Cette thèse s’inscrit dans le cadre général de la dépollution d’effluents gazeux faiblement chargés en Composés Organiques Volatils (COV). L’étude concerne l'oxydation de trois COV cibles (méthane, propène, et toluène) dans l'air à la pression atmosphérique dans d'une part un réacteur plasma de décharge à barrière diélectrique (DBD) pulsée et un réacteur catalytique utilisés séparément et d'autre part, dans un réacteur hybride associant le réacteur plasma aux catalyseurs dans deux configurations: le catalyseur au coeur de la décharge et le catalyseur en post-décharge. Les catalyseurs sont à base de Pd, Mn, Cu, et Co supportés sur des billes de Al2O3. Ils ont été caractérisés par ICP-OES, TEM/EDX, XRD, XPS, et DRIFTS. L’efficacité de conversion des COV, la sélectivité en CO/CO2, ainsi que la nature et les concentrations des produits formés pour les trois molécules avec les trois systèmes ont été étudiées en fonction de la température du gaz, de l'énergie injectée, de la concentration des COV, de la taille du support, du type de métal et sa teneur, et de la vitesse volumique horaire. Dans tous les cas, l’activation des catalyseurs à basse température a été démontrée quand ces derniers sont couplés au plasma et les principaux produits de réaction identifiés et quantifiés par spectroscopie infrarouge à transformée de Fourier. Le couplage plasma-catalyseur améliore de façon significative l’efficacité de conversion du méthane, du propène, et du toluène dans l’air ainsi que la sélectivité en sous-produits. L'effet de synergie entre le plasma et les catalyseurs pour la conversion des COV a été démontré dès lors que le plasma est généré directement au sein du réacteur catalytique. / The focus of this thesis is the application of non-thermal plasma and catalysis in chemical processing, in particular for the removal of Volatile Organic Compounds (VOC) diluted in air. In a first part, the oxidation of three pollutants (methane, propene, and toluene) is studied experimentally in a pulsed dielectric barrier discharge (DBD) reactor and in a catalyst reactor working independently. In a second part, a hybrid plasma-catalyst reactor either in a single-stage or in a two-stages configuration, in which the catalyst is located inside or downstream from the plasma reactor, respectively. Catalyst materials based on Pd, Mn, Cu, and Co supported on alumina beads were tested and characterized by ICP-OES, TEM/EDX, XRD, XPS, and DRIFTS. Products were analyzed and quantified by infrared spectroscopy. Achieved VOCs removal efficiencies and CO/CO2 selectivity, as well as nature and concentrations of the formed products, were evaluated as function of many factors, particularly the specific input energy, the gas temperature, the initial VOCs concentration, the nature of catalyst (size support, metal loading), and the hourly space velocity. It has been successfully demonstrated that the combination of plasma and catalyst in the both configurations has many benefits compared to traditional thermal-catalysis and plasma alone treatment including a lowering of the catalyst operating temperature, an improvement of the conversion of VOCs at similar temperatures, and a better end-products selectivity and energy efficiency. The mutual interaction lead to a synergistic effect in plasma-catalysis especially when the discharge is in direct contact with the catalyst whatever the VOCs studied.

Indiana University-Purdue University Indianapolis (IUPUI) / Eagle Creek Reservoir (ECR), located in the Midwestern U.S., is a freshwater limnic system plagued by seasonal Harmful Algal Blooms (HABs) which generate water-fouling Geosmin (GSM) and 2-Methylisoborneol (MIB) Taste and Odor (T&O) compounds. Past investigations of T&O event dynamics have identified Actinomycetes as responsible for MIB production and several genera of cyanobacteria for GSM production. During 2018, a temporally and spatially expansive sampling regimen of the reservoir was carried out and a battery of biological, chemical, physical, and hyperspectral experiments performed. The resulting data was analyzed using time series, cross-correlation, lag time, and multivariate analyses as well as machine learning algorithms to pick apart and interrogate any relationships between HABs, T&O events, and environmental parameters. The results show that local weather and watershed conditions exert significant control over the state of the reservoir and the behavior of the algal community. GSM and MIB peaked during early May under well-mixed, cold, and nutrient-rich water column conditions, then declined under summer thermal stratification before making a small resurgence during late season mixing. Bloom die-off and decay was effectively ruled out as a mechanism controlling T&O concentrations, and no links were found between T&O concentrations and algal biomass. Strong evidence was found that GSM/MIB concentrations were a response by bloom microbes to changing nutrient conditions within the reservoir, and it was determined that nutrient fluxes from the watershed 30-40 days prior to peak T&O concentrations are likely instrumental in the development of the slow- ix growing microbes characteristic of the reservoir. Attempts were made to assess spatial and temporal variability but no significant spatial differences were identified; differences between sampling sites were far smaller than differences between different sampling dates. The findings here add to the growing body of literature showing T&O and HAB dynamics are more closely linked to the relative abundance and speciation of nutrients than other parameters. Additionally, these findings carry important implications for the management of ECR and other similar freshwater reservoirs while highlighting the importance of reducing watershed eutrophication.

Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are two atmospheric pollutants produced by motor vehicles using carbonaceous fuels. As a part of the Mexico City Project, measurements of BC, PPAHs and many other gas- and particle-phase emissions were measured in Mexico City using a mobile laboratory during the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003). The main goal of this research is to estimate emissions of BC and particulate PAHs (PPAHs) for Mexico City's vehicle fleet. The emissions of gas-phase pollutants such as carbon monoxide (CO), total nitrogen oxides (NOy) and volatile organic compounds (VOC) are also estimated. The mobile lab has previously been used to chase vehicles and measure their emissions, but analysis has traditionally focused on determining emission factors of individual vehicles associated with specific chasing events. The laboratory continuously samples ambient air from an inlet at the front of the van, and it is always "seeing" exhaust plumes from the vehicles around it while driving through traffic. We have developed an algorithm that automatically identifies the exhaust plume measurement points, which are then used as the basis for calculation of emission factors. In the nearly 90 hours of on-road sampling during the field campaign, we have identified ~30,000 exhaust measurement points. The large sample size enables us to estimate fleet-average emission factors and thus the emission inventory. Motor vehicles are estimated to emit annually 1,960 tons of BC, 56.2 tons of PPAHs, 1,320,000 tons of CO, 125,000 tons of NOy and 2440 tons of VOCs. The spatial and temporal patterns of BC and PPAHs in different locations with in MCMA are also studied. / Master of Science

Ein nicht-invasiver Atemtest zur Lungenkrebsdetektion setzt Kenntnis über lungenkrebsspezifische Substanzen voraus. Die Identifizierung von Lungenkrebsbiomarkern in der Atemluft war das Ziel dieser Arbeit. Leichtflüchtige organische Substanzen (VOC) wurden als Zielkomponenten ausgewählt. Für die VOC-Analytik wurde eine SPME-GC-MS-Methode entwickelt und sowohl auf Modellsysteme als auch auf Realproben angewendet. Drei Lungenadenokarzinomzelllinien wurden in-vitro untersucht. Die VOC-Analyse wurde mit drei verschiedenen Probenahmestrategien durchgeführt und es war ein deutlicher Hintergrundeinfluss der eingesetzten Einwegzellkulturflaschen auf das analysierte VOC-Profil feststellbar. Trotzdem konnten signifikante Unterschiede zwischen Tumorzellen und zellfreien Nährmedien beobachtet werden: 1-Propanol wurde von den Zellen produziert, während der Gehalt einiger Aldehyde sank. Die eingeschränkte Ähnlichkeit des gewählten Zellkulturmodells mit realen Atemluftproben bedingt eine geringe Eignung dieser Ergebnisse für die Biomarkerableitung. Ein Gasmodell auf Basis angefeuchteter, synthetischer Luft wurde als Grundlage für die qualitätsgesicherte, quantitative VOC-Analyse der realen Atemluftproben konzipiert. Diese Modellluft wurde mit 24 Zielsubstanzen (Alkane, Aromaten, sauerstoffhaltige Spezies) sowie 3 Matrix-VOC mit starker Dominanz in den Atemluftproben (Isopren, Aceton, 2-Propanol) angereichert. In Kooperation mit zwei Berliner Kliniken wurden 37 Atemluftproben von Lungenkrebspatienten und 23 Proben von Gesunden gesammelt. Die Anwendung von 1-Butanol als univariater Marker erlaubt eine Erkennung von Lungenkrebs mit einer Sensitivität von 92% und Spezifität von 78%. Durch lineare Diskriminanzanalyse konnte ein Set aus 4 VOC (1-Butanol, 2-Butanon, 2-Pentanon, n-Hexanal) ermittelt werden, welches ebenfalls eine Sensitivität von 92% und mit 87% eine höhere Spezifität aufwies. Gegebenenfalls handelt es sich bei diesen Substanzen jedoch nur um allgemeine Krankheitsmarker. / A non-invasive breath test for lung cancer detection would be favorable but knowledge on lung cancer specific substances is required. This work aims at the identification of potential lung cancer biomarkers in breath. Volatile organic compounds (VOC) were chosen as targets and a SPME-GC-MS method was developed to analyze the VOC profiles of model systems and real samples. Three lung adenocarcinoma cell lines were investigated in-vitro. The VOC analysis, carried out with 3 different sampling strategies, was influenced by the VOC background of the used disposable culture vessels. Changes in the VOC profiles of cell lines compared to cell-free culture media were obvious: 1-propanol was released by the tumor cells whereas the content of some aldehydes was diminished. The similarity of this model system with real breath samples of lung cancer patients was seen to be insignificant. Consequently, these cell cultures were not suitable for biomarker identification. A gaseous model consisting of humidified synthetic air was developed. It was fortified with 24 target VOC (alkanes, aromatics and oxygenated species) as well as 3 matrix compounds (isoprene, acetone and 2-propanol) dominating patients’ VOC profiles in breath. This model was used for the quality assured quantitative VOC analysis in real breath samples. In cooperation with two hospitals 37 single mixed expiratory breath samples from lung cancer patients and 23 from healthy controls were collected. Applying 1-butanol as an univariate biomarker patients and controls were discriminated with a sensitivity of 92% and a specificity of 78%. Linear discriminant analysis displayed a set of 4 VOC (1-butanol, 2-butanone, 2-pentanone, n-hexanal) with similar sensitivity but higher specificity of 87%. However, these potential biomarkers might rather be a consequence of illness in general.

Naturnahe Verfahren im Management bast- und holzbesiedelnder Insekten basieren auf der Ausnutzung olfaktorischer Reaktionen dieser Insekten und teilweise auch derer Antagonisten auf Semiochemikalien käferbürtigen und baumbürtigen Ursprungs. Verfahren, die im Rahmen der Forschungsarbeit verfolgt wurden, waren zum überwiegenden Teil das Wirkungsprinzip Allochthoner Kairomone sowie Abwehrverfahren bei denen Nichts-Wirtsbaum-Volatile zum Einsatz kommen. Als biologischer Detektor von zu identifizierenden Semiochemikalien aus Laubwaldhabitaten wurde der Ameisenbuntkäfer Thanasimus formicarius verwendet. Von T. formicarius ist eine stark generalistische Lebensweise bekannt, die zur Annahme verleitet, dass dieser auch als Prädator an diversen Laubholz besiedelnden Borkenkäferarten auftritt. Entsprechend wurden als Beuteobjekte in Laubwaldhabitaten die Arten Trypodendron domesticum, Trypodendron signatum, Leperisinus varius und Scolytus intricatus vermutet und schwerpunktartig untersucht. Mittels GC-MS/EAD-Analysen konnte nachgewiesen werden, dass T. formicarius Substanzen aus den Habitaten in Wäldern von Rot-Buche, Gemeiner Esche und Eiche wahrnehmen kann. Für einen Teil der von T. formicarius wahrgenommenen Substanzen wurden Dosis-Antwort-Kurven aufgenommen, um Erkenntnisse über die Wahrnehmungsschwelle bei T. formicarius zu erhalten und eine mögliche Bedeutungen der Substanzen in der olfaktorischen Orientierung im Laubwaldhabitat abzuleiten. Die Ergebnisse verdeutlichten, dass T. formicarius neben käferbürtigen Substanzen auch eine Vielzahl von pflanzenbürtigen Volatilen wahrnehmen kann. Dabei wurden für einige dieser Substanzen sehr geringe Wahrnehmungsschwellen festgestellt, was eine besondere Bedeutung der Substanzen in der olfaktorischen Orientierung von T. formicarius vermuten lässt. Substanzen, von welchen eine signifikante Wahrnehmung von T. formicarius erfasst werden konnte, wurden in Olfaktometerexperimenten auf verhaltensmodifizierende Wirkungen beim Ameisenbuntkäfer untersucht. Die in Laborexperimenten auf Wahrnehmung von T. formicarius getesteten Substanzen wurden letztlich in Fallenfangexperimente und Fangholzexperimente eingebunden. Ein Anflug von T. formicarius auf die in den Laborexperimenten erprobten Substanzen, konnte in Fallenfangexperimenten im Freiland, bei der Verwendung der zu erprobenden Substanzen als Einzelsubstanzen, kaum beobachtet werden. Auch die Kombination der Einzelsubstanzen zu Mixturen erzeugte keine nennenswerten Attraktivitäten auf T. formicarius und andere Prädatoren im Freiland. Dennoch schienen die Substanzen aufgrund ihrer teilweise repellenten Wirkung auf bast- und holzbesiedelnde Insekten geeignet, um zumindest in naturnahen Managementverfahren eingesetzt zu werden. Den Ergebnissen der Fallenfang- und Fangholzexperimente entsprechend können die aus dem Nadelwaldhabitat stammenden Pheromondispenser Sexowit® und Chalcogran als Allochthone Kairomone im Laubwaldhabitat empfohlen werden. Darüber hinaus scheint eine Applikation von exo-Brevicomin und endo-Brevicomin als Allochthone Kairomone im Nadelwaldhabitat denkbar, muss jedoch noch am Fangholz geprüft werden. Aus den Fallenfangexperimenten konnten zudem Substanzen abgeleitet werden, welche sich im Monitoring von bast- und holzbesiedelnden Insekten aus Laub- und Nadelwaldhabitaten eignen. / Nature-based methods in the regulation of bark and wood boring insects are based upon the use of olfactory responses of these insects and also partly of their antagonists to semiochemicals that originate from bark and wood boring insects or their host plants. Methods used during this research were the Allochthonous Kairomones principle and defense methods with non-host volatiles. Thanasimus formicarius was used as biological detector for identifying semiochemicals from deciduous forest habitats. T. formicarius is known to be a highly generalist predator, which led to the assumption that T. formicarius may occur as predator of various bark and wood boring insects living on deciduous tree species. Accordingly, Trypodendron domesticum, Trypodendron signatum, Leperisinus varius and Scolytus intricatus were assumed to be prey species in deciduous forest habitats and hence focused on in this study. A GC-MS/EAD analysis demonstrated that T. formicarius is able to perceive substances from the habitats of European beech, common ash and oak. For some of the perceived substances dose-response-curves were recorded to obtain knowledge about the perception threshold of T. formicarius and to derive the potential importance of the substances in the olfactory orientation in deciduous forest habitats. The results show that T. formicarius is able to recognize a variety of plant-derived volatiles as well as substances from bark and wood boring insects. For some of these substances very low perception thresholds were determined, suggesting a particular importance of these substances in the olfactory orientation of T. formicarius. Substances that were found to be significantly perceived by T. formicarius were further examined in olfactometer experiments in order to test for behavior-modifying effects. Substances that were tested for perception by T. formicarius in the laboratory experiments were finally included in trapping experiments and trap log experiments. When used as single compounds, low numbers of T. formicarius were attracted to substances used in trapping experiments. Also the combination of single substances to mixtures produced no significant attractions of T. formicarius and other predators in trapping experiments. However, some of the substances seemed to be appropriate for using in nature-based management methods because of repellent effects to bark and wood boring insects. According to the results of trapping and trap log experiments, pheromone dispensers such as Sexowit® and chalcogran from coniferous forest habitats can be recommended as Allochthonous Kairomones in deciduous forest habitats. In addition, an application of exo- and endo-brevicomin as Allochthonous Kairomones in coniferous forest habitats seems possible, but still has to be tested with trap log experiments. In addition within these experiments substances were detected that can be used in the monitoring of bark and wood boring insects in coniferous and deciduous forest habitats.

Naturnahe Verfahren im Management bast- und holzbesiedelnder Insekten basieren auf der Ausnutzung olfaktorischer Reaktionen dieser Insekten und teilweise auch derer Antagonisten auf Semiochemikalien käferbürtigen und baumbürtigen Ursprungs. Verfahren, die im Rahmen der Forschungsarbeit verfolgt wurden, waren zum überwiegenden Teil das Wirkungsprinzip Allochthoner Kairomone sowie Abwehrverfahren bei denen Nichts-Wirtsbaum-Volatile zum Einsatz kommen. Als biologischer Detektor von zu identifizierenden Semiochemikalien aus Laubwaldhabitaten wurde der Ameisenbuntkäfer Thanasimus formicarius verwendet. Von T. formicarius ist eine stark generalistische Lebensweise bekannt, die zur Annahme verleitet, dass dieser auch als Prädator an diversen Laubholz besiedelnden Borkenkäferarten auftritt. Entsprechend wurden als Beuteobjekte in Laubwaldhabitaten die Arten Trypodendron domesticum, Trypodendron signatum, Leperisinus varius und Scolytus intricatus vermutet und schwerpunktartig untersucht. Mittels GC-MS/EAD-Analysen konnte nachgewiesen werden, dass T. formicarius Substanzen aus den Habitaten in Wäldern von Rot-Buche, Gemeiner Esche und Eiche wahrnehmen kann. Für einen Teil der von T. formicarius wahrgenommenen Substanzen wurden Dosis-Antwort-Kurven aufgenommen, um Erkenntnisse über die Wahrnehmungsschwelle bei T. formicarius zu erhalten und eine mögliche Bedeutungen der Substanzen in der olfaktorischen Orientierung im Laubwaldhabitat abzuleiten. Die Ergebnisse verdeutlichten, dass T. formicarius neben käferbürtigen Substanzen auch eine Vielzahl von pflanzenbürtigen Volatilen wahrnehmen kann. Dabei wurden für einige dieser Substanzen sehr geringe Wahrnehmungsschwellen festgestellt, was eine besondere Bedeutung der Substanzen in der olfaktorischen Orientierung von T. formicarius vermuten lässt. Substanzen, von welchen eine signifikante Wahrnehmung von T. formicarius erfasst werden konnte, wurden in Olfaktometerexperimenten auf verhaltensmodifizierende Wirkungen beim Ameisenbuntkäfer untersucht. Die in Laborexperimenten auf Wahrnehmung von T. formicarius getesteten Substanzen wurden letztlich in Fallenfangexperimente und Fangholzexperimente eingebunden. Ein Anflug von T. formicarius auf die in den Laborexperimenten erprobten Substanzen, konnte in Fallenfangexperimenten im Freiland, bei der Verwendung der zu erprobenden Substanzen als Einzelsubstanzen, kaum beobachtet werden. Auch die Kombination der Einzelsubstanzen zu Mixturen erzeugte keine nennenswerten Attraktivitäten auf T. formicarius und andere Prädatoren im Freiland. Dennoch schienen die Substanzen aufgrund ihrer teilweise repellenten Wirkung auf bast- und holzbesiedelnde Insekten geeignet, um zumindest in naturnahen Managementverfahren eingesetzt zu werden. Den Ergebnissen der Fallenfang- und Fangholzexperimente entsprechend können die aus dem Nadelwaldhabitat stammenden Pheromondispenser Sexowit® und Chalcogran als Allochthone Kairomone im Laubwaldhabitat empfohlen werden. Darüber hinaus scheint eine Applikation von exo-Brevicomin und endo-Brevicomin als Allochthone Kairomone im Nadelwaldhabitat denkbar, muss jedoch noch am Fangholz geprüft werden. Aus den Fallenfangexperimenten konnten zudem Substanzen abgeleitet werden, welche sich im Monitoring von bast- und holzbesiedelnden Insekten aus Laub- und Nadelwaldhabitaten eignen. / Nature-based methods in the regulation of bark and wood boring insects are based upon the use of olfactory responses of these insects and also partly of their antagonists to semiochemicals that originate from bark and wood boring insects or their host plants. Methods used during this research were the Allochthonous Kairomones principle and defense methods with non-host volatiles. Thanasimus formicarius was used as biological detector for identifying semiochemicals from deciduous forest habitats. T. formicarius is known to be a highly generalist predator, which led to the assumption that T. formicarius may occur as predator of various bark and wood boring insects living on deciduous tree species. Accordingly, Trypodendron domesticum, Trypodendron signatum, Leperisinus varius and Scolytus intricatus were assumed to be prey species in deciduous forest habitats and hence focused on in this study. A GC-MS/EAD analysis demonstrated that T. formicarius is able to perceive substances from the habitats of European beech, common ash and oak. For some of the perceived substances dose-response-curves were recorded to obtain knowledge about the perception threshold of T. formicarius and to derive the potential importance of the substances in the olfactory orientation in deciduous forest habitats. The results show that T. formicarius is able to recognize a variety of plant-derived volatiles as well as substances from bark and wood boring insects. For some of these substances very low perception thresholds were determined, suggesting a particular importance of these substances in the olfactory orientation of T. formicarius. Substances that were found to be significantly perceived by T. formicarius were further examined in olfactometer experiments in order to test for behavior-modifying effects. Substances that were tested for perception by T. formicarius in the laboratory experiments were finally included in trapping experiments and trap log experiments. When used as single compounds, low numbers of T. formicarius were attracted to substances used in trapping experiments. Also the combination of single substances to mixtures produced no significant attractions of T. formicarius and other predators in trapping experiments. However, some of the substances seemed to be appropriate for using in nature-based management methods because of repellent effects to bark and wood boring insects. According to the results of trapping and trap log experiments, pheromone dispensers such as Sexowit® and chalcogran from coniferous forest habitats can be recommended as Allochthonous Kairomones in deciduous forest habitats. In addition, an application of exo- and endo-brevicomin as Allochthonous Kairomones in coniferous forest habitats seems possible, but still has to be tested with trap log experiments. In addition within these experiments substances were detected that can be used in the monitoring of bark and wood boring insects in coniferous and deciduous forest habitats.

Varieties of Capitalism theory predicts that the skill specificity of workers determines their demand for social protection. In this thesis, I test this assumption using a measure of occupational mobility between pre- and post-unemployment, which I apply to European workers in different skill groups as defined by Fleckenstein et al., (2011). Using this measure as an indicator of the portability of workers' skills, I then evaluate whether the lower marketability of human capital investments is associated with greater demand for unemployment protection. The findings demonstrate that whilst this relationship is apparent in certain countries, notably Coordinated Market Economies such as Germany, the assumptions do not apply across institutional settings. Consequently, skill specificity cannot explain variation in attitudes towards unemployment protection policies between countries.

Ce travail montre la mise en œuvre d'une technique originale pour le chauffage rapide et bien contrôlé de catalyseurs sous forme de films minces déposés sur un structurant métallique. L'utilisation d'un système à induction électromagnétique adapté à un réacteur catalytique de type annulaire nous a permis d'étudier un certain nombre de matériaux catalytiques, déposés sur acier inoxydable, dans une perspective d'oxydation totale en CO2 et H2O de composés organiques volatiles (COV) présents dans l'air. La combustion de l'isopropanol et du toluène par l'oxygène de l'air a été étudiée en utilisant différents catalyseurs déposés sous forme de films minces: 1%Pt/Al2O3, 0,3%Pt/SnO2, 1%Pt/SnO2 et 1%Pt/YSZ. Les solides ont été préparés par imprégnation des oxydes correspondants par H2PtCl6 puis ont été déposés sur le support d'acier inoxydable par électrophorèse. Les principaux paramètres relatifs au mode de chauffage ont été étudiés de même que l'influence sur la conversion des COV de différents facteurs tels que la quantité de catalyseur, le pourcentage de platine ou la nature du support oxyde employé. Les informations fournies par ce système innovant ont également été comparées pour validation à celles obtenues à l'aide d'un système classique (microréacteur en quartz à lit traversé chauffé de manière conventionnelle) pour une réaction de référence qui est l'oxydation de CO en CO2. Le système décrit dans cette étude présente d'une part un intérêt pratique pour le traitement rapide de contaminations accidentelles de l'air ambiant, mais est aussi un très bon moyen d'obtenir des paramètres cinétiques fiables dans le domaine des catalyseurs en films minces utilisés dans de nombreux réacteurs structurés / This study shows the development of an innovative technique for a fast and well-controlled heating of catalysts deposited as thin films on a metallic support. The use of an electromagnetic induction system fitted to an annular catalytic reactor enabled us to study some catalytic materials deposited on stainless steel. The target application was the abatement of volatile organic compounds (VOCs) in the air. Isopropyl alcohol and toluene combustion by the oxygen was studied on various thin films catalysts, i.e. : 1%Pt/Al2O3, 0,3%Pt/SnO2, 1%Pt/SnO2 et 1%Pt/YSZ. Solids were prepared by wet impregnation of the corresponding oxides by H2PtCl6 and were deposited on the stainless steel support using an electrophoretic deposition technique. The main parameters of the heating system were investigated as well as the influence on VOCs abatement of various parameters such as the thickness of catalyst film, the platinum amount and the nature of the oxide. For validation purpose, the data provided by this innovative system were also compared to the ones provided by a classical one (quartz plug-through microreactor heated in a conventional way) in a reference reaction which was CO oxidation into CO2. The system described in this study shows on the one hand a real practical interest for fast remediation of indoor air polluted by VOCs, and on the other hand is a very powerful tool for obtaining kinetic data about thin layer catalysts used in many structured reactors

La détection et l'identification de bactéries pathogènes revêt une grande importance dans de nombreux domaines tels que la santé et l’industrie agroalimentaire. Dans ce contexte, les travaux de thèse s’intéressent à détection non invasive de Salmonella via la fraction volatile de son métabolome dont les métabolites volatils caractéristiques sont le sulfure d’hydrogène et la cadavérine. Ils illustrent également le concept de substrats osmogènes libérant des mCOV exogènes sous l’action d’enzyme spécifique d’Escherichia coli. Un premier capteur colorimétrique capable de distinguer le sulfure d’hydrogène du méthanethiol a été préparé. Il s’agit d’une matrice de silicate nanoporeuse dopée avec les réactifs N,N-diméthyl-p-phénylènediamine et ions Fe3+. Une bonne stabilité de l’intermédiaire réactionnel issu de ces réactifs, la quinonediimine (QD), est obtenue pour une forte concentration d’acide chlorhydrique. La réaction entre QD et 1000 ppm de sulfure d’hydrogène et de méthanethiol entraîne l’apparition respective d’une coloration verte et rouge-marron du capteur. Le capteur fluorimétrique de cadavérine, basé sur la formation d’un complexe fluorescent entre le Naphthol AS-BI déméthylé (ArOH) et la cadavérine, permet de détecter 250 ppb de cadavérine. La preuve de concept de substrats osmogènes a été illustrée avec la détection de p-nitrophénol (pNP) et de β-naphthylamine (β-NA) libérés en présence d’enzymes de E. coli, β-D-glucuronidase et L-alanine- β-naphthylamidase. Les capteurs nanoporeux produits, de taille de pores contrôlée, peuvent détecter 100 ppm de pNP, composé coloré (jaune) et 100 ppm de β-NA, composé fluorescent, ou encore 100 ppm de β-NA par dérivation chimique de ce dernier avec le diméthyl-p-aminocinnamaldéhyde (formation d’un produit rouge). En milieu biologique, l’eau est un interférent majeur. / Microbial contamination of food and biological samples is a big issue in the industry as much as in the medical field. In that context, the present thesis brings innovative solutions. A first explored way is the identification of Salmonella by detecting and measuring the specific metabolomics volatile organic compounds (mVOC) released, H2S and cadaverine. Another new concept is the use of osmogenic substrates able to release mVOC under the action of specific enzyme of Escherichia coli.A first colorimetric sensor able to discriminate H2S from CH3SH was produced, using a nanoporous silicate matrix doped with N,N-dimethyl-p-phenylenediamine and Fe3+ ions. A very acidic medium is needed to stabilize the “key” intermediate of the reaction, the quinonediimine species (QD), which gives with H2S and CH3SH a green and red-brown product, respectively. The fluorimetric sensor of cadaverine is based on the formation of a fluorescent complex between AS-BI demethylated Naphthol and cadaverine and can detect 250 ppb of cadaverine. A proof of concept of osmogenic substrates is given with the detection of p-nitrophenol (pNP) et de β-naphthylamine (β-NA) released under the action of Escherichia coli enzymes, β-D-glucuronidase et L-alanine- β-naphthylamidase. Various nanoporous sensors are produced with tailored pore size, which can detect 100 ppm of the yellow pNP, 100 ppm of the fluorescent β-NA and 100 ppm of the red product issued from the derivation of β-NA with dimethyl-p-aminocinnamaldehyde. In biological media, water remains the major interfering agent.

Les matériaux polymères sont aujourd'hui très présents dans notre environnement et deviennent irremplaçables pour de nombreuses applications : emballage, textile, mobilier,... La connaissance du cycle de vie de ces matériaux, de la production à leur destruction, devient importante pour nos sociétés. Par exemple ces matériaux peuvent émettre des Composés Organiques Volatils qui sont souvent toxiques et leur impact sur le milieu doit être évalué. L’objectif de ce travail de thèse a été de développer une méthode au laboratoire pour identifier et quantifier ces émissions. La difficulté provient de la grande diversité des composés qui peuvent être émis. Par ailleurs la méthode nécessite une fréquence de mesure élevée (temps réel) souvent incompatible avec les techniques actuelles. Une solution analytique couplant un four et un spectromètre de masse haute résolution associé à une méthode d’ionisation chimique contrôlée a été développée. Celle-ci est basée sur un spectromètre FT-ICR compact à bas champ magnétique : BTrap. Les points forts de cette technique sont la très haute résolution en masse qui permet de mesurer la masse exacte des composés et la détection multi composés, simultanée sur toute la gamme de masse. L’ionisation chimique contrôlée permet l'ionisation douce et quantitative des molécules d’intérêt. Le transfert de proton à partir de l’ion H₃O⁺ (PTRMS) a montré son potentiel pour la détection des COV dans de nombreux domaines. Après une présentation du contexte et du besoin, le dispositif expérimental développé est détaillé. La validation de celui-ci pour l'analyse de gaz traces a été effectuée au LPGP, sur un système de dépollution par plasma froid. Les résultats de dégradation de l'acétaldéhyde en fonction des conditions de fonctionnement du réacteur sont présentés.L’ionisation par PTR conduit habituellement à la molécule protonée ce qui simplifie l’identification. Cependant des fragmentations peuvent être observées. L’utilisation d’un précurseur d’ionisation chimique plus lourd et moins réactif que H₃O⁺ pourrait minimiser ces phénomènes. L’utilisation du diflurobenzène protoné a été testée et comparée à celle de l’ion H₃O⁺. Pour cela, des études cinétiques ont été menées sur une série d’alcools connus pour fragmenter avec H₃O⁺, et confirment l'intérêt du nouveau précurseur.Le poly(méthacrylate de méthyle) (PMMA) est un matériau très répandu : plexiglass. Sa dégradation est a priori relativement simple puisqu’il s’agit très majoritairement d’une dépolymérisation, accompagnée de la formation de produits minoritaires. En conséquence, son étude nous a paru intéressante pour la mise au point et la validation de la méthode. La dégradation du PMMA a été étudiée sous atmosphère inerte, puis oxydante. Les résultats obtenus sont présentés : produits émis, bilan en masse, et apport du suivi en temps réel de la dégradation, montrant en particulier que les produits minoritaires sont émis après le monomère.Enfin une dernière partie de conclusion présente les perspectives pour cette nouvelle méthode. / Polymeric materials are now ubiquitous in our environment and become irreplaceable for many applications such as packaging, textile or furniture. Knowledge of the life cycle of these materials from production to destruction becomes important for our societies. For instance, plastics may release Volatile Organic Compounds: VOCs are often toxic and their impact on the environment must be evaluated. The aim of this thesis work is the development of a laboratory method for identification and quantification of these emissions. The difficulty arises from the wide variety of compounds being potentially emitted. Moreover the desired method requires a high measurement rate ("real time") often incompatible with existing techniques. An analytical device coupling a furnace and a high-resolution mass spectrometer associated with a controlled chemical ionization method has been developed. This device is based on a low magnetic field FT-ICR compact mass spectrometer. The strengths of this technique are (i) high mass resolution allowing exact mass measurements, (ii) recording of the whole mass range simultaneously, allowing detection of a large variety of compounds. Controlled chemical ionization allows soft and quantitative ionization of molecules of interest. Proton transfer from H₃O⁺ ion (PTRMS) has shown its potentialities for VOC detection in many areas. After presenting the background and need, the developed experimental device is described in detail.The validation of this instrument for trace gas analysis has been performed at LPGP, using a nonthermal plasma depollution device. The results of acetaldehyde degradation according to operating conditions in the discharge reactor are presented.PTR ionization usually leads to the protonated molecule, so that identification is simplified. However fragmentations are sometimes observed. Use of a chemical ionization precursor ion heavier and less reactive than H₃O⁺ may minimize these drawbacks. Protonated difluorobenzene was selected as a precursor and its reactivity was tested and compared with H3O+ reactivity. In this purpose, kinetic studies were performed on a series of alcohols known for their fragmentation behavior with H₃O⁺. The results confirm the interest of the new precursor.Polymethyl methacrylate (PMMA) is a widespread material: plexiglass. Its degradation process is relatively simple since it consists in predominant depolymerization, along with formation of minor products. Consequently, PMMA study appeared interesting for method development and validation. Thermal degradation of PMMA has been studied under inert, then oxidative atmosphere conditions. The presented results include identification of minor products and mass balance under different temperature conditions. Real-time monitoring of VOC emission showed time differences in emission peaks of MMA monomer and minor products, each of them being emitted slightly later than MMA. Finally, a conclusive part presents the perspectives opened for this new method.