Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-03-20T16:13:20Z No. of bitstreams: 1 Dissertação RENATA BARBOSA ALVIM.pdf: 2783575 bytes, checksum: 8dc5864bf21a2fc4b34dc2c0ab8e0e97 (MD5) / Made available in DSpace on 2017-03-20T16:13:20Z (GMT). No. of bitstreams: 1 Dissertação RENATA BARBOSA ALVIM.pdf: 2783575 bytes, checksum: 8dc5864bf21a2fc4b34dc2c0ab8e0e97 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica, Niterói, RJ. / As atividades humanas estão provocando alterações substanciais no ciclo do Nitrogênio. Tais alterações resultam no aumento das formas reativas, na distribuição das suas diversas formas nos sistemas aquáticos e na geração de gases de N, considerados importantes reguladores de processos químicos e físicos na atmosfera. Um desses gases gerados é o N2O, que além de ser um dos gases do efeito estufa, contribui para o consumo do O3 estratosférico. O presente estudo teve como objetivo avaliar os impactos provocados na distribuição das espécies de N dissolvidas, às cargas de N e às emissões de N2O, provenientes do despejo de águas residuais urbanas não tratadas nas águas fluviais da bacia hidrográfica do rio Paquequer (Teresópolis, RJ). O rio Paquequer nasce em uma Unidade de Conservação Ambiental, o PARNASO, no entanto, os impactos começam quando o rio deixa o parque e segue em direção ao perímetro urbano do município, onde recebe elevada carga de águas residuais urbanas. Posteriormente, atravessa áreas onde se desenvolvem atividades rurais, até desaguar no rio Preto. As coletas foram realizadas no mês de agosto (2010), período caracterizado pela estiagem, ao longo da bacia hidrográfica do rio Paquequer e de seus principais afluentes. Foram efetuados medidas in situ de pH, condutividade, temperatura, além das análises de NH4+, NO2-, NO3-, NTD, concentração e fluxo de N2O. O NTD variou de 580 a 9996 μg N L-1, valores estes encontrados respectivamente dentro da unidade de conservação e no perímetro urbano do município. Nos 4 pontos de amostragem localizados em áreas sujeitas a pouca influência direta das atividades humanas (3 na unidade de conservação), predominou o NOD em relação às formas inorgânicas de N, sendo que destas predominou o NO3- em relação às demais. Nestes 4 pontos, os níveis de NH4+ e NO2- foram inferiores a 20 μg N L-1. Nos trechos mais poluídos da bacia do Paquequer predominaram o NH4+ e o NOD. As emissões de N2O variaram de 0,7 a 201 μg N m-2 h-1 na calha principal do Paquequer e de 1.1 a 9.9 μg N m-2 h-1 nos 3 tributários investigados. Nos locais situados dentro dos limites do PARNASO e no córrego Príncipe, setores não, ou muito pouco, sujeitos à descarga de esgotos, as emissões variaram de 0,7 a 6,1 μg N m-2 h-1. As maiores emissões ocorreram dentro e no limite do perímetro urbano inferior, com valores na faixa de 68 a 201 μg N m-2 h-1. As concentrações de NH4+ e N2O mostram correlação estatisticamente significativa (r2 = 0,73)‚ sugerindo que a produção desse óxido nas águas poluídas da bacia do Paquequer possa estar associada predominantemente ao processo de nitrificação, do qual surge como subproduto na etapa de oxidação do NH4+. / Human activities are causing substantial changes in the nitrogen cycle. These changes result in an increase in reactive forms, the distribution of its various forms in aquatic systems and the generation of gases N, considered important regulators of chemical and physical processes in the atmosphere. A greenhouse gas generated is N2O, which besides being one of the greenhouse gas, contributes to the consumption of stratospheric O3. The present study was to evaluate the impacts caused in the distribution of species of dissolved N, N loads and emissions of N2O from the discharge of untreated urban wastewater of the Paquequer basin (Teresópolis, RJ). The river rises in a Paquequer Unit of Environmental Conservation, PARNASO, however, the impacts begin when the river leaves the park and goes toward the urban perimeter, where it receives high load of wastewater. Later, through areas where rural activities are developed, before flowing into the Preto river. Samples were collected in august (2010), a period characterized by drought, along the basin river Paquequer and its main tributaries. In situ measurements of pH, conductivity, temperature and the analysis of NH4+, NO2-, NO3-, NTD, N2O concentration and flow were made in that region. The NTD ranged from 580 to 9996 μg N L-1, respectively these values are found within the conservation area and the urban perimeter. In the four sampling points located in areas subject to little direct influence of human activities (3 in the conservation unit) predominated in NOD compared to inorganic forms of N, and NO3- these predominated over the others. In these four points, the levels of NO2- and NH4+ were less than 20 μg N L-1. In the most polluted parts of the Paquequer basin predominate NH4+ and NOD. N2O emissions ranged from 0.7 to 201 μg N m-2 h-1 in the main channel of Paquequer and from 1.1 to 9.9 μg N m-2 h-1 in three tributaries investigated. In places within the boundaries of Parnassus and Principe stream , not sectors, or very little, subject to the discharge of sewage, emissions ranged from 0.7 to 6.1 g N m-2 h-1. The highest emissions occurred within and just outside the city limits lower, with values ranging from 68 to 201 μg N m-2 h-1. The concentrations of NH4+ and N2O show a statistically significant correlation (r2 = 0.73), suggesting that the production of oxides in the polluted waters of the Paquequer basin may be predominantly associated with the process of nitrification, which arises as a byproduct in the oxidation step NH4+.

Le protoxyde d’azote (N2O) est un gaz à effet de serre (GES) important et la principale substance attaquant la couche d'ozone. Les sols agricoles sont la principale source anthropique de ce GES. La concentration de N2O dans l'atmosphère est en constante augmentation, mais nous manquons de connaissances sur les facteurs contrôlant sa production et sa consommation dans les sols. La réduction du N2O en N2 par des microorganismes porteurs du gène codant pour la N2O réductase (nosZ) est le seul processus biologique capable de réduire ce GES. Des études récentes ont mis en évidence un clade précédemment inconnu de réducteurs du N2O qui interfère de manière significative avec la quantité de N2O produite dans les sols. Cette thèse a cherché à mieux comprendre l'écologie des réducteurs du N2O dans les sols agricoles.Une combinaison d'expériences d'incubation en laboratoire mais aussi d’expériences en plein champs a été utilisée pour essayer de mieux comprendre la production de N2O dans le sol, en analysant l’influence conjointe des producteurs et réducteurs de N2O. Nous avons aussi évalué l’impact des pratiques agricoles et leurs potentiels à modifier ces communautés microbiennes. Suite aux essais réalisés en laboratoire, nous avons montré que l'ajout d'une souche non-dénitrifiante Dyadobacter fermentans,possédant la N2O réductase NosZII, permettait de réduire la production de N2O dans 1/3 des sols testés. Certains sols sont même devenus consommateurs de N2O suite à l'ajout de la souche nosZII. Cette expérience a démontré la contribution des bactéries nosZII non-dénitrifiantes dans la consommation de N2O dans le sol.D’autre part, nos analyses en contexte agricole ont montré que les pratiques agricoles testées ont peu d’influence sur les communautés microbiennes considérées, les exceptions étant le travail du sol (labour), et le système de culture (annuel ou pérenne). L’intensifiant du travail du sol induit une augmentation de la diversité de nosZII. Nous observons le même phénomène dans le système de culture annuel comparé au système de culture pérenne. D’autres résultats nous permettent aussi d’affirmer que le clade récemment identifié de réducteurs du N2O est plus sensible aux variables environnementales que le clade précédemment connu (nosZI). Les variations de propriétés du sol, notamment pH et C:N structurent les communautés microbiennes appartenant à ces 2 clades indiquant une spécialisation de niche pour chacun de ces deux clades de N2O-réducteurs.Pour mieux comprendre les relations entre les communautés microbiennes et les processus impliqués, nous avons évalué les activités potentielles de dénitrification et de nitrification, et les émissions de N2O in situ. La production potentielle de N2O et l'activité potentielle de dénitrification ont été utilisées pour calculer le ratio de production de N2O (N2O:N2). La diversité du clade nosZII est négativement corrélée au ratio N2O:N2, et explique à elle seule la plus grande part de variance observée du ratio N2O:N2. Les variations de production potentielle de N2O et d'activité potentielle de dénitrification sont elles expliquées principalement par les variations de propriétés du sol. Afin de mieux évaluer la contribution des différents facteurs édaphiques et microbiologiques aux variations d’émission in situ de N2O, 70000 mesures ont été subdivisées en différentes gammes d’émission de N2O, d‘émissions dites de base à des émissions élevées. Fait intéressant, les variations d’émissions in situ de N2O dites de base sont seulement liées à des variations du pH du sol, alors que les variations d’émissions dites élevées sont également fortement associées aux variations de diversité des communautés microbiennes. Parmi les variables microbiennes importantes, nous avons constaté que la diversité des nosZII est négativement liée aux émissions de N2O in situ dites élevées.En conclusion, nos résultats mettent en évidence l’importance du clade nosZII pour le cycle du N2O dans le sol (...). / Nitrous oxide (N2O) is an important greenhouse gas (GHG) and the main ozone depleting substance. Agricultural soils are the main anthropogenic-induced source of this GHG. The concentration of N2O in the atmosphere is steadily increasing, but we still lack knowledge on the factors controlling its production and consumption in soils. The reduction of N2O to N2 by microorganisms harboring the N2O reductase gene (nosZ) is the only known biological process able to consume this GHG. Recent studies revealed a previously unknown clade of N2O-reducers which was shown to be important to the N2O sink capacity of soils. This thesis seeks to gain a greater understanding on the ecology of N2O-reducers in agricultural soils. A combination of laboratory incubation and field experiments were used to gain knowledge on the importance of N2O-producers and N2O-reducers to the soil N2O production. Additionally, the potential of agricultural practices to modify those microbial communities were assessed.We showed experimentally, in laboratory incubations, that the addition of a non-denitrifying strain Dyadobacter fermentans, which possesses the previously unaccounted N2O reductase NosZII, reduced N2O production in 1/3 of the tested soils. Remarkably, after addition of the nosZII strain, some soils became a N2O sink, as negative rates were recorded. This experiment provided unambiguous evidence that the overlooked non-denitrifying nosZII bacteria can contribute to N2O consumption in soil.Our evaluation of agricultural field experiments showed limited impact of agricultural practices on the microbial communities except for tillage management, and differences observed between an annual and a perennial cropping system. Increasing tillage management enhanced nosZII diversity. Higher diversity of the nosZII clade was also observed in the annual cropping system than in the perennial cropping system. Overall, the recently identified clade of N2O-reducers was more sensitive to environmental variables than the previously known clade (nosZI). The community structure of these two groups was explained by common and uncommon soil properties suggesting niche specialization between the two N2O-reducers.In an attempt to understand the relationship between the microbial communities and process rates, we assessed the potential denitrification and nitrification rates, and in situ N2O emissions. Potential N2O production and potential denitrification activity were used to calculate the denitrification end-product ratio. The diversity of nosZII was negatively related to the N2O:N2 ratio and explained the highest fraction of its variation (26%), while the potential N2O production and potential denitrification activity were mainly explained by the soil properties. To better evaluate the contribution of different factors to the in situ emissions, more than 70000 N2O measurements were subdivided into different ranges, from low to high rates. Interestingly, the low range of in situ N2O emissions was only related to soil pH, while the high ranges were also strongly related to the microbial communities. This result suggests that the “base-line” N2O emissions might be more regulated by soil edaphic conditions than by microorganisms, the lasts being more important for the high emissions ranges. Among the significant microbial variables, we found that the diversity of nosZII was negatively related to the high ranges of in situ N2O emissions.In conclusion, our results highlight the relevance of the second clade of N2O-reducers to the fate of N2O in soil. Our results also suggest niche differentiation between the two N2O-reducing clades with nosZII being more responsive to environmental variables. Agricultural practices showed limited impact on the two guilds. Further research is needed to test the niche specialization between the two groups, to disentangle their controlling factors, and to evaluate their potential for N2O mitigation.

Du fait de l’omniprésence de l’homme au sein du compartiment intérieur, y passant jusqu’à 90% de son temps au cours d’une journée, il est devenu essentiel de caractérisé correctement l’atmosphère et donc les polluants présent dans ce milieu. Ce travail de thèse prend la suite d’une étude menée au sein de notre laboratoire montrant une importante présence de radicaux hydroxyles dans cette atmosphère. Le polluant précurseur des radicaux supposé au cours de cette étude est l’acide nitreux (HONO), présent dans des quantités de l’ordre du ppb pour l’intérieur. Ce travail de thèse a donc eu pour but, dans un premier temps de caractériser la photolyse de l’acide nitreux conduisant à la formation de radicaux hydroxyles, et dans un second temps d’établir ses différentes voies de formation, directes et indirectes, afin de quantifier ses sources dans les atmosphères intérieures. / People in Western societies spend about 90% of their time indoors, predominantly within indoor places. The residence time of the airborne indoor pollutants is much longer due to the smaller volumes compared to the outdoor atmosphere and low air exchange rates. Therefore, a comprehensive understanding of indoor air quality is essential.Nitrous acid (HONO) is an emerging indoor pollutant because 1) it can lead to human respiratory tract irritation and formation of carcinogenic nitrosamines, and 2) it can be effectively photolyzed leading to a pulse of hydroxyl radicals (OH).The PhD work here presented is focused on understanding of the formation processes of oxidizing species such as HONO and, hence, OH radicals in the built environment.

Les activités humaines ont généré une augmentation importante de la concentration de gaz à effet de serre (GES) au cours des 150 dernières années, ce qui est relié à plusieurs problèmes environnementaux, tels que le réchauffement planétaire et les changements climatiques. Le secteur agricole contribue de 8 à 10% aux émissions totales de GES dans l'atmosphère, et les principaux GES émis sont le dioxyde de carbone (CO2), le méthane (CH4) et l'oxyde nitreux (N2O). Le contrôle et la quantification de ces émissions requièrent des technologies qui permettent de les capturer et ou les dégrader, par exemple par adsorption. L'objectif du présent projet est de caractériser des matériaux qui puissent être utilisés comme adsorbants des GES et de décrire leurs cinétiques d'adsorption afin d'avoir l'information qui permet de sélectionner des adsorbants pour capturer le CH4 et le N2O à des basses concentrations et à température et pression ambiantes. Pour adsorber le CH4, des adsorbants commerciaux et synthétiques ont été utilisés. Les adsorbants choisis ont été des zéolithes, un biocharbon conditionné au laboratoire et un ZIF (« Zeolitic imidazolate framework », ZIF-8) synthétisé au laboratoire. Ce dernier a été employé aussi pour adsorber du N2O. La capacité d'adsorption de CH4 et de N2O a été évaluée pour chaque adsorbant par de tests dynamiques d'adsorption du gaz sous conditions ambiantes. Ces matériaux ont été caractérisés physiquement et chimiquement afin de corréler leurs propriétés avec la capacité d'adsorption de CH4 et/ou de N2O. Des isothermes d'équilibre ont été utilises pour modéliser les donnés expérimentales. Parmi les différents matériaux utilisés lors de l'adsorption du CH4 à 30 ºC et à pressions partielles de CH4 inférieures à 0,40 kPa, les biocharbons présentent la capacité d'adsorption la plus élevée, suivis par le ZIF-8 et les zéolithes commerciales / Human activities contributed with a significant increase in GHG concentrations over the past 150 years and they are related to environmental issues, such as global warming and climate change. The agricultural sector contributes 8 to 10% of total GHG emissions to the atmosphere, being carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) the main GHGs emitted. The control and quantification of these emissions requires technologies which can capture and or degrade these GHG, for example by adsorption. The objective of this project is to characterize adsorbents and to describe their adsorption kinetics in order to select the most suitable for the adsorption of CH4 and N2O at low concentration and at ambient temperature. For CH4 adsorption, commercial and synthesized adsorbents were tested. The selected adsorbents were commercial zeolites, laboratory conditioned biochar and synthesized ZIF ("Zeolitic imidazolate framework"). ZIF was also used for N2O adsorption. The adsorption capacity of CH4 and N2O for each adsorbent was evaluated by dynamic adsorption tests of the gas under atmospheric conditions. These materials were physically and chemically characterized in order to correlate its properties with its CH4 and/or N2O adsorption capacity. The experimental data of gas adsorption were fitted by equilibrium isotherms. Among the different materials used for CH4 adsorption at 30 ºC and partial pressures lower than 0.40 kPa, biocharbons presented the highest adsorption capacity, followed by ZIF- 8 and commercial zeolites

Nos últimos anos a produção e o uso de biocombustíveis têm aumentado de forma acelerada e têm sido considerados como uma das alternativas em relação ao uso de combustíveis fósseis. Esse rápido crescimento tem levantado muitas perguntas, ainda sem respostas, sobre o verdadeiro impacto dos biocombustíveis sobre o meio ambiente. O Brasil é considerado o maior produtor mundial de cana-de-açúcar e parte dessa produção é destinada à produção de etanol. Contudo, com a expansão e intensificação das áreas cultivadas com canade- açúcar, há um aumento no uso de fertilizantes nitrogenados e na geração de resíduos como vinhaça e torta de filtro. O uso destes resíduos como fonte de nutrientes tem sido adotado como forma de reduzir o uso de fertilizantes sintéticos e as emissões de gases do efeito estufa (GEE; N2O, CH4 e CO2). Assim, o objetivo deste trabalho foi estimar as emissões desses gases, a partir do solo durante o ciclo produtivo da cana-de-açúcar, na fase planta, com aplicação de compostos orgânicos (vinhaça e torta de filtro), além de fertilizante nitrogenado mineral (ureia). O experimento foi conduzido no Município de Jaú, São Paulo, em um plantio de cana da variedade IACSP95-5000, cultivada em um Latossolo Vermelho. As coletas tiveram inicio em maio de 2010 e se estenderam até março de 2011. Os fluxos foram medidos utilizando o método de câmaras estáticas. O delineamento deste experimento consistiu em seis tratamentos, distribuídos em quatro blocos (repetições) com cinco parcelas (tratamentos), com os tratamentos: (T1) adição de nitrogênio (N), fósforo (P) e potássio (K) via fertilizantes minerais; (T2) adição de P e K via fertilizantes minerais, sem N; (T3) adição de N e K minerais e P via torta de filtro; (T4) adição de N e P minerais e K via vinhaça; (T5) adição de N mineral, P via torta de filtro e K via vinhaça; e (T0) sem adição de compostos orgânicos e fertilizantes minerais. Logo após o plantio e a aplicação dos fertilizantes minerais e dos compostos orgânicos (vinhaça e torta de filtro), coletas intensivas foram realizadas nos dias 1, 2, 5, 6, 8, 12, 17, 20, 24, 28 e 32. Depois do período de amostragem intensiva, as coletas foram realizadas mensalmente. As emissões de N-N2O e C-CO2 mais elevadas foram encontradas durante o período intensivo de coletas, a partir dos tratamentos onde houve adição de fertilizante mineral associado aos compostos orgânicos. Os fluxos de C-CH4 foram negativos em sua maioria o que indica um consumo deste gás pelo solo. O uso de compostos orgânicos juntamente com fertilizantes minerais na área de estudo potencializou a emissão dos gases C-CO2 e N-N2O. O fator de emissão N2O para estes tratamentos está acima do estimado pelo IPCC (1%) / Recently, the production and use of biofuels have increased rapidly and have been considered as one of the alternatives in relation to the use of fossil fuels. This rapid increase has raised many questions about the real impact of biofuels on the environment. Brazil is considered the world\'s largest producer of sugar cane and part of this production is used to produce ethanol. However, with the expansion and intensification of areas cultivated with sugar cane, there is an increase in the use of nitrogen fertilizers and residues of the ethanol industry such as vinasse and filter cake. The use of such residues as a source of nutrients has been adopted as an alternative to reduce the use of mineral fertilizers and the greenhouse gas emissions (N2O, CH4 and CO2). The aim of this study was to estimate greenhouse gas emissions from the soil cultivates with sugar cane in plant stage with use of organic compounds (vinasse and filter cake), and mineral nitrogen as fertilizers (urea). The experiment was conducted in the city of Jau, Sao Paulo, in an Oxisol. The collections started in May 2010 and lasted until March 2011. Fluxes were measured using the static chambers method. The design of this experiment consisted of six treatments in four blocks (replicates) with five plots per block (treatments), as follows: (T1) addition of nitrogen (N), phosphorus (P) and potassium (K) via mineral fertilizers; (T2) addition of P and K via mineral fertilizers, and no N; (T3) addition of mineral N and P, and K via filter cake; (T4) addition of mineral N and P, and K via vinasse, (T5) addition of mineral N, P and K, and filter cake and vinasse, and (T0) without any addition. Intensive collections were made immediately after planting and application of the mineral fertilizers and organic compounds in the days 1, 2, 5, 6, 8, 12, 17, 20, 24, 28 and 32. After the period of intensive sampling, samples were collected monthly. Elevated emissions of N2O-N and CO2-C were observed during the period of intensive sampling, from the treatments where the mineral fertilizers associated with organic compounds were applied. CH4-C fluxes were mostly negative indicating a consumption of this gas by the soil. The use of organic compounds associated with mineral fertilizers in this study increased the emission of CO2-C and N2O-N. The N2O-N emission factor for these treatments is higher than estimated by the IPCC (1%)

Etude de la relation structure-activité de complexes bio-inspirés de la réductase de l'oxyde nitreux N2O est un puissant gaz à effet de serre et est impliqué dans la destruction de la couche d'ozone, ce qui rend sa dégradation très intéressante. Il s'agit d'un intermédiaire du cycle catalytique de la nitrification bactérienne. En effet, en biologie une métalloenzyme est capable de réduire N2O à deux électrons en N2 et H2O. Le site actif de la réductase de l'oxyde nitreux, le centre CuZ, renferme l'unique association de quatre ions cuivre pontés par un ion sulfure. Afin d'obtenir des complexes capables d'activer N2O et d'approfondir la compréhension du mécanisme catalytique de l'enzyme nous avons élaboré des modèles inspirés du centre CuZ. Il s'agit de complexes dinucléaires de cuivres possédant le motif {Cu2(µ-S)} supposé indispensable à l'activation de N2O. Les complexes à valence mixtes décrits dans ces travaux ont été complétements caractérisés et leur activité vis-à-vis de la réduction de N2O a été évaluée. Ces complexes constituent le premier modèle de ce type capable de réduire N2O. Des études spectroscopiques, électrochimiques et théoriques nous ont également permises de proposer un mécanisme réactionnel, passant par la formation d'un adduit complexe-N2O. Nous avons également pu mettre en évidence le rôle crucial de la molécule d'eau, ligand exogène des complexes, dans ce mécanisme. En parallèle, la stabilité en solution de différentes liaisons disulfures présentes au sein de ligands tétranucléants, en présence de CuII, a été évaluée. La réactivité de la liaison disulfure est dépendante de la fixation des ions cuivre à proximité des atomes de soufres. Trois ligands possédants des substituants aminés différents ont été testés, chacun présentant une réactivité particulière. Nous avons montré pour l'un de ces ligands que l'oxydation de la liaison disulfure pouvait être réalisée en absence d'oxydant fort, l'eau jouant le rôle de nucléophile. / Structure-activity relationships in copper complexes bio-inspired from nitrous oxide reductase N2O is a powerful greenhouse gas and is involved in the ozone layer destruction, which makes it degradation very interesting. N2O is an intermediate of the catalytic cycle of bacterial nitrification. Indeed, in biology a metalloenzyme can reduce N2O with two electrons to N2 and H2O. The active site of nitrous oxide reductase, the CuZ center, contains a unique combination of four copper ions bridged by a sulfide ion. In order to obtain complexes able to activate N2O and deepen the understanding of the catalytic mechanism of the enzyme we have developed models based on the CuZ center. Binuclear copper containing the {Cu2(μ-S)} pattern that is supposed essential to N2O activation have been synthetized. Mixed valent complexes described in this work were fully characterized and their activity toward N2O was evaluated. These complexes are the first model like this capable of N2O reduction. Spectroscopic, electrochemical and theoretical studies have also allowed us to propose a reaction mechanism, which passes through the formation of an adduct complex-N2O. We were also able to highlight the crucial role of the exogenous water molecule in this mechanism. In parallel, the solution stability of different disulfide bonds present in tetranucleating ligands in the presence of CuII was evaluated. The reactivity of the disulfide bond is dependent upon the binding of copper ions near sulfur atoms. Three ligands with different amino groups were tested, each having a specific reactivity. We have shown for one of them that the oxidation of the disulfide bond could be carried out in the absence of strong oxidizer, water acting as the nucleophil

This master thesis deals with the greenhouse effect, various gases and methods of measurement. On the greenhouse effect is viewed from its historical dating, despite changes in atmospheric composition. It contains a theoretical analysis of the individual gases. It focuses on the most harmful greenhouse gases such as water vapor, carbon dioxide, nitrous oxide, methane, ozone, chlorofluorocarbons and halons. Analysis methods for detection of gaseous substances. Part of this work is focus on the detection of nitrogen dioxide, chloro-fluorocarbon and methane. The data is processed using a ATmega’s microcontroller and then sent to an Internet server thingspeak.com. If the device proves successful, will be used as a laboratory exercise in the course Ecology in electronics.

This semester thesis deals with the greenhouse effect, various gases and methods of measurement. On the greenhouse effect is viewed from its historical dating, despite changes in atmospheric composition and reactions of individual institutions. It contains a theoretical analysis of the individual gases. It focuses on the most harmful greenhouse gases such as water vapor, carbon dioxide, nitrous oxide, methane, ozone, chlorofluorocarbons and halons. Analysis methods for detection of gaseous substances. Part of this work is focus on the detection of nitrogen dioxide and chloro-fluorocarbon. The data is processed using a microcontroller and then sent to an Internet server thingspeak.com. If the device proves successful, will be used as a laboratory exercise in the course Ecology in electronics.

N2O est le troisième plus important gaz à effet de serre ainsi qu’un des principaux gaz responsables de la dégradation de la couche d’ozone. Une approche bio-inspirée de la N2Oréductase (N2Or), enzyme réduisant N2O via un site actif comportant quatre ions cuivre pontés par un atome de soufre, aide au design de nouveaux systèmes. Six complexes à valences mixtes comportant un motif Cu2(µ-S) considéré comme minimum pour avoir une activité ont alors été synthétisés. Il a été démontré que la structure de ces centres métalliques est affectée par le solvant utilisé. Dans un solvant non coordinant comme l’acétone, tous les complexes possèdent une liaison intermétallique et une valence délocalisée à température ambiante. En revanche en solvant coordinant, la coordination de molécules d’acétonitrile rend impossible la formation de liaison intermétallique et localise la valence.Pour tester l’activité N2Or de ces complexes, un prototype permettant un bullage constant en cuve UV a été conçu. L’objectif est de mettre au point une réduction catalytique de N2O en utilisant un réducteur sacrificiel et une source de proton. Le gaz utilisé lors des tests semble cependant contenir une faible quantité de O2 empêchant la caractérisation des activités. Une optimisation visant à purifier N2O avant les tests est en cours.Par ailleurs, les réductions de O2 à deux électrons pour former H2O2 (un oxydant doux) et à quatre électrons pour former H2O (réaction utilisée dans les piles à combustibles) en font un domaine attractif. Il a été démontré que tous les complexes synthétisés lors de ces travaux sont capables de réduire catalytiquement O2 dans l’acétone et que seulement celui sans position échangeable est actif dans l’acétonitrile. Ce dernier a de plus montré une capacité à changer de sélectivité (H2O2 vs H2O) en fonction de la concentration en réducteur sacrificiel utilisé. / N2O is the third most important global warming gas and one of the most aggressive gas against ozone layer. A bio-inspired approach from N2Oreductase (N2Or), enzyme catalysing the two electron reduction of N2O with a four sulfur-bridged copper ions centre, helps for the design of new systems. Six mixed valent copper complexes containing the minimum Cu2(µ-S) core were then synthetized. It has been shown that these structures are affected by solvents in solution. Indeed, in a non-coordinating solvent like acetone, all these complexes have an intermetallic bond and a delocalized valence at room temperature. However in a coordinating solvent, the acetonitrile coordination makes it impossible to form a Cu-Cu bond and localize the valences.To test the N2Or activity, a prototype allowing a constant N2O bubbling in a UV cuve using a closed system was designed. The aim is to develop a catalytic reduction using sacrificial reductant and proton source. However, the gas bottle used for activity tests seems to contain a small amounts of O2 preventing results interpretation. The aim is now to optimize the prototype by adding a system that can purify N2O before activity tests.In a second time, the O2 reduction using two electrons to produce H2O2 (a soft oxidant) or four electron to produce H2O (useful in fuel cells) are of interest. It has been shown that all these new complexes are capable of catalytically reducing O2 in acetone and that only the one without exchangeable position can do it in acetonitrile. The latter has also demonstrate its ability to change its selectivity to produce H2O2 or H2O by changing the sacrificial reductant concentration. These results bring interesting insights for O2 activation with bio-inspired copper complexes.

L’atmosphère est un milieu complexe, loin d’être parfaitement homogène. Elle contient de nombreuses particules, sous formes solides ou liquides, dénommées aérosols. Ces particules peuvent affecter l’équilibre radiatif de la planète, la qualité de l’air dans les milieux urbains et changer la composition chimique de l’atmosphère malgré leur présence à des très faibles teneurs. Par ailleurs, au niveau du sol, la phase gazeuse atmosphérique peut interagir avec la végétation et le bâtiment, tout particulièrement en zone urbaine. Ce travail se situe donc dans le cadre général de l’étude des réactions photoinduites à l’interface air/solide afin de pouvoir comprendre et décrire leur rôle dans la pollution atmosphérique (principalement urbaine). Cette étude a comme objectif principal l’étude de l’influence du rayonnement solaire sur les cinétiques hétérogènes des réactions impliquant le dioxyde d’azote et des surfaces organiques (pyrene, fluoranthene, phénanthrène) pures et des surfaces organiques/inorganiques (pyrene/KNO3, pyrene/Fe2O3, pyrene/KNO3/Fe2O3) simulant le dépôt urbain. De telles réactions n’ont pas encore été étudiées. Ces travaux ont été menés expérimentalement à l’aide de réacteurs de type « tube à écoulement » couplé à un détecteur spécifique du gaz en trace étudié. Après avoir mis en évidence une capture photoinduite sur ces surfaces, nous avons montré que la capture de NO2 dépend de plusieurs paramètres tels que la concentration de NO2, l’humidité relative, le flux photonique avec l’identification des produits de réactions, en l’occurrence l’acide nitreux HNO2, le monoxyde d’azote, les ions nitrites et le 1‐nitropyrene. L’acide nitreux détecté est un élément favorisant les pics de pollution photochimique à l’ozone. Ainsi ce travail est une avancée importante dans ce champ de recherche. / The atmosphere contains a wide variety of solid and liquid particles, named Aerosol. These particles can affect the radiatif balance, air quality in urban environment and can change the composition of the atmosphere. The atmospheric gas phase can react with the vegetation and the buildings containing the urban grime. This work is focused on the investigations of the heterogeneous chemistry between atmospheric gas phase and the urban grime. The aim of the present work is to study the effect of the irradiation on the heterogeneous kinetic of NO2 on pur organic films (pyrene, fluoranthene, phenanthrene) and on organic/inorganic films (pyrene/KNO3, pyrene/Fe2O3, pyrene/KNO3/Fe2O3) as a first attempt to simulate the complexity of the urban grime. A coated flow tube reactor coupled with a NOx analyzer is used to study this kinetic. This work demonstrates the effect of solar radiation on the heterogeneous reaction between gasphase NO2 and the urban grime. The uptake coefficient calculated is a function of the initial NO2 concentration, the relative humidity and the irradiation intensity. We identified after this reaction the formation of nitrous acid and nitric oxide, nitrite ions and 1‐nitropyrene.The nitrous acid is an important compound which dissociates to form the hydroxyl radical and can promote the ozone formation. The results discussed herein suggest that PAHcontaining urban grime on windows and buildings may be a key player in urban air pollution.