Ziel der vorliegenden Arbeit war die Charakterisierung des Wachstumsverhaltens von Mikroorganismen auf Alkanen am Beispiel des Bodenbakteriums Rhodococcus opacus 1CP. Unter Einsatz kalorimetrischer Methoden konnte das Wachstumsverhalten von 1CP auf Glucose und Alkanen mit sehr guter Reproduzierbarkeit aufgezeichnet werden. In Abhängigkeit der Substrateigenschaften wurden Änderungen der Wachstumskinetik registriert, welche auf die Aggregation der Zellkultur zurückgeführt werden konnten. Die kalorimetrischen Befunde zum Aggregationsverhalten wurden mittels Gaschromatographie und Partikelgrößenbestimmung bestätigt. Durch Biotensidquantifizierung in kalorimetrisch aufgezeichneten Kultivierungen von 1CP auf Alkanen konnte eine wachstumsassoziierte Biotensidbildung nachgewiesen werden. Elementaranalytische Untersuchungen ergaben eine Variation der Biomassezusammensetzung von 1CP in Abhängigkeit der C-Quelle. Unter Berücksichtigung von Biomasse- und Biotensidbildung wurden Summenreaktionen für die Wachstumsprozesse formuliert und durch Verifikation mit kalorimetrisch ermittelten Enthalpien des Substratumsatzes bestätigt.

Alkane monooxygenases (encoded by the alkB gene) are a group of microbial enzymes that catalyze the first reaction of alkane degradation. Studies to determine the diversity and prevalence of alkB genotypes in the environment have focused on culturable organisms. The goal of this research was to use culture-independent methods (DGGE, clone library) to identify and characterize alkB genes, and to determine their prevalence in Arctic contaminated soils. General alkB PCR degenerate primers (alkB-Mc) were designed using the conserved nucleotide sequences of the Histidine I Box and Histidine III Box. General alkB-Mc and alkM (Acinetobacter spp. alkane monooxygenase genes) primers were used to screen the soils for the presence of alkane monooxygenase genotypes. A predominance of the Rhodococcus spp. alkB genotypes and the absence of alkM genotypes in these soils was found. alkB PCR fragments amplified from the soils were analyzed by DGGE (Denaturing Gradient Gel Electrophoresis). BlastN and blastX results of the DGGE bands sequences showed that they were similar to Rhodococcus spp. alkB genotypes (~80-90% DNA identity and ~80-90% amino acid homology). An alkB clone library was built using the general alkB-Mc primer set, screened by RFLP (Restriction Fragment Length Polymorphism) and characterized by sequencing of alkB clones. BlastN and blastX results of the alkB clone sequences showed the presence of divergent alkB genotypes (≤ 70% DNA identity and ≤ 67% of amino acid homology to data base sequences). The alignment of the clone-derived amino acid sequences to confirm functional alkane monooxygenase sequences revealed the presence of Histidine Box II and the HYG motif in all of the deduced amino acid clone sequences. These results indicate that the alkB sequences from the clone library represent novel alkB sequences. Both alkB DGGE and clone library techniques were independently able to identify alkB genotypes from High G+C microorganisms as predominant in the 1A03 soil sample. Nevertheless, only the clone library approach identified putative novel alkB sequences. Mineralization of hexadecane and naphthalene was clearly observed at subzero temperatures (-5ºC) in Arctic contaminated soils, proving that the indigenous microbial communities could mineralize these representative hydrocarbons at subzero temperatures in an environment that is predominantly frozen for most of the year.

Depuis quelques années, nous assistons à une prise de conscience croissante des effets à long terme des polluants chimiques sur l'environnement et la santé humaine. Il est donc nécessaire d'étudier non seulement leurs propriétés écotoxicologiques mais également leurs propriétés physicochimiques tels que la tension de vapeur (ou volatilité) et leur solubilité dans l'eau. L'Europe, quant à elle, a introduit la réglementation REACH (Registration, Evaluation and Autorisation of CHemicals) qui est entrée en vigueur le 1 juin 2007 dont le principal objectif est une meilleure connaissance des propriétés environnementales et sanitaires des substances chimiques. De même dans l’industrie, la détermination de la tension de vapeur des corps purs est une donnée indispensable pour les opérations de purification et de séparation. Dans ce but nous avons amélioré un appareil à saturation de gaz inerte existant au laboratoire. Une fois le bon fonctionnement de l’appareil vérifié (par mesure de la tension de vapeur d’un composé de référence : le phénanthrène) nous avons étudié des n-alcanes compris entre le C30 et le C60 ainsi que 8 hydrocarbures aromatiques polycycliques dans un large domaine de température (20 à 320 °C) et de pression (10-1 Pa à 10-7 Pa). Les résultats obtenus ont été comparés avec la littérature lorsque celle-ci est disponible. La détermination des tensions de vapeur de composés inorganiques d’intérêt industriel : tétrachlorure de Zirconium (ZrCl4) et le tétrachlorure d’hafnium (HfCl4) a été également entreprise. Les résultats expérimentaux des hydrocarbures polyaromatiques nous ont permis l’amélioration d’une équation d’état cubique (dérivée de celle de Peng-Robinson) dont les paramètres sont estimés par une méthode de contribution de groupes développée par Rauzy-Coniglio. Les tensions de vapeur prédites par le modèle sont en bon accord avec les valeurs expérimentales / For a few years, we have attended an increasing importance of the long-term effects of the chemical pollutants on the environment and human health. It is thus necessary to study not only their ecotoxicological properties but also their physico-chemical properties such as the vapor pressure (or volatility) and aqueous solubility. In Addition, the introduction of the regulation REACH (Registration, Evaluation and Authorization of CHemicals) in June 2007 whose main objective is a better knowledge of the environmental and medical properties of chemical substances has increased the necessity of compound characterization. From an industrial point of view, the determination of the vapor pressure of the pure substances is an essential data in many unit operations such as purification and separation. Thus, we improved an apparatus with saturation of inert gas existing at the laboratory. Once the good performance of the apparatus checked (by measurement of the vapor pressure of a reference compound: phenanthrene) we studied N-alkanes ranging between C30 and C60 and 8 polycyclic aromatic hydrocarbons in a broad temperature range (20 to 320°C) and of pressure (10-1 Pa with 10-7 Pa). The obtained results were compared with the literature when available. In addition, determination of the vapor pressure of inorganic compounds of industrial interest : zirconium tetrachloride (ZrCl4) and the hafnium tetrachloride (HfCl4) was also undertaken. The experimental results of polyaromatic hydrocarbons have allowed us to improve a cubic equation of state (derivative of Peng-Robinson EOS) whose parameters are estimated by a method of contribution of groups developed by Rauzy-Coniglio. The predicted vapor pressures were in good agreement with the experimental values

The study of adsorption of n-alkanes in zeolite pores represents both a fundamental problem in molecular thermodynamics and also a problem with substantial industrial importance. Until mid 19th century, adsorption was mainly used for purification processes such as removal of H2S and mercaptans from natural gas and organic matter from water. However, with the emergence of molecular sieves, especially zeolites, adsorption processes have become an attractive alter- native to distillation in large scale separation of mixtures that have low relative volatility into streams each enriched in one of the components. The pore di- ameters of molecular sieves are of the order of molecular diameters and hence selective adsorption can be achieved by both a difference in adsorbate-adsorbent interactions of various species and obstruction by the pore walls to some of the species in the mixture. The existing adsorption theories such as Henry’s law, Langmuir adsorption model and BET isotherm are incapable of predicting the adsorption isotherms of n-alkanes in zeolite pores. The reason is that in microporous adsorbents, the sorbate molecular mechanisms are influenced by geometrical constraints also. This limitation in the use of theory can be overcome by developing a molecular model and using computers to mimic the real system. This nature of simulation is called molecular simulations. With the development of advanced algorithms, improved force-field parameters and very high computational power of present day computers, molecular simulations have become an important tool in studying adsorption on micro-porous materials. Adsorption experiments of mixtures of long chain alkanes into silicalite under liquid phase conditions show selectivity inversion and azeotrope formation. These effects are due to the subtle interplay between the size of the adsorbed molecules and pore topology of the adsorbent. The underlying molecular mechanisms responsible for selective uptake of one of the components cannot be obtained from experiments but can be realized through simulations. Therefore, in this study, the selective uptake of lighter component during liquid phase adsorption of C14/C15 and C15/C16 n-alkane binary mixtures in the zeolite silicalite is understood through configurational bias grand canonical Monte Carlo (CB- GCMC) molecular simulation technique and a course-grained siting analysis. The simulations are conducted under conditions of low and high loading. The siting pattern of the adsorbates inside the zeolite pores is used to explain the selectivity as seen in experiments.

Ziel der vorliegenden Arbeit war die Charakterisierung des Wachstumsverhaltens von Mikroorganismen auf Alkanen am Beispiel des Bodenbakteriums Rhodococcus opacus 1CP. Unter Einsatz kalorimetrischer Methoden konnte das Wachstumsverhalten von 1CP auf Glucose und Alkanen mit sehr guter Reproduzierbarkeit aufgezeichnet werden. In Abhängigkeit der Substrateigenschaften wurden Änderungen der Wachstumskinetik registriert, welche auf die Aggregation der Zellkultur zurückgeführt werden konnten. Die kalorimetrischen Befunde zum Aggregationsverhalten wurden mittels Gaschromatographie und Partikelgrößenbestimmung bestätigt. Durch Biotensidquantifizierung in kalorimetrisch aufgezeichneten Kultivierungen von 1CP auf Alkanen konnte eine wachstumsassoziierte Biotensidbildung nachgewiesen werden. Elementaranalytische Untersuchungen ergaben eine Variation der Biomassezusammensetzung von 1CP in Abhängigkeit der C-Quelle. Unter Berücksichtigung von Biomasse- und Biotensidbildung wurden Summenreaktionen für die Wachstumsprozesse formuliert und durch Verifikation mit kalorimetrisch ermittelten Enthalpien des Substratumsatzes bestätigt.

<p>The increase in shale gas exploitation has motivated the studies towards new processes for converting light alkanes into higher valuable chemicals, including fuels. The works in this dissertation focuses on two processes: propane dehydrogenation and ethylene oligomerization. The former involves the conversion of propane into propylene and hydrogen, while the latter converts light alkenes into higher molecular weight products, such as butylene and hexene. </p> <p>The thesis project focuses on understanding the effect of geometric effects of Pt alloy catalysts for propane dehydrogenation and the methodologies for their characterization. Pt-Co bimetallic catalysts were synthesized with increasing Co loadings, characterized and evaluated for its propane dehydrogenation performance. In-situ synchrotron X-Ray Powder Diffraction (XRD) and X-Ray Absorption (XAS) were used to identify and differentiate between the intermetallic compound phases in the nanoparticle surface and core. Difference spectra between oxidized and reduced catalysts suggested that, despite the increase in Co loading, the catalytic surface remained the same, Pt₃Co in a Au₃Cu structure, while the core became richer in Co, changing from a monometallic Pt fcc core at the lowest Co loading to a PtCo phase in a AuCu structure at the highest loading. Co^II single sites were also observed on the surface, due to non-reduced Co species. The catalytic performance towards propane dehydrogenation reinforced this structure, as propylene selectivity was around 96% for all catalysts, albeit the difference in composition. The Turnover Rate (TOR) of these catalysts was also similar to that of monometallic Pt catalysts, around 0.9 s^-1, suggesting Pt was the active site, while Co atoms behaved as non-active, despite both atoms being active in their monometallic counterparts.</p> <p>In the second project, a single site Co^II catalyst supported on SiO₂ was evaluated for ethylene oligomerization activity. The catalyst was synthesized, evaluated for propane dehydrogenation, propylene hydrogenation and ethylene oligomerization activities and characterized <i>in-situ</i> by XAS and EXAFS and H₂/D₂ exchange experiments. The catalysts have shown negligible conversion at 250^oC for ethylene oligomerization, while a benchmark Ni/SiO₂ catalyst had about 20% conversion and TOR of 2.3x10^-1 s^-1. However, as the temperature increased to above 300^oC, ethylene conversion increased significantly, reaching about 98% above 425^oC. <i>In-situ</i> XANES and EXAFS characterization suggested that H₂ uptake under pure H₂ increased in about two-fold from 200^oC to 500^oC, due to the loss of coordination of Co-O bonds and formation of Co-H bonds. This was further confirmed by H₂/D₂ experiments with a two-fold increase in HD formation per mole of Co. <i>In-situ</i> XAS characterization was also performed with pure C­₂H₄ at 200^oC showed a similar trend in Co-O bond loss, suggesting the formation of Co-alkyl, similarly to that of Co-H. The <i>in-situ</i> XANES spectra showed that the oxidation state remained stable as a Co²⁺ despite the change in the coordination environment, suggesting that the reactions occurs through a non-redox mechanism. These combined results allowed the proposition of a reaction pathway for dehydrogenation and oligomerization reactions, which undergo a similar reaction intermediate, a Metal-alkyl or Metal-Hydride intermediates, activating C-H bonds at high temperatures.</p>

L’aérosol organique secondaire (AOS), fraction majoritaire de l’aérosol submicronique, joue un rôle important sur la santé, l’environnement et le climat. L’évaluation de son impact constitue un véritable enjeu pour la communauté scientifique. Toutefois, nos connaissances actuelles sur les processus de formation d’AOS et sa composition chimique sont encore très lacunaires, et en l’occurrence, limitent le développement des modèles atmosphériques permettant de quantifier les impacts des AOS sur la qualité de l’air et le système climatique. Ainsi, l’objectif de ce travail est de produire un ensemble de données expérimentales fournissant des points de contrainte afin d’évaluer et d’améliorer les modèles. Pour ce faire, la formation d’AOS a été étudiée à partir de la photooxydation d’un précurseur modèle, le n-dodécane, dans la chambre de simulation atmosphérique CESAM. La composition chimique a été élucidée par des techniques spectrométriques et chromatographiques permettant d’identifier les différentes espèces constituant la phase gazeuse et particulaire. En particulier, de nouveaux mécanismes en phase condensée ont été proposés afin d’expliquer la formation des acides carboxyliques et des lactones, identifiés pour la première fois dans l’AOS d’un alcane. Ces derniers pourront être implémentés dans les modèles. Une grande diversité de conditions environnementales, telles que la température, l’humidité relative et la présence/absence de particules préexistantes, a été prise en compte dans ces travaux. Notamment, l’étude de l’influence de la température a mis en évidence une faible sensibilité de ce paramètre sur les rendements de production d’AOS. Tandis que l’étude sur l’effet de l’humidité relative, elle, a montré que l’ajout d’eau dans le système réactionnel au-delà de 5% abaisse les rendements d’AOS de près d’un facteur 2 en comparaison à des conditions sèches. Ainsi, la formation potentielle d’AOS sous ces différentes conditions a permis d’aboutir à des paramétrisations directement utilisables par les modélisateurs. Une caractérisation des effets de paroi dans CESAM, i.e. les pertes en phase gazeuse et particulaire, a également été menée / Secondary Organic Aerosol (SOA), the major fraction of the submicron aerosol, plays a key role on health, environment and climate. The evaluation of its impacts is a real challenge for the scientific community. Our current knowledge of SOA formation processes and chemical composition is still very deficient and limit the development of atmospheric models to quantify the impacts of SOA on air quality and climate system. Therefore, the aim of this work is to produce a set of experimental data to use to constrain and improve the models. To do that, the SOA formation has been studied from the photooxidation of a model precursor, n-dodecane, in the CESAM environmental chamber. The chemical composition has been investigated by spectrometric and chromatographic techniques which allowed us to identify the reaction products constituting the gaseous and particulate phases. In particular, new condensed phase mechanisms have been proposed to explain the formation of carboxylic acids and lactones, identified for the first time. These could be implemented in the models. A wide variety of environmental conditions, such as temperature, relative humidity and the presence/absence of preexisting particles, have been taken into account in this work. The study of the temperature influence has shown a low sensitivity of this parameter on the SOA production. While the study relative humidity effect has shown that adding water to the reaction system beyond 5% lowers SOA yields by almost a factor of 2 in comparison to dry conditions. The SOA formation potential, under these conditions, has been evaluated, and resulted in parameterizations which could be useful for modelers. Furthermore, a characterization of the wall effects in CESAM, i.e. gas and particulate phase wall losses, has been carried out

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