Methane (CH4) is a potent greenhouse gas contributing to the warming of Earth's atmosphere. Lakes are a natural source of CH4, where CH4 generally is produced in oxygen depleted sediments. Ebullitive CH4 is regulated naturally in the oxic-anoxic interface of lakes by methane oxidizing bacteria, methanotrophs uses CH4 as a substrate when O2 is present. Lakes in boreal regions are among the largest sources of CH4 emissions, CH4 oxidation can mitigate some of the CH4 emissions from lakes. Gaps in knowledge and data remain regarding net fluxes of CH4, indicating that there are processes unaccounted for. Previous research highlights the variability of CH4 emissions and oxidations rates in lakes, there is lacking knowledge on what drives the variability of oxidation rates and total emissions. It’s been suggested that availability of phosphorus (P) has a positive relationship with increased oxidation rates. Moreover, availability of trace elements has been suggested to affect aerobic CH4 oxidation, but there is a lack of knowledge on these factors in natural lake waters. In this study incubations with lake water from two different lakes, Gårasjön and Kisasjön, were prepared with different treatments of P and/or trace elements. We investigate how this can affect the rate of CH4 oxidation when incubated in specific conditions. Our results indicate that treatments with added P had a greater tendency to exhibit higher rates of methane oxidation in both lakes, while treatments with trace elements and P had varied oxidation rates depending on the lake. This suggests that when there are no limitations of the substrates CH4 and O2, the oxidations rates in lakes might be limited by the availability of P and the specific lake conditions can influence CH4 oxidation.

Bactérias metanotróficas são capazes de utilizar metano como única fonte de carbono e energia, e sua importância no ambiente está relacionada à mitigação das emissões deste gás para a atmosfera. Os manguezais brasileiros são altamente produtivos, apresentam potencial para a produção de metano, e infere-se que a comunidade metanotrófica seja fundamental neste ecossistema. O escopo do projeto foi pesquisar a diversidade taxonômica e funcional de bactérias metanotróficas presentes em sedimento do manguezal de Bertioga (SP, Brasil), através de novas técnicas de cultivo e enriquecimento, incluindo a técnica de DNA-SIP com utilização do metano como substrato marcado, o que permite estudar o papel das bactérias não cultiváveis na oxidação do CH4. Consórcios que utilizam metano para o crescimento foram obtidos nos pontos estudados. Representando a microbiota ativa (DNA marcado), foram identificadas metanotróficas clássicas da família Methylococcaceae, além de grupos de micro-organismos cujo papel no ciclo do CH4 é incerto, como os da Família Methylophilaceae e do Filo TM7. / Methanotrophic bacteria are able to use methane as sole carbon and energy source, and its importance in the environment is related to the mitigation of methane emissions to the atmosphere. Brazilian mangroves are highly productive, have potential to methane production, and it is inferred that methanotrophic community is of great importance for this ecosystem. The scope of the project was to investigate the functional and taxonomic diversity of methanotrophic bacteria present in sediments from Bertioga´s mangrove (SP, Brazil), through new techniques of cultivation and enrichment, including the technique of DNA-SIP with the use of methane as a labeled substrate, which allows to study the role of non-culturable bacteria in the oxidation of CH4. Microbial consortia using methane for growth were obtained from studied samples. Representing the active microbiota (labeled DNA), were identified classic metanotrophs belonging to Family Methylococcaceae, and groups of micro-organisms whose role in methane cycle is uncertain, as the Family Methylophilaceae and the Phylum TM7.

Bactérias metanotróficas são capazes de utilizar metano como única fonte de carbono e energia, e sua importância no ambiente está relacionada à mitigação das emissões deste gás para a atmosfera. Os manguezais brasileiros são altamente produtivos, apresentam potencial para a produção de metano, e infere-se que a comunidade metanotrófica seja fundamental neste ecossistema. O escopo do projeto foi pesquisar a diversidade taxonômica e funcional de bactérias metanotróficas presentes em sedimento do manguezal de Bertioga (SP, Brasil), através de novas técnicas de cultivo e enriquecimento, incluindo a técnica de DNA-SIP com utilização do metano como substrato marcado, o que permite estudar o papel das bactérias não cultiváveis na oxidação do CH4. Consórcios que utilizam metano para o crescimento foram obtidos nos pontos estudados. Representando a microbiota ativa (DNA marcado), foram identificadas metanotróficas clássicas da família Methylococcaceae, além de grupos de micro-organismos cujo papel no ciclo do CH4 é incerto, como os da Família Methylophilaceae e do Filo TM7. / Methanotrophic bacteria are able to use methane as sole carbon and energy source, and its importance in the environment is related to the mitigation of methane emissions to the atmosphere. Brazilian mangroves are highly productive, have potential to methane production, and it is inferred that methanotrophic community is of great importance for this ecosystem. The scope of the project was to investigate the functional and taxonomic diversity of methanotrophic bacteria present in sediments from Bertioga´s mangrove (SP, Brazil), through new techniques of cultivation and enrichment, including the technique of DNA-SIP with the use of methane as a labeled substrate, which allows to study the role of non-culturable bacteria in the oxidation of CH4. Microbial consortia using methane for growth were obtained from studied samples. Representing the active microbiota (labeled DNA), were identified classic metanotrophs belonging to Family Methylococcaceae, and groups of micro-organisms whose role in methane cycle is uncertain, as the Family Methylophilaceae and the Phylum TM7.

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Ce travail porte sur l’étude de systèmes catalytiques innovants par la technique d’échange isotopique (EI) permettant d’apprécier des propriétés fondamentales (activation des molécules en surface, mobilité et réactivité des atomes de réseau) pour comprendre les mécanismes de réaction mis en jeu en catalyse hétérogène et développer des systèmes plus performants. Aussi, l’identification d’espèces adsorbées intermédiaires est possible en couplant la spectrométrie de masse (analyse de la phase gaz) à l’observation de la surface catalytique par spectroscopie DRIFT.L’EI 16O/18O montre des effets de dispersion ou de synergie de LaMnO3 (LM) supportée sur YSZ ou TiO2 expliquant les performances de cette structure pérovskite pour l’oxydation catalytique de C7H8 via un mécanisme suprafacial. L’activité en EI C16O2/C18O2 démontre la mobilité exceptionnelle des atomes O de réseau de YSZ dès 150 °C via la formation d’espèces (hydrogéno)carbonates en surface. En catalyse d’oxydation, à T < 800 °C, cette mobilité est pourtant limitée par l’activation d’O2 à la surface de YSZ. La solution proposée ici est la génération préalable d’une espèce oxygène réactive sur un lit de matériau réductible type LM. Le double-lit LM-YSZ montre d’excellentes performances pour abaisser la température d’oxydation de CH4 à 425 °C via un mécanisme Mars van Krevelen (MvK) où les atomes O de YSZ participent à la réaction par l’intermédiaire d’espèces formiates.L’EI 14N/15N est également utilisé dans ce travail pour analyser la réactivité des atomes N de réseau dans les nitrures métalliques. En particulier, Co3Mo3N et Ni2Mo3N montrent des propriétés remarquables, dépendant de la méthode de préparation ou du prétraitement appliqué. Leur comportement suggère la participation des atomes N dans la réaction de synthèse de NH3 sur le principe d’un mécanisme MvK. / This work concerns the study of new catalytic systems by isotopic exchange (IE) technique allowing to appreciate basic properties (molecules surface activation, mobility and reactivity of lattice atoms) to better understand catalytic mechanisms and to develop efficient catalysts. The identification of intermediate adsorbed species is possible by coupling mass spectrometry (gas-phase analysis) with the catalytic surface analysis by DRIFT spectroscopy.IE 16O/18O shows dispersal and synergetic effect of supported LaMnO3 perovskite (LM) on YSZ or TiO2 which explain catalytic performances of this perovskite structure for toluene oxidation via a suprafacial mechanism. IE C16O2/C18O2 activity demonstrates the remarkable lattice O atoms mobility of YSZ from 150 °C via adsorbed (hydrogeno)carbonates. To the contrary, in oxidation catalysis, under 800 °C, this mobility is very limited by O2 activation on YSZ surface. The solution proposed in this work is the previous generation of reactive oxygen species on a first catalytic bed of reducible material as LM. LM+YSZ dual-bed shows very efficient activity to reduce methane oxidation temperature at 425 °C via a Mars-van Krevelen (MvK) mechanism in which lattice O atoms of YSZ take part in the reaction by intermediate formate species.IE 14N/15N is thereafter used to analyse lattice N atoms reactivity of metal nitrides materials. In particular, Co3Mo3N and Ni2Mo3N show interesting properties depending on preparation or pre-treatement routes. This behaviour supposes that ammonia synthesis reaction could be procced via MvK type mechanism with the participation of lattice N of this nitrides.

Ce travail se concentre sur le développement de systèmes catalytiques capable d’oxyder complètement le méthane à basse température. Le sujet principal concerne la conception d'une nouvelle génération de catalyseurs à base de palladium qui sont résistants aux composés soufrés et à l'eau.<p>Notre objectif a été atteint grâce à l'utilisation d'un support oxyde mixte produit par sol-gel. En effet, nos catalyseurs de palladium supporté sur un oxyde de silicium dopé au titane se sont révélés être résistants à l’empoisonnement au soufre et présentent des performances élevées pour la conversion du méthane.<p>En variant les quantités de TiO2, il a été montré que les performances atteignent un maximum pour une composition en masse de 10% TiO2. Les analyses structurelles et de surface ont montré que nos supports mixtes contiennent des liens Ti-O-Si. Nous pensons que ces liens sont responsables de l’activité accrue du catalyseur.<p>Par ailleurs, les catalyseurs contenant du titane présentent une tolérance supérieure vis-à-vis du SO2 lorsque celui-ci est ajouté aux réactifs ou que le catalyseur est exposé à une atmosphère de SO2 pur à 350°C pendant 15 heures. Nous avons mis en évidence par XPS que les sites Ti-O-Si sont également responsables de cette tolérance aux composés soufrés. Ceci est accompli par l'insertion du SO2 dans le support qui forme des liens soit Ti-O-SOx•••Si soit Si-O-SOx•••Ti. L’analyse XPS a également montré que sur le long terme, l’exposition au SO2 conduit à la formation d’une couche de PdSO4 de 18 à 20 Å. Étonnamment, les catalyseurs sont capables de récupérer entièrement leur activité initiale après ce traitement. Cette régénération se produit grâce à un mécanisme concerté avec le méthane permettant la décomposition totale du PdSO4. Par ailleurs, des études en présence d'eau ont montré que ces propriétés restent inchangées.<p>L'état du palladium a également été étudié et nous a permis de prouver qu’une activation/stabilisation du catalyseur est nécessaire. Celle-ci est réalisée en présence des réactifs par de légères modifications chimiques du support et de la phase de palladium. En effet, l'augmentation de l'activité du catalyseur a été corrélée avec une augmentation des quantités de Ti3+ et Pd0. La présence de palladium métallique dans le catalyseur semble être l'élément clé dans l'activation des liaisons C-H.<p>Enfin, nous avons étudié l'influence de la taille/la dispersion des particules de palladium sur la vitesse de réaction. L'utilisation de synthèses en phase liquide nous a permis de produire des solutions colloïdales de particules de palladium avec des tailles contrôlées. Cette étude a révélé que la combustion du méthane est une réaction sensible à la structure. Néanmoins, un meilleur contrôle de la forme des nanoparticules devrait être réalisé pour déterminer les facteurs structurels influençant la réaction./ The present work focuses on the development of highly efficient catalytic systems able to completely oxidize methane at low temperature in order to comply with modern environmental legislation. The main subject concerns the design of a new generation of palladium-based catalysts that are sulfur and water resistant. <p>Our goal was achieved through the use of a mixed oxide support produced by sol-gel. In fact, palladium-supported on titanium-doped silica catalysts have proven to be sulfur tolerant and exhibit high performances for the methane conversion. <p>Varying the amounts of TiO2 showed that the performance reached an optimum for a 10 wt.% TiO2 loading. According to the structural and surface analyses, the mixed oxides contained Ti-O-Si linkages, believed to be responsible for the better activity as compared to PdO supported on pure oxides. <p>Moreover, the titania-containing catalysts exhibited a superior tolerance towards SO2 when either adding it to the reactants or feeding it as a pure pretreatment atmosphere at 350°C (15 hour on stream). We evidenced using XPS that the Ti-O-Si sites are also responsible for the higher sulfur tolerance of the catalysts by the insertion of SO2 in the support forming either Ti-O-SOx•••Si or Si-O-SOx•••Ti. XPS analyses also evidenced that the long-term SO2-treatment leads to the formation of PdSO4 with a thickness of 18 to 20 Å. However, the catalysts can entirely recover their initial activity after this treatment. This regeneration was proven to be occurring through a concerted mechanism with methane leading to the total decomposition of PdSO4. Moreover, studies in presence of water showed that these properties remained unchanged.<p>The state of the palladium was also investigated and allowed us to evidence that an activation/stabilization of the catalyst is necessary. This is achieved in presence of the reactants by slight and subtle changes in both the support and the palladium phase. The increase of the catalyst activity was correlated with an increase of Ti3+ and Pd0 fractions. The presence of metallic palladium in the catalyst seems to be the key element in the activation of the C-H bonds. <p>Finally, we have studied the influence of the size/dispersion of the palladium particles on the reaction rate. The use of wet-chemistry synthesis allowed us to produce colloidal solutions of palladium with controlled particles sizes. This study revealed that the methane combustion is a structure sensitive or demanding reaction. Nevertheless, a better control of the shape of the nanoparticles should be achieved to determine the structural factor influencing the reaction.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished