Im Rahmen der vorliegenden Arbeit wird die CH4-Oxidation an LaFeO3-Katalysatoren unter CH4-reichen und O2-reichen Reaktionsbedingungen betrachtet. Durch Analyse der Struktur-Aktivitätsbeziehungen wird gezeigt, dass eine Kombination von hoher BET-Oberfläche und großer Anzahl an 6-fach von Sauerstoff koordinierten perowskitischen Fe3+-Spezies für eine hohe CH4-Oxidationsaktivität vorteilhaft ist. Mit dem aktivsten LaFeO3-Perowskit kann Sauerstoff unter technisch relevanten Bedingungen bereits bei Temperaturen unterhalb von 350 °C vollständig aus Biogas entfernt werden. Mit einem auf dem Langmuir-Hinshelwood-Mechanismus basierenden kinetischen Modell kann die Methanoxidation unter CH4-reichen Bedingungen erfolgreich simuliert werden. Weiterhin kann der aktivste LaFeO3-Katalysator unter O2-reichen Bedingungen zur Oxidation von Formaldehyd im Abgas magerer Gasmotoren im Temperaturbereich von 350 bis 500 °C eingesetzt werden.:1. Einleitung und Problemstellung 1 2. Einführung in die Literatur 5 2.1. Die Perowskitstruktur 5 2.2. Verwendung von Perowskiten als Katalysatoren 7 2.2.1. CH4-Oxidation 7 2.2.2. CO-Oxidation 12 2.2.3. Oxidation weiterer Kohlenwasserstoffe 14 2.2.4. Minderung von Stickoxiden 16 2.2.5. Weitere katalytische Anwendungen 17 2.3. Katalytische CH4-Oxidation an Edelmetallkatalysatoren 18 2.4. Reaktive Sauerstoffspezies von Perowskitkatalysatoren 20 3. Experimenteller Teil 22 3.1. Synthese von LaFeO3-Katalysatoren 22 3.1.1. PVA-Synthese 22 3.1.2. Citratsynthese 23 3.1.3. Pechini-Synthese 24 3.1.4. NH3-Selbstverbrennung 24 3.1.5. Glycinselbstverbrennung 25 3.1.6. Herstellung von Granulaten 25 3.1.7. Herstellung beschichteter Wabenkatalysatoren 26 3.2. Verwendete Laborapparatur 27 3.3. Charakterisierung der Katalysatoren 28 3.3.1. N2-Physisorption 29 3.3.2. Temperaturprogrammierte Desorption von NH3 30 3.3.3. Temperaturprogrammierte Reduktion mit H2 31 3.3.4. Röntgendiffraktometrie 33 3.3.5. Mößbauerspektroskopie 34 3.3.6. Röntgenphotoelektronenspektroskopie 35 3.4. Katalytische Untersuchungen 36 3.4.1. CH4-Oxidation an LaFeO3-Pulverkatalysatoren im CH4-Überschuss 36 3.4.2. Hydrothermale Alterung des aktivsten LaFeO3-Katalysators 39 3.4.3. Experimentelle Untersuchungen zum Isotopenaustausch mit 18O2 39 3.4.4. Katalytische Aktivitätsmessungen unter sauerstoffreichen Reaktionsbedingungen 41 3.4.5. Testung beschichteter Waben unter sauerstoffreichen Reaktionsbedingungen 42 3.4.6. Untersuchungen zur Verweilzeitverteilung 43 4. Auswertung und Diskussion der Ergebnisse 45 4.1. CH4-Oxidationsaktivität und physikalisch-chemische Eigenschaften der mittels verschiedener Synthesetechniken hergestellten LaFeO3- Katalysatoren 45 4.2. Struktur-Aktivitätskorrelation der mittels Citratsynthese hergestellten LaFeO3-Katalysatoren 49 4.3. Einfluss der Substitution von La durch Ce oder K auf die CH4- Oxidationsaktivität von LaFeO3-Katalysatoren 68 4.4. Einfluss der Raumgeschwindigkeit auf die CH4-Oxidationsaktivität des aktivsten LaFeO3-Katalysators 79 4.5. Einfluss des O2- und CH4-Gehalts im Gasstrom auf die CH4- Oxidationsaktivität des aktivsten LaFeO3-Katalysators 81 4.6. Einfluss der hydrothermalen Alterung auf die CH4-Oxidationsaktivität des aktivsten LaFeO3-Katalysators 84 4.7. Isotopenaustausch mit 18O2 87 4.8. Kinetische Modellierung der CH4-Oxidation unter CH4-reichen Bedingungen am aktivsten LaFeO3-Katalysator 95 4.8.1. Formalkinetischer Ansatz 97 4.8.2. Kinetischer Ansatz auf Basis eines Langmuir-Hinshelwood-Mechanismus 103 4.8.3. Vergleich der beiden kinetischen Modelle 110 4.9. CH4-Oxidation an LaFeO3-Katalysatoren im Sauerstoffüberschuss 112 4.10. Kombinierte Entfernung von CH4, CO und Formaldehyd an mit dem aktivsten LaFeO3-Katalysator beschichteten Mullit-Wabenträgern aus dem Abgas von mager betriebenen Gasmotoren 117 4.11. Anwendung des kinetischen Langmuir-Hinshelwood-Modells auf die CH4- Oxidation am aktivsten LaFeO3-Katalysator unter O2-reichen Reaktionsbedingungen 123 5. Zusammenfassung und Ausblick 130 6. Literaturverzeichnis 134 7. Verzeichnis der verwendeten Formelzeichen 145 8. Anhang 148

Hidroeletricidade tem o potencial para mitigar as mudanças climáticas, embora a pegada de carbono desta fonte de energia ainda é questionada. O metano é um dos principais gases de efeito estufa e a emissão deste gás é ignorada nas avaliações de impacto ambiental de hidrelétricas. Fluxos de metano resultam do balanço entre dois processos microbianos: metanogênese e oxidação do metano. Dados coletados em reservatórios brasileiros, indicaram os parâmetros que configuram a distribuição destas comunidades microbianas. Descobrimos que o balanço entre a oxidação de metano e metanogênese, quantificada por abundâncias de genes (mcrA e pmoA), resulta em diferentes quantidades de metano. Para medir o efeito da mudança do uso do solo após a construção de um reservatório, avaliamos o potencial metanogênico com amostras em microcosmos simulando condições de alagamento. Informações geradas neste trabalho contribuirão para alcançar o desafio de projetos hidrelétricos: redução das emissões de gases de efeito estufa e garantir o fornecimento de energia no Brasil. / Hydropower has the potential to mitigate climate change, although carbon footprint of this renewal energy source is still questioned. Methane is one of the main greenhouse gases, but emission of this gas is ignored in environmental assessments of hydroelectricity impact. Methane fluxes result from the balance between two microbial processes: methanogenesis and methane oxidation. From data collected in Brazilian reservoirs we identify parameters that shape the balance of microbial communities related to methane We found that balance between metanogênese and methane oxidation, quantified by mcrA and pmoA gene abundances, result in different values for methane emissions. In order to measure the effect of land use change after a reservoir construction, we evaluate methanogenic potential from samples incubated in microcosms simulating flooded and anoxic conditions. Information acquired in this work will contribute to achieve the challenge for future hydropower projects: settles the reduction of emissions greenhouse gases and guarantee the supply of energy demands.

Methane derived authigenic carbonate (MDAC) precipitation occurs within marine sediments as a byproduct of the microbial anaerobic oxidation of methane (AOM). While these carbonates form in chemical and isotopic equilibrium with the fluids from which they precipitate, burial diagenesis and recrystallization can overprint these signals. Plane polarized light (PPL) and cathodoluminescent (CL) petrography have allowed for detailed characterization of carbonate phases and their subsequent alteration. Modern MDACs sampled offshore in northern Cascadia (n =33) are compared with paleoseep carbonates (n =13) uplifted on the Olympic Peninsula in order to elucidate primary vs. secondary signals, with relevance to interpretations of the carbonate record. The modern offshore environment (S. Hydrate Ridge and Barkley Canyon) is dominated by metastable acicular and microcrystalline aragonite and hi-Mg calcite (HMC) that with time will recrystallize to low-Mg calcite (LMC). The diagenetic progression is accompanied by a decrease in Mg/Ca and Sr/Ca ratios while variation in Ba/Ca depends upon the Ba-concentration of fluids that spur recrystallization. CL images discern primary carbonates with high Mn/Ca from secondary phases that reflect the Mn- enrichment that characterizes deep sourced fluids venting at Barkley Canyon. Methane along the Cascadia continental margin is mainly of biogenic origin, where reported strontium isotopic values reflect a mixture of seawater with fluids modified by reactions with the incoming Juan de Fuca plate. In contrast, the Sr-isotopic composition of carbonates and fluids from Integrated Ocean Drilling Program (IODP) Site U1329 and nearby Barkley Canyon point to a distinct endmember (lowest ⁸⁷Sr/⁸⁶Sr = 0.70539). These carbonates also show elevated Mn/Ca and δ¹⁸O values as low as -12‰, consistent with a deep-source of fluids feeding thermogenic hydrocarbons to the Barkley Canyon seeps. Two paleoseep carbonates sampled from the uplifted Pysht/Sooke Fm. have ⁸⁷Sr/⁸⁶Sr values similar to those of the anomalous Site U1329 and Barkley Canyon carbonates (⁸⁷Sr/⁸⁶Sr = 0.70494 and 0.70511). We postulate that the ⁸⁷Sr-depleted carbonates and pore fluids found at Barkley Canyon represent migration by the same type of deep, exotic fluid as is found in high permeability conglomerate layers down to 190 mbsf at Site U1329, and which fed paleoseeps in the Pysht/Sooke Fm. These exotic fluids likely reflect interaction with the 52-57 Ma igneous Crescent Terrane, which is located down-dip from both Barkley Canyon and Site U1329. This previously unidentified endmember fluid in northern Cascadia may have sourced cold seeps in this margin since at least the late Oligocene. / Graduation date: 2012

The Batumi Seep Area, offshore Georgia, Black Sea, has been intensively cored (gravity cores and TV-guided multi-cores) to investigate the methane turnover in the surface sediments. The seep area is characterized by vigorous methane gas bubble emanations. Geochemical analyses show a microbial origin of the methane and a shallow fluid source. Anaerobic methane oxidation rapidly consumes the SO4 2- within the top 5-20 cm, but significant upward fluid advection is not indicated by the porewater profiles. Hence, the Batumi Seep Area must be dominated by methane gas seepage in order to explain the required CH4 flux from below. 1-D transport-reaction modelling constrains the methane flux needed to support the observed SO4 2- flux as well as the rate of near-surface hydrate formation. The model results correlate well with the hydro-acoustic backscatter intensities recorded and mapped bubble release sites using the sonar of a ROV.

Hidroeletricidade tem o potencial para mitigar as mudanças climáticas, embora a pegada de carbono desta fonte de energia ainda é questionada. O metano é um dos principais gases de efeito estufa e a emissão deste gás é ignorada nas avaliações de impacto ambiental de hidrelétricas. Fluxos de metano resultam do balanço entre dois processos microbianos: metanogênese e oxidação do metano. Dados coletados em reservatórios brasileiros, indicaram os parâmetros que configuram a distribuição destas comunidades microbianas. Descobrimos que o balanço entre a oxidação de metano e metanogênese, quantificada por abundâncias de genes (mcrA e pmoA), resulta em diferentes quantidades de metano. Para medir o efeito da mudança do uso do solo após a construção de um reservatório, avaliamos o potencial metanogênico com amostras em microcosmos simulando condições de alagamento. Informações geradas neste trabalho contribuirão para alcançar o desafio de projetos hidrelétricos: redução das emissões de gases de efeito estufa e garantir o fornecimento de energia no Brasil. / Hydropower has the potential to mitigate climate change, although carbon footprint of this renewal energy source is still questioned. Methane is one of the main greenhouse gases, but emission of this gas is ignored in environmental assessments of hydroelectricity impact. Methane fluxes result from the balance between two microbial processes: methanogenesis and methane oxidation. From data collected in Brazilian reservoirs we identify parameters that shape the balance of microbial communities related to methane We found that balance between metanogênese and methane oxidation, quantified by mcrA and pmoA gene abundances, result in different values for methane emissions. In order to measure the effect of land use change after a reservoir construction, we evaluate methanogenic potential from samples incubated in microcosms simulating flooded and anoxic conditions. Information acquired in this work will contribute to achieve the challenge for future hydropower projects: settles the reduction of emissions greenhouse gases and guarantee the supply of energy demands.

De grandes quantités de méthane sont générées dans les sédiments marins, mais l'émission dans l'atmosphère de ce gaz à effet de serre important est en partie contrôlé par oxydation anaérobie de méthane couplé à la réduction de sulfate (SR AOM). AOM-SR est médiée par des méthanotrophes anaérobies (ANME) et bactéries sulfato-réductrices (SRB). AOM-SR est non seulement la régulation du cycle du méthane, mais il peut être utile appliquée pour la désulfuration des eaux usées industrielles au détriment du méthane comme source de carbone. Cependant, il a une bouilloire jambe pour contrôler et comprendre pleinement ce processus, principalement en raison de la lenteur croissante de l'ANME. Cette recherche a étudié de nouvelles approches pour contrôler et enrichiront ANME AOM SR et SRB dans le but final de la conception d'un bioréacteur approprié pour AOM SR à la pression ambiante et la température. Ceci a été réalisé en étudiant l'effet de (i) la pression et (ii) l'utilisation de différents composés du soufre comme accepteurs d'électrons sur AOM, (iii) la caractérisation de la communauté microbienne et (iv) L'identification des facteurs contrôlant la croissance des ANME et SRB .Théoriquement, le méthane des pressions partielles élevées favorisent AOM-SR, en plus de méthane sera dissoute et biodisponible. La première approche impliquait l'incubation d'un sédiments marins peu profonds (lac marin Gravelines) sous des gradients de pression. De manière surprenante, la plus haute AOM-SR activité a été obtenue à basse pression (MPa 00:45), montrant l'actif ANME méthane préféré faible disponibilité sur haute pression (10, 20, 40 MPa). Fait intéressant, ook l'abondance et la structure des différents types de ANME et CVN Piloté par pression.En outre, les micro-organismes présents dans les sédiments d'oxydation anaérobie de méthane ont été enrichies avec du méthane en tant que substrat dans le filtre de percolateur (BTF) aux conditions ambiantes. Autres composés de soufre (sulfate, thiosulfate et en soufre élémentaire) ont été utilisés comme accepteurs d'électrons. Quand a été utilisé comme thiosulfate accepteur d'électrons, son dismutation en sulfate et de sulfure a été la conversion de soufre dominant, mais les taux les plus élevés UTILE AOM-SR ont été enregistrés dans ce BTF. Par conséquent, AOM peut être directement couplé à la réduction ou thiosulfate, ou à la réduction du sulfate produit par le thiosulfate de dismutation. De plus, l'utilisation de thiosulfate a déclenché l'enrichissement ou SRB. D'autres termes, on a obtenu le plus haut ou l'enrichissement ANME Lorsque seul le sulfate a été utilisé comme accepteur d'électrons.Dans un BTF avec du sulfate en tant qu'accepteur d'électrons, tous deux ANME et SRB ont été enrichies à partir de sédiments marins et les flux de carbone à l'intérieur des micro-organismes enrichis ont été étudiés par fluorescence in situ échelle hybridation nanomètres spectrométrie de masse d'ions secondaires (SIMS Nano-FISH). Les résultats préliminaires montrent l'absorption du méthane par un groupe spécifique de SRB.ANME et SRB adaptée aux conditions de sédiments profonds ont été enrichis dans un BTF à la pression ambiante et de la température. Le BTF est une combinaison bioréacteur de démarrage pour l'enrichissement ou lente des micro-organismes en croissance. De plus, peut être utilisé thiosulfate pour activer les sédiments et enrichir la communauté SRB plus d'enrichir la population stratégie ANME pour obtenir une haute AOM SR et plus rapide taux de croissance ANME et SRB pour les applications futures / Large amounts of methane are generated in marine sediments, but the emission to the atmosphere of this important greenhouse gas is partly controlled by anaerobic oxidation of methane coupled to sulfate reduction (AOM-SR). AOM-SR is mediated by anaerobic methanotrophs (ANME) and sulfate reducing bacteria (SRB). AOM-SR is not only regulating the methane cycle but it can also be applied for the desulfurization of industrial wastewater at the expense of methane as carbon source. However, it has been difficult to control and fully understand this process, mainly due to the slow growing nature of ANME. This research investigated new approaches to control AOM-SR and enrich ANME and SRB with the final purpose of designing a suitable bioreactor for AOM-SR at ambient pressure and temperature. This was achieved by studying the effect of (i) pressure and of (ii) the use of different sulfur compounds as electron acceptors on AOM, (iii) characterizing the microbial community and (iv) identifying the factors controlling the growth of ANME and SRB.Theoretically, elevated methane partial pressures favor AOM-SR, as more methane will be dissolved and bioavailable. The first approach involved the incubation of a shallow marine sediment (marine Lake Grevelingen) under pressure gradients. Surprisingly, the highest AOM-SR activity was obtained at low pressure (0.45 MPa), showing that the active ANME preferred scarce methane availability over high pressure (10, 20, 40 Mpa). Interestingly, also the abundance and structure of the different type of ANME and SRB were steered by pressure.Further, microorganisms from anaerobic methane oxidizing sediments were enriched with methane gas as the substrate in biotrickling filters (BTF) at ambient conditions. Alternative sulfur compounds (sulfate, thiosulfate and elemental sulfur) were used as electron acceptors. When thiosulfate was used as electron acceptor, its disproportionation to sulfate and sulfide was the dominating sulfur conversion, but also the highest AOM-SR rates were registered in this BTF. Therefore, AOM can be directly coupled to the reduction of thiosulfate, or to the reduction of sulfate produced by thiosulfate disproportionation. Moreover, the use of thiosulfate triggered the enrichment of SRB. Differently, the highest enrichment of ANME was obtained when only sulfate was used as electron acceptor.In a BTF with sulfate as electron acceptor, both ANME and SRB were enriched from marine sediment and the carbon fluxes within the enriched microorganisms were studied through fluorescence in-situ hybridization-nanometer scale secondary ion mass spectrometry (FISH-NanoSIMS). Preliminary results showed the uptake of methane by a specific group of SRB.ANME and SRB adapted to deep sediment conditions were enriched in a BTF at ambient pressure and temperature. The BTF is a suitable bioreactor for the enrichment of slow growing microorganisms. Moreover, thiosulfate can be used to activate the sediment and enrich the SRB community to further enrich the ANME population as strategy to obtain high AOM-SR and faster ANME and SRB growth rates for future applications

La construction des biosystèmes d’oxydation passive du méthane (BOPM) est une option économique et durable pour réduire les émissions de méthane des sites d’enfouissement de déchets et des effets subséquents du réchauffement climatique. Les BOPM sont constitués de deux couches principales: la couche d'oxydation du méthane (MOL) et la couche de distribution du gaz (GDL). L'oxydation du méthane se produit dans la MOL par les réactions biochimiques des bactéries méthanotrophes, et la GDL est construite sous la MOL pour intercepter et distribuer les émissions fugitives de biogaz à la base de la MOL. Fondamentalement, l'efficacité d'un BOPM est définie en fonction de l'efficacité d'oxydation du méthane dans la MOL. Par conséquent, il est indispensable de fournir des conditions adéquates pour les activités bactériennes des méthanotrophes. En plus des paramètres environnementaux, l'intensité et la distribution du biogaz influencent l'efficacité des BOPM, et ils peuvent rendre le matériau de la MOL - avec une grande capacité d'accueillir les activités bactériennes - inutilisables en termes d'oxydation du méthane sur place. L'effet de barrière capillaire le long de l'interface entre la GDL et la MOL peut provoquer des émissions localisées de méthane, due à la restriction ou la distribution non uniforme de l’écoulement ascendant du biogaz à la base de la MOL. L'objectif principal de cette étude est d'incorporer le comportement hydraulique non saturé des BOPM dans la conception des BOPM, afin d’assurer la facilité et la distribution adéquates de l'écoulement du biogaz à la base de la MOL. Les fonctions de perméabilité à l'air des matériaux utilisés pour construire la MOL des BOPM expérimentaux au site d’enfouissement des déchets de St Nicéphore (Québec, Canada), ainsi que celles d'autres de la littérature technique, ont été étudiés pour évaluer le comportement d'écoulement non saturé du gaz dans les matériaux et pour identifier le seuil de migration sans restriction du gaz. Ce dernier seuil a été introduit en tant que un paramètre de conception avec lequel le critère de conception recommandé ici, c’est à dire la longueur de la migration sans restriction de gaz (LMSG), a été défini. La LMSG est considérée comme la longueur le long de l'interface entre la GDL et la MOL où le biogaz peut migrer à travers la MOL sans restriction. En réalisant des simulations numériques avec SEEP/W, les effets de la pente de l'interface, des paramètres définissant la courbe de rétention d'eau, de la fonction de la conductivité hydraulique du matériau de la MOL sur la valeur de la LMSG (représentant la facilité d'écoulement du biogaz à l'interface) et de la distribution de l'humidité (et par conséquent celle du biogaz) ont été évalués. Selon les résultats des simulations, la conductivité hydraulique saturée et la distribution des tailles de pores du matériau de la MOL sont les paramètres les plus importants sur la distribution de l'humidité le long de l'interface. Ce dernier paramètre influe également sur la valeur du degré de saturation et donc la facilité du biogaz à la base de la MOL. La densité sèche du matériau de MOL est un autre paramètre qui contrôle la facilité d'écoulement ascendant du biogaz. Les limitations principales de la présente étude sont associées au nombre de matériaux de MOL testés et à l'incapacité de SEEP/W de considérer l'évapotranspiration. Toutefois, compte tenu des hypothèses raisonnables dans les simulations et en utilisant les données de la littérature, on a essayé de réduire ces limitations. En utilisant les résultats des expériences et des simulations numériques, des étapes et des considérations de conception pour la sélection du matériau de MOL et de la pente d'interface ont été proposées. En effet,le comportement hydraulique non saturé des matériaux serait intégré dans les nécessités de conception pour un BOPM efficace, de sorte que la capacité maximale possible d'oxydation du méthane du matériau de la MOL soit exploitée. / Abstract : Implementation of passive methane oxidation biosystems (PMOB) is a cost effective and sustainable solution to eliminate the methane emissions of landfills to the atmosphere and ensuing global warming effects. PMOBs consist of two main layers: methane oxidation layer (MOL) and gas distribution layer (GDL). The oxidation of methane occurs in MOL through the biochemical reactions of methanotrophic bacteria, and GDL is constructed beneath the MOL to intercept and distribute the fugitive biogas emissions at the base of MOL. Basically, the efficiency of a PMOB is defined based on the methane oxidation efficiency in MOL. Therefore, it is indispensable to provide adequate conditions for the bacterial activities of methanotrophs. In addition to the environmental parameters, the intensity and the distribution of the biogas reaching the MOL material influence the efficiency of PMOBs, and they may cause the MOL material possessing great capacity to host the bacterial activities to be unserviceable in terms of in field methane oxidation. The capillary barrier effect along the GDL MOL interface may provoke localized surface methane emissions, resulted from the restricted and/or non uniform distribution of upward flow of biogas at the base of MOL. The main focus of present study is to incorporate the unsaturated hydraulic behavior of PMOBs into the design of PMOBs, providing adequate ease and distribution of upward flow of biogas at the base of MOL. The air permeability functions of the materials used to construct the MOL of experimental PMOBs at the St Nicephore landfill (Quebec, Canada), along with other materials from the technical literature, were studied to evaluate the unsaturated gas flow behavior of the materials and to identify the threshold of unrestricted gas migration. This latter threshold was introduced as a design parameter based on which the recommended design criterion herein, i.e. the length of unrestricted gas migration (LUGM), was defined. LUGM is considered as the length along the GDL MOL interface along which biogas can migrate upwards without restriction. Performing sets of numerical simulations in SEEP/W, the effect of slope of interface and the parameters defining the water retention curve and hydraulic conductivity function of MOL material on value of LUGM (representing the ease of upward flow of biogas at the interface) and distribution of moisture (and therefore biogas) along the GDL MOL interface were assessed. The saturated hydraulic conductivity and the pore size distribution of the MOL material were the most influencing parameters in distribution of moisture along the interface. The latter parameter influences also the value of degree of saturation and therefore, the ease of biogas at the base of MOL. Dry density of MOL material is another parameter that controls the ease of upward flow of biogas. The main limitations of the present study are associated with the number of tested MOL materials and the inability of SEEP/W in considering the evapotranspiration. However, considering reasonable assumptions in simulations and using the data from the literature, it was attempted to reduce the limitations. Based on the results of experiments and numerical simulations, some design steps and considerations for selection of the MOL material and the slope of interface were suggested that incorporate the unsaturated hydraulic behavior into the design necessities for an efficient PMOB so that the maximum possible methane oxidation capacity of MOL material is exploited.

Freshwater lakes constrain its methane (CH4) emissions through CH4 oxidation. CH4 includes three carbon (C) isotopes; the stable isotopes 12C,13C and the unstable and more uncommon isotope 14C. Methanotrophs (i.e. methane oxidizing bacteria) oxidize the lighter isotope more rapidly. Changes in relative isotopic composition can therefore be used to calculate how much CH4 is oxidized in a system. This study investigates an annual CH4 oxidation in a freshwater lake. Water samples and bubbles of CH4 gas were collected once a month, from March to November, in lake Gundlebosjön. The CH4 gas was separated from the water samples with a headspace extraction technique. The concentration and isotopic composition of CH4 was analyzed in a cavity ring down spectrometer. The isotopic data was used in two mathematical models, based on open-steady state and closed systems. It was found that the stable isotope method to estimate CH4 oxidation was only useful during periods when clear concentration and isotope differences could be observed in the water column. CH4 oxidation could only be estimated in the water column in August, and in the surface layer in June and July. / Utsläppen av metan (CH4) från sötvattensjöar begränsas genom CH4 oxidation. Det är två stabila kolisotoper som dominerar i CH4; 12C och 13C. Den ostabila kolisotopen 14C finns även i CH4, men den är mer ovanlig i naturen. Metantrofer (metanoxiderande bakterier) oxiderar den lättare kolisotopen snabbare. Förändringar i isotopsammansättningen kan användas för att beräkna hur mycket CH4 som oxideras i ett system. Denna studie undersöker en årlig CH4 oxidation i en sötvattensjö. Vattenprover och bubblor av CH4-gas samlades en gång i månaden, från mars till november, i Gundlebosjön. CH4 gasen separerades från vattenproverna med en ”headspace extraction” teknik. Koncentration och isotopsammansättningen av CH4 analyserades i en ”cavity ring down spectrometer”. Isotopdata användes i två matematiska modeller, baserade på öppet-stabilt tillstånd och stängt system. Den stabila isotopmetoden för att uppskatta CH4 oxidation var endast användbar under perioder då tydliga skillnader i koncentrationen och isotopsammansättningen kunde observeras i vattenpelaren. CH4 oxidation kunde endast uppskattas i vattenpelaren i augusti, och i vattenpelarens ytskikt i juni och juli.

No description available.

<p dir="ltr">Partial methane oxidation (PMO) to methanol is a desirable route for upgrading natural and shale gas resources to liquid chemical intermediates and has been extensively studied on Cu-zeolites. Prior work has studied the stoichiometric PMO reaction on O₂-activated Cu-zeolites, leading to several proposals for candidate O_x-bridged Cu active site structures. More recent studies have investigated the catalytic PMO reaction and have reported that Cu-chabazite (CHA) zeolites tend to exhibit the highest methane oxidation rate (per Cu) among other Cu-zeolite topologies. Multiple studies have reported that decreasing the Cu site density and increasing the framework Al density increase the selectivity towards methanol, but have proposed different mechanistic explanations. Here, we study the influence of Cu active site distribution, which was altered by varying the extraframework Cu site density and the arrangement of framework Al atoms, on the kinetic parameters governing continuous PMO. The number of redox active Cu species was quantified through linear combination fitting of XANES spectra collected under <i>in situ</i> and transient conditions after reactant (O₂) cut-off, and the Cu speciation was investigated with XAS. Total methane oxidation rates and individual product formation rates (CH₃OH, CO, CO₂), normalized per total Cu, increased with Cu density because this influenced the speciation of Cu formed during the reaction. All Cu-CHA samples showed PMO rates that were nearly first-order in CH₄ pressure, consistent with prior reports that C-H activation in CH₄ is the rate limiting step. Samples with differing framework Al arrangement, but fixed extraframework Cu density, showed formation rates of over-oxidation products (e.g., CO₂) that had different apparent reaction orders in O₂, implying differences in the Cu active sites formed during reaction. Changes to Cu oxidation states were monitored with <i>in situ</i> XAS. Samples were first subjected to an oxidative pretreatment (723 K, 5 kPa O₂) and then to catalytic PMO conditions to reach steady-state. Steady-state XANES spectra collected after O₂ was removed from the reactant stream showed the expected reduction from Cu(II) to Cu(I), and the fraction of CH₄-reducible Cu(II) sites decreased with increasing Cu content; increasing the CH₄ pressure ten-fold increased the number of CH₄-reducible sites by a factor of ~1.5. These spectroscopic and kinetic observations suggest there are a mixture of Cu site types that are present during catalysis, each with different intrinsic reactivity toward CH₄ and selectivity to CH₃OH. To rationalize these observations, a reaction mechanism is proposed for a two-site model and used to derive rate expressions that describe apparent reaction orders for the total CH₄ oxidation rate and product formation rates on Cu-CHA zeolites of varying Cu content.</p><p dir="ltr">Additional routes for CH₄ activation include partial CH₄ oxidation over Fe zeolites that convert CH₄ at ambient temperature following an activation in nitrous oxide (N₂O), or through CH₄ dehydroaromatization (DHA) to benzene over Mo zeolites under non-oxidative conditions. Prior work on PMO over Fe-zeolites has identified candidate active site structures, but the influence of zeolite structural properties on ion-exchanged Fe speciation remains unclear. This work sought to understand the interaction of Fe with the zeolite framework during solvent-assisted deposition procedures and subsequent thermal treatments. In pursuit of this objective, Fe uptake isotherms were measured, and Fe speciation was characterized with UV-Vis spectroscopy and H₂ temperature programmed reduction (H₂ TPR). Increased framework Al site pairing increased the uptake of Fe in CHA zeolites, and high temperature treatments (723 K) resulted in the formation of oligomeric Fe structures as indicated by UV-vis. In CH₄ DHA over Mo-MFI, a principal challenge is the irreversible loss of catalytic reactivity with repeated reaction-regeneration cycles, attributed to dealumination of the zeolite structure during high-temperature oxidative regeneration treatments that produce steam. CHA zeolites are known to be more resistant to dealumination than MFI, but its smaller pore structure prevents diffusion of benzene and other aromatic products leading to rapid coking. This work attempted to address the diffusion limitations for benzene in Mo-CHA by synthesizing crystals with nanoscale dimensions by incorporating a surfactant into the crystallization procedure, generating solids with a flake-like morphology.</p><p dir="ltr">The overarching strategy in this work was to influence the speciation of metal sites and complexes in zeolites by controlling the density and arrangement of anionic Al anchoring sites within the framework and the density of extraframework metal species. In the case of Cu-zeolites, the amount of Cu present on the material influences the structures that form during catalysis that influences both the rate and selectivity of catalytic PMO.</p>