The ongoing changes in the extent and the properties of sea ice, associated with the warming climate, are affecting the polar ecosystem and the interactions between the atmosphere, sea ice and the underlying waters. How sea ice biogeochemistry will change in the foreseeable future is currently uncertain, but is a crucial problem to tackle.<p>To better understand how sea ice biogeochemistry could change, we investigated the factors regulating the distribution of some dissolved compounds (e.g. nutrients, dissolved organic matter (DOM)) and gaseous compounds (e.g. Ar, O2, N2, CH4) in sea ice, from ice growth to ice decay. The results were obtained from a 19-day indoor experiment in Hamburg (Germany) and a five-month-long field survey in Barrow (Alaska). They were then compared to the physical properties of the ice (temperature, salinity, and other derived parameters such as brine volume fraction) and different biological parameters (bacterial activity, bacterial abundance, chlorophyll-a and phaeopigments).<p>Our work indicates that the physical properties of sea ice exert a strong influence on the distribution of the biogeochemical compounds in the ice, through their impact on brine dynamics, gas bubble formation and ice permeability. We have described 4 stages of brine dynamics, which affect the distribution of the dissolved compounds (e.g. silicate and DOM) in sea ice. However, inert gas (Ar) shows a different dynamic in comparison to the dissolved compounds, indicating a different transport pathway. We suggest that the formation of gas bubbles in sea ice is responsible for that different transport pathway, because gas bubbles should move upward owing to their buoyancy in comparison to brine, while dissolved compounds are drained downward due to gravity. Our observations further indicate that the critical permeability threshold for the upward gas bubble transport should range between 7.5 and 10 % of brine volume fraction, which is higher than the 5 % suggested for the downward brine transport. Increasing ice permeability and prolonged gas exchange tend to draw gas concentrations toward their solubility values, except when the under-ice water is supersaturated relative to the atmosphere (e.g. CH4) or when in-situ production occurs in sea ice (e.g. O2).<p>Because ammonium and O2 obviously accumulate in the ice layers where convection is limited, we suggest that the changes of these biogeochemical compounds in sea ice depend on the competing effect between the physical transport and the biological activity; the biological impact on these biogeochemical compounds in sea ice is obvious when the biological production rate exceeds largely the physical transport rate. We further discussed on the potential of using Ar and N2 as inert tracers to correct the physical controls on O2 and to determine the net community production in sea ice.<p>In addition to the physical and biological controls, the chemical properties of some biogeochemical compounds (e.g. nitrate, ammonium, DOM) may further influence their distribution in sea ice; further investigations are however needed to confirm this.<p>Finally, based on our findings, we present an update of the processes regulating the distribution of gases in sea ice, with references to recent observations supporting each of the process. We also provide some insights on how sea ice biogeochemistry could change in the future and the research priorities for an accurate quantification of these changes.<p><p>Les changements dans l’extension et les propriétés de la glace de la mer, liés au réchauffement climatique, affectent l’écosystème polaire, ainsi que les interactions entre l’atmosphère, la glace de mer et l’eau sous-jacente. Cependant, des incertitudes subsistent quant aux changements potentiels qui affecteront la biogéochimie de la glace de mer dans un futur proche.<p>Afin de mieux comprendre les changements potentiels qui affecteront la biogéochimie de la glace de mer, nous avons étudié les facteurs qui influencent la distribution de certains composés dissouts (e.g. nutriments, matière organique dissoute (DOM)) et gazeux (e.g. Ar, O2, N2, CH4) au sein de la glace de mer, depuis la croissance de la glace, jusqu’à sa fonte. Les résultats ont été obtenus à partir d’une expérience de 19 jours dans un bassin expérimental à Hambourg (Allemagne) et une étude de terrain de 5 mois à Barrow (Alaska). Ils ont été ensuite comparés aux propriétés physiques de la glace (température, salinité et autres paramètres dérivés) et à des paramètres biologiques (activité bactérienne, abondance bactérienne, chlorophylle-a et phaeopigments).<p>Nos travaux ont montré que les propriétés physiques de la glace exercent une forte influence sur la répartition des composes biogéochimiques dans la glace de mer, à travers leur impact sur la dynamique des saumures, la formation de bulles de gaz et la perméabilité de la glace. Nous avons décrit 4 stades dans la dynamique des saumures qui influencent la distribution des composés dissouts (e.g. silice et DOM) dans la glace. Cependant, le gaz inerte étudié (Ar) montre une dynamique différente de celle des composés dissouts, indiquant un mécanisme de transport différent. Nous suggérons que la formation de bulles de gaz dans la glace de mer est le mécanisme responsable de cette différence, parce que les bulles de gaz devraient migrer vers le haut, à cause de leur différence de densité par rapport aux saumures, alors que les saumures sont drainées vers le bas à cause de la gravité. Nos observations montrent également que le seuil critique de perméabilité pour l’ascension des bulles de gaz devrait se trouver entre 7.5 et 10 % de volume relatif en saumure ;seuil qui est plus élevé que les 5 % suggérés pour le transport de saumure vers le bas. L’augmentation de la perméabilité de la glace et les échanges de gaz prolongés tendent à amener les concentrations de gaz vers leur valeur de solubilité, sauf lorsque l’eau sous-jacente présente une sursaturation parrapport à l’atmosphère (e.g. CH4), ou lorsque une production in-situ se produit au sein de la glace (e.g. O2).<p>Etant donné que l’ammonium et O2 s’accumulent clairement dans les couches de glace où la convection est limitée, nous suggérons que les variations de ces composés biogéochimiques dans la glace dépendent de la balance entre le transport physique et l’activité biologique ;l’impact de cette dernière sur les composés biogéochimiques est particulièrement visible lorsque le taux de production biologique du composé excède largement la vitesse d’élimination du composé par le transport physique. Nous avons ensuite discuté du potentiel d’utiliser Ar et N2 comme traceurs inertes pour corriger l’impact des processus physiques sur les variations de O2, afin de déterminer la production communautaire nette dans la glace de mer.<p>Les propriétés chimiques de certains composés biogéochimiques (e.g. nitrate, ammonium, DOM) pourraient également influencer leur répartition au sein de la glace de mer, en plus des processus physiques et biologiques. Cependant, il est nécessaire d’avoir plus d’études à ce sujet pour confirmer cela.<p>Enfin, sur base de nos résultats, nous présentons une mise à jour des processus qui régulent la répartition des gaz dans la glace de mer, avec des références à des observations récentes qui illustrent chacun des processus. Nous donnons également un aperçu des changements qui pourraient affecter la biogéochimie de la glace de mer à l’avenir, et des pistes de recherches pour une quantification précise de ces changements. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

No description available.

No description available.

Dans le cadre du projet Européen GTS Next, nous avons obtenu des nouvelles contraintes sur l’âge des étages du Crétacé Supérieur à partir de plusieurs techniques de géochronologie et d’interprétations stratigraphiques au Canada et au Japon. Dans le bassin sédimentaire du Western Interior Canada, nous proposons une nouvelle détermination de l’âge de la limite Crétacé - Tertiaire (K/Pg) enregistrée dans la coupe de Red Deer River (Alberta). Il a été possible de calibrer par cyclostratigraphie haute-résolution cette série sédimentaire fluviatile non-marine et d’identifier 11-12 cycles associés à la précession orbitale de la Terre. En considérant la technique 40Ar/39Ar intercalibrée avec la cyclostratigraphie, l’âge apparent de la base du chron magnétique C29r suggère que la limite K/Pg se trouve entre un minimum et un maximum de l’excentricité, avec une durée pour C29r de 66.30 ± 0.08 à 65.89 ± 0.08 Ma. En supposant que le cycle contenant le niveau de charbon soit associé à un cycle de précession, l’âge révisé de la limite Crétacé - Tertiaire est donné par la plus jeune des populations de zircon datée par U-Pb à 65.75 ± 0.06 Ma.La limite Campanien – Maastrichtien est également enregistrée dans ce même bassin canadien, et se trouve à environ 8 m sous le niveau de charbon No. 10 dans la formation de Horseshoe Canyon. L’étude cyclostratigraphique montre que le dépôt de cette séquence sédimentaire est directement influencé par les changements du niveau marin dû à la précession et dominés par l’excentricité Notre travail montre que la position de la limite Campanien – Maastrichtien dans ce bassin sédimentaire du Western Canada est placée à environ 2.5 cycles d’excentricité au dessus d’un niveau de téphra de la base de la coupe dont l’âge U-Pb est donné par la plus jeune population des zircons, et ~4.9 Myr avant la limite Crétacé - Tertiaire. Nous en déduisons un âge absolu de 70.65 ± 0.09 Ma pour la limite Campanien – Maastrichtien, ce qui est ~1.4 Myr plus jeune que les études récemment publiées.Enfin, à partir des isotopes du carbone et des foraminifères planctoniques enregistrés au centre d’Hokkaido (Pacifique Nord-Ouest), les coupes Crétacé du groupe Yezo ont été corrélée avec les séries européennes et nord-américaines. Plusieurs niveaux de téphra prélevés au sein des coupes de Kotanbetsu et Shumarinai ont été datés par les méthodes 40Ar/39Ar and U-Pb. Deux d’entre eux, placés de part et d’autre de la limite Turonien – Coniacien, ont donné des âges de 89.31 ± 0.11 et 89.57 ± 0.11 Ma, ce qui suggère un âge de 89.44 ± 0.24 Ma pour cette limite. En combinant notre résultat avec les âges récemment publiés, nous pouvons proposer un âge de 89.62 ± 0.04 Ma pour la limite Turonien – Coniacien. / As part of the wider European GTS Next project, I propose new constraints on the ages of the Late Cretaceous, derived from a multitude of geochronological techniques, and successful stratigraphic interpretations from Canada and Japan. In the Western Canada Sedimentary Basin, we propose a new constraint on the age of the K/Pg boundary in the Red Deer River section (Alberta, Canada). We were able to cyclostratigraphically tune sediments in a non-marine, fluvial environment utilising high-resolution proxy records suggesting a 11-12 precession related cyclicity. Assuming the 40Ar/39Ar method is inter-calibrated with the cyclostratigraphy, the apparent age for C29r suggests that the K/Pg boundary falls between eccentricity maxima and minima, yielding an age of the C29r between 65.89 ± 0.08 and 66.30 ± 0.08 Ma. Assuming that the bundle containing the coal horizon represents a precession cycle, the K/Pg boundary is within the analytical uncertainty of the youngest zircon population achieving a revised age for the K/Pg boundary as 65.75 ± 0.06 Ma. The Campanian - Maastrichtian boundary is preserved in the sedimentary succession of the Horseshoe Canyon Formation and has been placed ~8 m below Coal nr. 10. Cyclostratigraphic studies show that the formation of these depositional sequences (alternations) of all scales are influenced directly by sea-level changes due to precession but more dominated by eccentricity cycles proved in the cyclostratigraphic framework and is mainly controlled by sand horizons, which have been related by autocyclicity in a dynamic sedimentary setting. Our work shows that the Campanian - Maastrichtian boundary in the Western Canada Sedimentary Basin coincides with ~2.5 eccentricity cycles above the youngest zircon age population at the bottom of the section and ~4.9 Myr before the Cretaceous - Palaeogene boundary (K/Pg), and thus corresponds to an absolute age of 70.65 ± 0.09 Ma producing an ~1.4 Myr younger age than recent published ages. Finally, using advances with terrestrial carbon isotope and planktonic foraminifera records within central Hokkaido, Northwest Pacific, sections from the Cretaceous Yezo group were correlated to that of European and North American counterparts. Datable ash layers throughout the Kotanbetsu and Shumarinai section were analysed using both 40Ar/39Ar and U-Pb methods. We successfully dated two ash tuff layers falling either side of the Turonian - Coniacian boundary, yielding an age range for the boundary between 89.31 ± 0.11 Ma and 89.57 ± 0.11 Ma or a boundary age of 89.44 ± 0.24 Ma. Combining these U-Pb ages with recent published ages we are able to reduce the age limit once more and propose an age for the Turonian - Coniacian boundary as 89.62 ± 0.04 Ma.

Cette thèse porte sur l'étude de micro-plasmas froids à la pression atmosphérique générés à partir de différents réacteurs des configurations basées sur le principe des Décharges à Barrière Diélectrique (DBD) et alimentés par des générateurs de tension impulsionnelle et sinusoïdale. Les plasmas sont formés dans des gaz nobles tels que l'hélium et l'argon (gaz vecteurs), et également dans des mélanges réalisés avec des gaz moléculaires tels que l'azote et l'oxygène afin de produire des Espèces Réactives de l’Azote et de l’Oxygène (ERA, ERO). La (ré)activité chimique du plasma est ainsi supposée être accrue, permettant le traitement de matériaux inertes ou vivants pour diverses applications (fonctionnalisation de surfaces, inactivation de cellules, régénération de tissus vivants, etc.). La caractérisation des plasmas étudiés est réalisée en enregistrant les aspects électriques et optiques en fonction des paramètres élémentaires, comme l’amplitude et la fréquence de la tension, le débit du gaz, la configuration des électrodes, et le rapport cyclique dans le cas du régime pulsé. Ainsi, la (ré)activité chimique des plasmas est évaluée tandis que au même temps les mécanismes de la génération des plasmas et les façons de l’optimisation de la chimie sont dévoilées. Finalement, nous examinons l'efficacité du plasma dans le domaine biomédical en traitant divers systèmes biologiques (bactéries, liposomes, cellules) sans effets thermiques. / The present PhD thesis is devoted to the study of atmospheric pressure cold micro-plasmas produced in different Dielectric Barrier Discharge (DBD) reactors which are driven by pulsed or sinusoidal high voltages. Noble gases such as helium and argon are used as carrier gases, whereas admixtures with nitrogen and oxygen are studied as well. The formation of Reactive Nitrogen and Oxygen Species (RNS, ROS) is thus achieved, and the possibility of improving the chemical (re)activity of the plasmas is demonstrated. This is of interest in the treatment of inert or living materials (e.g. surface functionalization, cell inactivation, living tissue regeneration, etc.). Plasmas are characterized by recording electrical and optical features as a function of principal operational parameters, including voltage amplitude and frequency, gas flow rate, electrode configuration, and voltage duty cycle in the case of pulsed waveform. The physico-chemical (re)activity of the plasmas is thus evaluated, while at the same time mechanisms on the plasma generation and paths for chemistry optimization are unveiled. Finally, the efficiency of the plasma in relation to biomedical applications is tested by treating different biological systems (bacteria, liposomes, cells) while preventing any thermal effect.

.

<p>Atoms, molecules and clusters all constitute building blocks of macroscopic matter. Therefore, understanding the electronic and geometrical properties of such systems is the key to understanding the properties of solid state objects.</p><p>In this thesis, some atomic, molecular and cluster systems (clusters of O₂, CH₃Br, Ar/O₂, Ar/Xe and Ar/Kr; dimers of Na; Na and K atoms) have been investigated using synchrotron radiation, and in the two last instances, laser light. We have performed x-ray photoelectron spectroscopy (XPS) on all of these systems. We have also applied ultraviolet photoelectron spectroscopy (UPS), resonant Auger spectroscopy (RAS) and near-edge x-ray absorption spectroscopy (NEXAFS) to study many of the systems. Calculations using <i>ab initio</i> methods, namely density functional theory (DFT) and Møller-Plesset perturbation theory (MP), were employed for electronic structure calculations. The geometrical structure was studied using a combination of <i>ab initio</i> and molecular dynamics (MD) methods.</p><p>Results on the dissociation behavior of CH₃Br and O₂ molecules in clusters are presented. The dissociation of the Na₂ molecule has been characterized and the molecular field splitting of the Na 2<i>p</i> level in the dimer has been measured. The molecular field splitting of the CH₃Br 3<i>d</i> level has been measured and the structure of CH₃Br clusters has been determined to be similar to the structure of the bulk solid. The diffusion behavior of O₂, Kr and Xe on large Ar clusters, as a function of doping rate, has been investigated. The shake-down process has been observed from excited states of Na and K. Laser excited Na atoms have been shown to be magnetically aligned. The shake-down process was used to characterize the origin of various final states that can be observed in the spectrum of ground-state K.</p>

Atoms, molecules and clusters all constitute building blocks of macroscopic matter. Therefore, understanding the electronic and geometrical properties of such systems is the key to understanding the properties of solid state objects. In this thesis, some atomic, molecular and cluster systems (clusters of O2, CH3Br, Ar/O2, Ar/Xe and Ar/Kr; dimers of Na; Na and K atoms) have been investigated using synchrotron radiation, and in the two last instances, laser light. We have performed x-ray photoelectron spectroscopy (XPS) on all of these systems. We have also applied ultraviolet photoelectron spectroscopy (UPS), resonant Auger spectroscopy (RAS) and near-edge x-ray absorption spectroscopy (NEXAFS) to study many of the systems. Calculations using ab initio methods, namely density functional theory (DFT) and Møller-Plesset perturbation theory (MP), were employed for electronic structure calculations. The geometrical structure was studied using a combination of ab initio and molecular dynamics (MD) methods. Results on the dissociation behavior of CH3Br and O2 molecules in clusters are presented. The dissociation of the Na2 molecule has been characterized and the molecular field splitting of the Na 2p level in the dimer has been measured. The molecular field splitting of the CH3Br 3d level has been measured and the structure of CH3Br clusters has been determined to be similar to the structure of the bulk solid. The diffusion behavior of O2, Kr and Xe on large Ar clusters, as a function of doping rate, has been investigated. The shake-down process has been observed from excited states of Na and K. Laser excited Na atoms have been shown to be magnetically aligned. The shake-down process was used to characterize the origin of various final states that can be observed in the spectrum of ground-state K.

As part of the wider European GTS Next project, I propose new constraints on the ages of the Late Cretaceous, derived from a multitude of geochronological techniques, and successful stratigraphic interpretations from Canada and Japan. In the Western Canada Sedimentary Basin, we propose a new constraint on the age of the K/Pg boundary in the Red Deer River section (Alberta, Canada). We were able to cyclostratigraphically tune sediments in a non-marine, fluvial environment utilising high-resolution proxy records suggesting a 11-12 precession related cyclicity. Assuming the 40Ar/39Ar method is inter-calibrated with the cyclostratigraphy, the apparent age for C29r suggests that the K/Pg boundary falls between eccentricity maxima and minima, yielding an age of the C29r between 65.89 ± 0.08 and 66.30 ± 0.08 Ma. Assuming that the bundle containing the coal horizon represents a precession cycle, the K/Pg boundary is within the analytical uncertainty of the youngest zircon population achieving a revised age for the K/Pg boundary as 65.75 ± 0.06 Ma. The Campanian - Maastrichtian boundary is preserved in the sedimentary succession of the Horseshoe Canyon Formation and has been placed ~8 m below Coal nr. 10. Cyclostratigraphic studies show that the formation of these depositional sequences (alternations) of all scales are influenced directly by sea-level changes due to precession but more dominated by eccentricity cycles proved in the cyclostratigraphic framework and is mainly controlled by sand horizons, which have been related by autocyclicity in a dynamic sedimentary setting. Our work shows that the Campanian - Maastrichtian boundary in the Western Canada Sedimentary Basin coincides with ~2.5 eccentricity cycles above the youngest zircon age population at the bottom of the section and ~4.9 Myr before the Cretaceous - Palaeogene boundary (K/Pg), and thus corresponds to an absolute age of 70.65 ± 0.09 Ma producing an ~1.4 Myr younger age than recent published ages. Finally, using advances with terrestrial carbon isotope and planktonic foraminifera records within central Hokkaido, Northwest Pacific, sections from the Cretaceous Yezo group were correlated to that of European and North American counterparts. Datable ash layers throughout the Kotanbetsu and Shumarinai section were analysed using both 40Ar/39Ar and U-Pb methods. We successfully dated two ash tuff layers falling either side of the Turonian - Coniacian boundary, yielding an age range for the boundary between 89.31 ± 0.11 Ma and 89.57 ± 0.11 Ma or a boundary age of 89.44 ± 0.24 Ma. Combining these U-Pb ages with recent published ages we are able to reduce the age limit once more and propose an age for the Turonian - Coniacian boundary as 89.62 ± 0.04 Ma.

No description available.