C. Les valeurs de Δ47 sur 9 espèces de foraminifères présentent une excellente corrélation avec la température de calcification des organismes, estimée à partir des mesures isotopiques de l’oxygène. Les résultats obtenus confirment l’absence d’effets liés à l’écologie des foraminifères (effets vitaux et de taille des organismes) et démontrent que la salinité n’affecte pas les mesures de Δ47. Cette étude constitue une avancée méthodologique importante pour les futures études paléocéanographiques sur les foraminifères. La MPT correspond à une transition climatique marquée par un changement de fréquence des cycles glaciaires-interglaciaires (de 41 000 à 100 000 ans). La compréhension de cette période est un enjeu scientifique majeur pour appréhender la mise en place du climat actuel. Notre calibration Δ47-température a permis de quantifier les variations de températures au cours de la MPT en mer méditerranée (Section de Montalbano Jonico, sud de l’Italie) et particulièrement des stades isotopiques marins 31 et 19, considérés comme des analogues à l’Holocène. Les résultats indiquent que (i) les températures (Δ47) obtenues sont en adéquation avec les températures obtenues par d’autres paléothermomètres, (2) les températures permettent de retracer les changements de régime océanographique et hydrologique, et (3) la mesure du Δ47 est complément prometteur pour les études multi-méthodes en paléocéanographie. / The quantification of past oceanic temperature changes is a critical requirement for understanding the mechanisms which regulate climate variations. Classical methods of paleothermometry could suffer from well-known limitations related to ecology and/or to physico-chemical biases (sea water salinity, acidity…). This work focuses on clumped-isotope carbonate thermometry (Δ47). It aims to establish a calibration of Δ47 foraminifera and use it to study past climatic variations through the Mid-Pleistocene Transition (MPT). Our Δ47 calibration in planktonic and benthic foraminifera collected from modern marine sediment covers a temperature range of -2 to 25 °C. The clumped-isotope compositions of 9 species of foraminifera show a robust correlation with the calcification temperature, estimated from the measurements of oxygen-18. These results confirm the absence of bias linked to foraminifer ecology (species-specific and foraminifer size effects) and provide evidence that salinity does not affect the Δ47 thermometer. This study constitutes significant methodological progress for future paleoceanographic applications in foraminifera.The MPT is a climatic transition characterized by a shift in the frequencies of glacial-interglacial cycles (from 41 000 to 100 000 years). Understanding the MPT is a major scientific objective, which underlies our effort to study the establishment of our present climate. Our Δ47 calibration was used to quantify temperature changes through the MPT in the Mediterranea Sea (Montalbano Jonico section, south of Italy), and in particular the marine isotopic stages 31 and 19, which may be described as Holocene analogues. We find that (1) Δ47 temperatures are in good agreement with temperatures reconstructed from other paleothermometers, (2) these results allow reconstructing changes in past oceanographic and hydrologic regime, and (3) Δ47 measurement are a promising component of multi-proxy paleoceanographic studies.

Le bassin de Jaca (Pyrénées espagnoles) est un exemple classique de bassins d’avant pays, où les grandes lignes du remplissage sédimentaire, ainsi que la chronologie des failles ont été très étudiées. Il reste toutefois à mieux comprendre la paléo-hydrologie et l’histoire thermique du bassin, de manière à proposer un modèle de circulation des fluides pendant sa mise en place et sa déformation (Paléocène-Oligocène). Pour ce faire, ce travail propose d’analyser la répartition de la fracturation, d’étudier les conditions de formation des veines syn-tectoniques et de caractériser la maturité de la matière organique sur l’ensemble du paléobassin d’avant-pays de Jaca, des zones internes vers les zones externes.L’analyse pétrographique, géochimique et microthermométrique des veines montre que la grande majorité des fluides minéralisateurs sont à l’équilibre isotopique et thermique avec l’encaissant. Dans le détail, nous avons identifié 2 événements principaux de formation de veines dans la zone interne du bassin (Sierras Interiores), que nous proposons d’associer au fonctionnement des failles majeures dans le socle. Nous suggérons que les fluides circulent le long des niveaux de décollements et sont expulsés sur de courtes distances (< 10 km), au travers des réseaux de fractures, vers le bassin d’avant-pays. Le reste du bassin enregistre principalement des fluides locaux, parfois associés à l’infiltration d’eau météorique. L’analyse des températures d’enfouissement (50°C à 250°C), qui inclut des données de Δ47, montre une organisation N-S relativement homogène depuis les Sierras Interiores (fenêtre à gaz) jusqu’aux Sierras Exteriores (immature), avec des anomalies longitudinales marquées. Les modélisations thermiques 1D sur 9 puits virtuels suggèrent que les températures maximales vers les Sierras Interiores peuvent résulter d’un enfouissement sédimentaire, dont une grande partie est érodée actuellement. Nous proposons que ces parties érodées correspondent à des dépôts tardi-orogéniques conglomératiques déposés à proximité de la zone axiale. Les données suggèrent une répartition non homogène de ces dépôts selon un axe E-W, impliquant des transferts sédimentaires plus complexes qu’habituellement discutés. Au vu de nos résultats et des précédentes études, le modèle paléohydrologique et thermique du bassin de Jaca, et à plus grande échelle, de la chaîne plissée sud-pyrénéenne, est compartimenté à la fois dans l’espace et dans le temps, en lien avec à la propagation latérale et frontale de la déformation, qui contrôle l’ouverture du système. Le modèle paléohydrologique et thermique de la chaîne plissée sud-pyrénéenne constitue donc un potentiel analogue aux chaînes plissées dont le raccourcissement résulte d’une convergence oblique. / The Jaca basin (Spanish Pyrenees) is a classical example of a foreland basin, where the sedimentary filling and the calendar of thrust activation have been extensively studied. It remains to understand the paleohydrology and the thermal history of the basin, so as to provide a fluid flow model related to its formation and deformation (Paleoecene-Oligocene). To do this, this work proposes to analyze the distribution of fracturing, to study the conditions of formation of syn-tectonic veins and to characterize the maturity of organic matter throughout the Jaca foreland basin, from hinterland to external areas.Petrographical, geochemical and microthermometric analysis of veins show that the vast majority of mineralizing fluids are at the isotopic and thermal equilibrium with the host-rock. In detail, we identified two main events of vein precipitation in the inner part of the basin (Sierras Interiores), probably related to major basement thrust activations. We suggest that fluids flow along decollement levels and are expelled over short distances (<10 km), through fracture networks towards the foreland basin. The other part of the basin mainly record local fluids, sometimes associated with the infiltration of meteoric water. Analysis of burial temperatures (50 °C to 250 °C), which includes Δ47 data, shows a relatively homogeneous N-S organization from the Sierras Interiores (gas window) to Sierras Exteriores (immature), with strong longitudinal anomalies. Thermal 1D modelling of 9 virtual wells suggest that the maximum temperatures of Sierras Interiores result from sedimentary accumulation, whose a large amount is now eroded. We propose that this eroded thickness corresponds to late-orogenic conglomeratic deposits near the axial zone. The data suggest an inhomogeneous distribution of the deposits along an E-W axis, involving more complex sedimentary transfers than usually discussed. Given our results and previous studies, the paleohydrological and thermal model of the Jaca basin, and on a larger scale, of the South Pyrenean fold and thrust belt, is compartmentalized both in space and in time, in response to the propagation of and oblique deformational front, which controls the opening of the system. The paleohydrological and thermal model of the South Pyrenean fold and thrust belt is therefore a potential analogue to fold and thrust belt including shortening due to an oblique convergence.