La lignine est l'un des biopolymères les plus importants sur Terre. Elle est extraite des plantes et représente la plus grande source de noyaux aromatiques dans la biomasse. De nombreux projets ayant pour but la dépolymérisation de la lignine en molécules de faibles poids moléculaires, valorisables par les industries chimiques, sont de plus en plus développés au vu du fort potentiel de cette bio-ressource. Le but de notre projet était de développer un nouveau système catalytique pour la dépolymérisation de la lignine. Nous nous sommes intéressés à la conception de nouveaux catalyseurs homogènes et hétérogènes, basés sur la structure connue du complexe Fe(TAML). Nous avons étudié leurs réactivité et stabilité en conditions de catalyse oxydante, et les avons comparés aux caractéristiques du Fe(TAML) existant. Pour ce faire, l'étude catalytique a été réalisée sur des molécules modèles de la lignine, dans le but d'éviter les problèmes analytiques liés à la structure du polymère. Dans un premier temps, nous présenterons la stratégie de fonctionnalisation du ligand TAML connu afin d'obtenir de nouveaux complexes qui puissent être greffés sur un support de silice. Dans un deuxième temps, nous parlerons des résultats de la catalyse oxydante en conditions homogènes et hétérogènes, et de l'influence du changement de la structure des ligands sur l'activité des catalyseurs / Lignin is one of the most abundant biopolymers on earth. It is issued from plants and represents the largest source of aromatics in biomass. Projects aiming at depolymerizing lignin to obtain value-added small molecules for the chemical industry are more and more developed due to the high potential of this bio-resource. The goal of our project was to develop a new catalytic system for the depolymerization of lignin. We have been interested in designing new homogeneous and heterogeneous catalysts based on the known structure of the Fe(TAML) complex. We have studied their reactivity and stability under oxidative catalysis conditions, and have compared them to the characteristics of the existing Fe(TAML). To do so, the catalysis study has been realized on lignin small model molecules to avoid the analytical problems related to a polymer backbone. In a first hand, we will present the strategy of functionalization of the known TAML ligand to design new complexes to be grafted on a silica support. In a second hand, we will talk about the results of oxidative catalysis in homogeneous and heterogeneous conditions, and the influence of the ligand structure change on the activity of the catalysts

Vários países têm buscado investigar as emissões de gases do efeito estufa (GEE) e amônia (NH3) na atividade animal para melhor compreensão da dinâmica e excesso desses gases na atmosfera. As informações disponíveis na literatura sobre as emissões de GEE e NH3 em aviários são variáveis e incertas devido à diversidade e condições particulares das instalações, bem como das inúmeras diferenças no sistema de criação e das complexas interações observadas nos dejetos dos animais. A caracterização das emissões do setor avícola normalmente é realizada por monitoramento aéreo das concentrações dos gases dentro das instalações de produção. No entanto, alguns métodos adotados são insuficientes devido às interferências de outros gases, razão por que as medições podem não refletir, com exatidão, as emissões reais. Diante dessa complexidade, nesta pesquisa buscou-se aplicar técnicas que apresentam menores interferências, bem como desenvolver um sistema de amostragem para medir diretamente as emissões de N2O, CH4 e NH3 dos dejetos de frangos de corte. No desenvolvimento do método, utilizou-se como referência o princípio da câmara estática fechada e a análise por cromatografia gasosa (CG), para estimar as emissões de GEE. Para quantificação direta das emissões de NH3, adaptou-se um método semiaberto estático, baseado na captura, em meio ácido, do NH3 volatilizado dos dejetos das aves. Adicionalmente, buscou-se monitorar as emissões diárias de NH3, CH4 e N2O dos dejetos dos frangos, considerando o típico manejo de reutilização da cama de frango. Foram propostos modelos empíricos para as predições das emissões de N2O, CH4 e NH3, em função do número de reutilizações da cama, da idade das aves e de propriedades físico-químicas da cama de frango. As emissões acumuladas por quatro ciclos de criação permitiram calcular perdas anuais de 0,14, 0,35, e 72,0 g de N2O, CH4 e NH3 ave-alojada-1 ano-1, respectivamente. Considerando o número de frangos de corte alojados em 2015, a atividade avícola emitiu cerca de 545,1 Gg CO2eq pelo manejo dos dejetos nos aviários, correspondente a 0,04 kg CO2eq por kg de carne. Reduções de 21, 40 e 78% foram observadas nas emissões anuais de N2O, CH4 e NH3, respectivamente, ao utilizar (seis ciclos) a cama somente em um ciclo de criação. Contudo, um balanço de N foi conduzido para contabilizar as entradas e saídas de N na produção de frangos de corte durante os quatro ciclos de criação avaliados. A principal entrada de N no sistema foi pela ração, como entrada secundária, o N via cama de frango, o qual aumentou consideravelmente a cada ciclo de reutilização. Considerando que esta pesquisa apresenta uma metodologia aplicável e inovadora para determinar os fluxos de GEE em galpões abertos no país, os dados serão úteis para o inventário anual brasileiro das emissões de GEE oriundas dos dejetos da avicultura de corte. Os resultados são úteis também para incentivar novas pesquisas que possam avançar no conhecimento de impactos e alternativas de mitigação de GEE na produção de frangos de corte e, adicionalmente, conferir sustentabilidade à produção de carne no Brasil / Many countries have sought to investigate the emissions of GHG and ammonia (NH3) in livestock production to better understand the dynamics and the excess of these gases in the atmosphere. The information available in the literature on GHG emissions and NH3 in poultry houses are variable and uncertain due to the diversity and particular conditions of the facilities, as well as the numerous differences in the authoring system and the complex interactions observed in animal manure. The characterization of emissions from poultry sector is usually performed by monitoring of gas concentrations in the production facilities. However, some of the methods adopted are inadequated due to interference from other gases, thus, the measurements may not accurately reflect the actual emissions. In this context, this research developed a sampling system with lower interference that directly measure the emissions of N2O, CH4 and NH3 of broiler manure. The proposed methodology includes the principle of static chamber, and gas chromatography (GC) analysis to determine GHG emissions. For the direct quantification of NH3 emissions a semi-open static method was adapted based on the capture of volatilized NH3 from manure of broilers, in an acidic solution. In addition, the daily monitoring of NH3, CH4 and N2O emissions from broiler manure considered the reutilization of poultry litter, which is the usual management. Empirical models were proposed in the study to predict emissions of N2O, CH4 and NH3, depending on the number of reuses of the litter, the age of the birds and physicochemical properties of the litter. Cumulative emissions per production four cycle allowed us to calculate an annual loss of 0.14, 0.35 and 72.0 g N2O, CH4, NH3 bird-place-1 year-1, respectively. Considering the number of broilers grown in 2015, the poultry production chain emitted about 545.1 Gg CO2eq derived from poultry manure management, corresponding to 0.04 kg CO2 eq per kg meat. A reduction of 21, 40 and 78% was observed in the annual emissions of N2O, CH4 and NH3, respectively, when the litter is used in only one breeding cycle instead of six cycles. However, an N balance was conducted to account N inputs and outputs in the production of broiler during the four breeding cycles. The main entrance of N in the production system was the ration, as a secondary input, the N via poultry litter, which increased considerably each reuse cycle. This research presents an applicable and innovative methodology for determining GHG flows in open sheds houses in Brazil. The data presented will be useful to the Brazilian annual inventory of GHG emissions derived from poultry manure. Moreover the present data has the potential to prompt new research that might further the knowledge on the impacts and GHG mitigation alternatives in the production of broiler thus enhancing sustainability in meat production in Brazil

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-02-09T16:06:33Z No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Made available in DSpace on 2017-02-09T16:06:33Z (GMT). No. of bitstreams: 1 TESEDOUTORADO_ANA PAULA DA SILVA_2016.pdf: 3643578 bytes, checksum: aee17ef8cffb8a82bfd826eb5c41ddac (MD5) / Coordenação de Aperfeiçoamento de Pessoal Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências- Geoquímica, Niterói, RJ. / O Óxido nitroso (N2O) é um importante gás do efeito estufa que contribui para as mudanças climáticas globais através do aquecimento radiativo e depleção do ozônio estratosférico. Segundo o IPCC a concentração atmosférica de N2O aumenta a taxas de 0,2 a 0,3% anualmente, e aumentou do período pré-industrial de 270 ppb para 329 ppb em 2016. A emissão deste gás por solos resulta principalmente dos processos de nitrificação e desnitrificação. O melhor conhecimento da contribuição de cada processo poderá ajudar a prever e mitigar as emissões de N2O por solos. Os métodos atuais para a investigação das taxas brutas de nitrificação e desnitrificação envolvem aplicação de inibidores químicos e/ou marcadores isotópicos 15N, os quais alteram a composição da atmosfera do solo. Neste trabalho a teoria do método da separação barométrica de processos (BaPS) foi utilizada para quantificar as taxas brutas de nitrificação e desnitrificação através de medidas de variações da pressão do ar num sistema hermético e isotérmico sem aplicação de inibidores ou marcadores químicos. Câmaras para incubação do solo equipadas com sensores de pressão, temperatura, O2 e CO2 foram construídas e amostras de solo de uma região que emite altos fluxos de óxido nitroso localizada em Jardim Catarina em São Gonçalo (RJ) foram selecionadas para o estudo dos processos de produção do gás. O fluxo in situ foi medido e o resultado médio foi de 25 ngN2O-Ncm-2h-1. A alta emissão de N2O in situ foi observada após período de alagamento da área de amostragem pelas águas poluídas do Rio Alcântara. O método BaPS foi utilizado para determinar as taxas de respiração do solo, nitrificação bruta e desnitrificação em experimentos no laboratório. Os resultados mostraram que as taxas brutas de desnitrificação foram sempre maiores que as taxas brutas de nitrificação e que os maiores fluxos de N2O gerados estão associados ao processo de desnitrificação. / climate change through radiative warming and the depletion of stratospheric ozone. According to the IPCC, the concentration of N2O atmospheric increases at rates of 0.2 to 0.3% annually, and increased had risen from the pre-industrial period from 270 ppb to 324 ppb by 2011. Its emission from soils results mainly from denitrification and nitrification process. A better knowledge of the contribution of each process should help to predict and mitigate N2O emissions by soils. Current methods for investigation of gross nitrification and denitrification rates involve N tracers and acetylene inhibition techniques These methods have the disadvantage of introducing labeled material into soil or changing the composition of soil atmosphere. In this work, the barometric process separation technique (BaPS) was applied to quantify gross nitrification and denitrification rates by measuring air pressure variations in a hermetic and isothermal system without the application of chemical inhibitors or markers. Soil incubation chambers equipped with pressure, temperature, O2 and CO2 sensors were constructed and soil samples from a region known to emit high nitrous oxide flows located in Jardim Catarina, São Gonçalo (RJ) were selected for this study. In situ flow was measured and the mean result resulted in 25 ngN2O-Ncm-2h-1. The high N2O emission in situ was observed after a period of flooding in the polluted waters of the Alcântara River. The BaPS method was used to determine the rates of soil respiration, gross nitrification and denitrification. The results showed that the gross denitrification rate was always greater than nitrification and that the higher N2O fluxes generated are associated with the denitrification process

Ce travail porte sur le procédé NSR (NOx Storage-Réduction) de dépollution des gaz d'échappement automobile Diesel. Des catalyseurs contenant 2,12% Pt déposés sur alumine, cérine-zircone ou cérine modifiée, ont été caractérisés et évalués dans des conditions NSR, avec un regard particulier sur la sélectivité de la réduction des NOx. Les tests catalytiques sont effectués dans des conditions complexes : cycles 60s de stockage (mélange pauvre)/ 4s de réduction (mélange riche), avec des traces de réducteurs dans la voie pauvre et d’oxydant dans la voie riche. Des sélectivités importantes en N2O (gaz à effet de serre) ont pu être observées. Les émissions de N2O varient en fonction de la nature du support, de la température et des réducteurs mis en œuvre (C3H6, CO, H2 ou mélange C3H6+CO+H2). Dans certaines conditions, la présence de réducteur dans les phases pauvres contribue à la majorité du N2O émis lors des cycles NSR. Ces valeurs sont en bon accord avec les résultats obtenus en parallèle en régime stationnaire (SCR). A 200°C, H2 donne la plus grande sélectivité en N2O, essentiellement à cause de la réduction partielle des NOx en milieu pauvre. En revanche, à 300°C, C3H6 est le réducteur le plus sélectif en N2O, toujours avec une forte contribution des phases pauvres. Les résultats sont plus homogènes avec les catalyseurs supportés sur oxydes redox car ils favorisent la transformation des réducteurs dans la voie riche (réactions du gaz à l’eau et reformage de C3H6), conduisant à mélange réducteur moyenné. Les propriétés redox du support permettent aussi de limiter les émissions de NH3. / Lean reduction of NOx was studied on NSR (NOx storage-reduction) catalyst, with a special attention on N-compound selectivities. Platinum (2.12wt%) catalysts supported on various supports (alumina, ceria-zirconia and modified ceria) were characterized and evaluated in cycling conditions. Catalytic tests were performed and realistic and complex conditions: 60s for the storage phases (lean periods)/ 4s for the reduction (rich pulses). Gas mixture was composed of reducers and oxidants in both lean and rich atmosphere. In these conditions, high N2O emissions were measured (powerful greenhouse gas). The N2O selectivity depends on the redox properties of the support, the temperature and the chemical nature of the reducer (C3H6, CO, H2 or C3H6+CO+H2 mixture). In some conditions, more than half of the N2O production can occur during the storage phase, in lean condition. These results are in good agreement with those obtained in specific SCR tests. At 200°C, H2 lead to the higher N2O selectivity especially due to the partial NOx reduction in the lean period. At 300°C, N2O emission is mainly favoured with C3H6, with still a high contribution of the lean pulses. Results are less distinct with supported catalysts on redox material, due to the support involvement in the reducer transformation reactions (water gas shift and steam reforming), leading to a blend of reducers in the rich pulses. In addition, lower NH3 emissions were observed on platinum supported on redox oxides.

The greenhouse gases (GHG) emission in annual crops depends on soil conditions, climate and management of each site. Even the importance of no-till system in the grain production in the southern region of the country, the agricultural practices effect in the emission of the main greenhouse gases (CO2, N¬O and CH4) it is still little known, especially in Latossolos. Even more scarce are the works involving the use of pig slurry (PS) as fertilizer, the injection of PS or the use of nitrification inhibitors on GHG emissions under these conditions. Therefore, the aim of this study was to evaluate the GHG emissions in a Latossolo that is representative of Planalto of Rio Grande do Sul, in response to PS application method (injection x surface application) with or without the use of nitrification inhibitor Dicyandiamide (DCD). A field experiment was conducted in a Latossolo Vermelho aluminoférrico típico, near UFSM Campus in Frederico Westphalen, RS, from June 2014 to April 2015 with the wheat/corn no-till cropping system. The experimental was a randomized block design with four replicates with the following treatments: control (TEST), Mineral fertilizer (NPK), liquid pig slurry (PS) applied to surface (SUP), PS applied on surface with nitrification inhibitor DCD (SUP + IN), DLS injected into the soil (INJ) and PS injected with DCD (INJ + IN). GHG emissions were evaluated by static cameras, with GHG concentrations determined by gas chromatography . Most of the emissions of CO2 and N2O occurred in the summer during maize crop. The PS application increased N2O emission five times compared with TEST, regardless of PS application method. When DCD is used with manure N2O emissions were reduced by 50% with PS surface application and 32% when it was injected into the soil. The N2O emission factor ranged from 0,08 to 0.66% and it is lower than the average of 1 % of N applied established by IPCC. The CO2 emission was not affected by manure application during wheat crop season while increase until 69% in maize crop season. The higher emission was in SUP treatment and we realize that occurred additive effect of reapplication treatments. The soil is a CH4 sink independent treatment, with an average uptake of 277 g C-CH4 ha-1 in wheat crop and 266 g C-CH4 ha-1 in maize crop. The results of this study indicate that PS injection in Latossolo at a wheat/corn no-till cropping system does not increases the emission of CO2, N2O and CH4 in relation to surface application. Also, the addition of nitrification inhibitor DCD to PS helps to mitigate N2O emissions, regardless of the PS application method. / A emissão de gases de efeito estufa (GEE) em cultivos anuais depende das condições do solo, clima e do manejo de cada local. Apesar da importância na produção de grãos e do sistema de plantio direto (SPD) na região Sul do País, o efeito de práticas agrícolas sobre a emissão dos principais gases de efeito estufa (CO2, N2O e CH4) ainda é pouco conhecido, sobretudo em Latossolos. Ainda mais escassos são os trabalhos envolvendo o uso de dejetos líquidos de suínos (DLS) como fertilizante, a injeção dos DLS ou o uso de inibidores de nitrificação sobre a emissão de GEE nessas condições. Este trabalho foi realizado com o objetivo de avaliar a emissão de GEE em um Latossolo representativo do Planaltodo Rio Grande do Sul, em resposta ao modo de aplicação dos DLS (injeção x aplicação superficial) associado ou não ao uso do inibidor de nitrificação dicianodiamida (DCD). Um experimento de campo foi conduzido em um Latossolo Vermelho aluminoférrico típico, junto ao campus da UFSM em Frederico Westphalen, RS, de junho de 2014 a abril de 2015 com a sucessão trigo/milho em SPD. O delineamento experimental foi de blocos ao acaso, com quatro repetições dos seguintes tratamentos: Testemunha (TEST), Adubação Mineral (NPK),Dejetos líquidos de suínos (DLS) aplicados em superfície (SUP), DLS aplicados em superfície, com inibidor de nitrificação DCD (SUP+IN),DLS injetados no solo (INJ) e DLS injetados, com DCD (INJ+IN). As emissões de GEE foram avaliadas através de câmaras estáticas, com as concentrações de GEE determinadas por cromatografia gasosa. A maior parte das emissões de CO2 e N2O ocorreu no verão, durante o cultivo de milho. A aplicação dos DLS aumentou a emissão de N2O em relação tratamento TEST em cinco vezes, independente do modo de aplicação. Com o uso da DCD as emissões de N2O foram reduzidas em 50% com a aplicação superficial dos DLS e em 32% com a sua injeção no solo. O fator de emissão de N2O variou de 0,08 a 0,66%, sendo inferior ao estabelecido pelo IPCC, de 1% do N aplicado. A emissão de CO2 não foi afetada pela adição de dejetos no primeiro cultivo e sofreu incremento de até 69% no cultivo de milho, com a maior emissão no tratamento SUP, indicando efeito aditivo da reaplicação dos tratamentos. O solo atuou como dreno de CH4 independente do tratamento, com influxo médio de C-CH4 de 277 g ha- 1 no cultivo de trigo e 266 g ha-1 no milho. Os resultados deste trabalho indicam que a injeção dos DLS em Latossolo, na sucessão trigo/milho em SPD, não aumenta a emissão de CO2, N2O e CH4 em relação à aplicação superficial e que a adição do inibidor de nitrificação DCD aos DLS contribui para mitigar as emissões de N2O, independentemente do modo de aplicação dos DLS no solo.

Le projet de thèse a eu pour but l’étude de la formation et de l’élimination du N2O par des catalyseurs cuivre-zéolithe ou fer-zéolithe, utilisés pour le procédé de réduction catalytique sélective des NOx par l'ammoniac (NH3-SCR). Dans ce processus de réduction des NOx, les principales voies de formation de N2O sont la décomposition du nitrate d’ammonium (NH4NO3) et l’oxydation de NH3. L’étude bibliographique a montré une contribution plus importante de la décomposition du nitrate d’ammonium. La recherche s’est donc focalisée dans l’étude de la décomposition du nitrate d’ammonium en empruntant deux axes : la décomposition du NH4NO3 commercial et la formation in situ suivi de la décomposition du nitrate d’ammonium.Les catalyseurs, utilisés pour cette étude, ont été, tout d'abord, amplement caractérises par différentes techniques d’analyse physico-chimique afin de connaitre particulièrement la concentration et forme de déposition des métaux, l’acidité et la taille des cristaux.Après avoir abordé la décomposition du NH4NO3 commercial sans catalyseur, l'étude s'est orientée sur l'effet de l'interaction avec un catalyseur. La nature du gaz vecteur, les conditions hydrodynamiques et la quantité de NH4NO3 ont aussi été évaluées.La décomposition sous conditions statiques, i.e. sans entrainement du NH4NO3 liquide, conduit principalement le N2O. En revanche, les chemins réactionnels suivis sous conditions dynamiques dépendent du mode de déposition du nitrate d’ammonium. Les agrégats solides de nitrate d'ammonium en contact avec la surface externe du catalyseur se décomposent directement en N2O, surtout quand le nitrate d’ammonium liquide ne peut pas être entrainé par le gaz vecteur. L’absence de catalyseur favorise la décomposition vers l’azote par l’interaction entre le NH3 et du HNO3 libérés lors de la dissociation du NH4NO3. D’autre part, en présence d’un catalyseur, le NH3 formé tend à s’adsorber et à s’oxyder à plus haute température. La variation du gaz vecteur n'engendre pas d'effet significatif sur la décomposition du NH4NO3.La décomposition du nitrate d’ammonium formé in situ a été réalisée dans le but de se rapprocher des conditions du procédé NH3-SCR, où le nitrate d’ammonium se forme par l’interaction entre le NH3 et le NO2. La méthode expérimentale a été conçue pour maximiser la formation du nitrate d’ammonium selon les deux cas extrêmes pouvant être trouvés dans un système SCR : la saturation préalable du catalyseur en NH3 puis en NO2 (« NH3 experiment ») et l’inverse, saturation en NO2 puis NH3 (« NO2 experiment »). Dans ce cas plusieurs catalyseurs ont été préparés afin d’isoler certaines caractéristiques et évaluer leur impact. Les effets de la teneur en cuivre, du type de métal (Cu ou Fe), de la structure de la zéolite (CHA ou FER), de la méthode de préparation, de l’atmosphère de calcination et du gaz vecteur pendant la décomposition ont été étudiés. Les effets obtenus ont été corrélés avec les résultats de la caractérisation physicochimique des catalyseurs afin de déterminer les paramètres prépondérants des différences observées.La formation du N2O lors du « NH3 experiment » est toujours plus importante que celle obtenue dans le « NO2 experiment » et dépend fortement de la concentration en sites acides de Brönsted quelle que soit la structure de la zéolithe. En revanche, dans le « NO2 experiment », ce sont plutôt les espèces métalliques et sa localisation qui influencent la décomposition du nitrate d’ammonium. La taille des cristaux a aussi une influence. La méthode de préparation et l’atmosphère de calcination n’ont pas un effet très significatif. Le gaz vecteur influence seulement les émissions à haute température : la formation du N2O est plus importante en présence d’oxygène. / The thesis project focused on the study of the formation and elimination of N2O by copper-zeolite or iron-zeolite catalysts, used for selective catalytic reduction of NOx with ammonia (NH3-SCR). In the NOx reduction process the main N2O formation routes are the decomposition of the ammonium nitrate (NH4NO3) and the NH3 oxidation. Still, a literature review showed a more important contribution from the decomposition of ammonium nitrate. Therefore, the study was then concentrated on the decomposition of the ammonium nitrate in two axes: the decomposition of commercial NH4NO3 and the in situ formation followed by decomposition of ammonium nitrate.Besides, the catalysts used for this study, have been thoroughly characterized by different physicochemical techniques in order to, particularly, assess the concentration and deposition form of metals, the acidity and the size of the crystals.After performing the decomposition of commercial NH4NO3 without catalyst, the study has focused on the effect of interaction with a catalyst. The effect of the carrier gas, the hydrodynamic conditions and concentration of NH4NO3 were also studied.Under static conditions, i.e. without liquid NH4NO3 entrainment, the decomposition of the commercial ammonium nitrate mostly leads to N2O. In contrast, the reaction pathway under dynamic conditions depends on the deposition method of ammonium nitrate onto the catalyst. The solid aggregates in the outer surface of the catalyst decompose directly to N2O, especially when the liquid ammonium nitrate cannot be entrained by the carrier gas. The absence of a catalyst promotes the decomposition into nitrogen, formed by the interaction between the NH3 and HNO3 released upon the dissociation of NH4NO3. On the other hand, in the presence of a catalyst NH3 tends to adsorb and to be oxidized at higher temperatures. The carrier gas composition did not have a significant effect in the decomposition of NH4NO3.The decomposition of ammonium nitrate formed in situ was performed in order to get closer from what happens under SCR conditions, where the ammonium nitrate is formed by the interaction between NH3 and NO2. The experimental method was designed to maximize the formation of ammonium nitrate according to the two extreme conditions that may be found in a SCR system: firstly catalyst saturation by NH3 and then by NO2 (“NH3 experiment”) and then the reverse, saturation by NO2 and then by NH3 (“NO2 experiment”). In this study several catalysts were prepared in order to isolate certain characteristics and assess their impact. The effects of the copper loading, the type of metal (Cu and Fe), the structure of the zeolite (CHA or FER), the method of preparation, the calcination atmosphere and the carrier gas during decomposition were studied. These effects were correlated to the results of the physico-chemical characterization of the catalysts with the purpose of find the cause of the faced differences.The formation of N2O during the “NH3 experiment” is always greater than that obtained on the “NO2 experiment”, and strongly depends on the concentration of the Brönsted acid sites, regardless the zeolite structure. However, on the “NO2 experiment”, it is rather the metal species and its location that influence the decomposition of ammonium nitrate. The size of the crystals also has an influence. The preparation method and the calcination atmosphere do not have a significant effect. The carrier gas impacts on the high temperature emission: the formation of N2O is greater in the presence of oxygen.

Die Nutzung von verlustmindernden Verfahren im Stickstoff- und Phosphorkreislauf gewinnt aufgrund ökonomischer, ökologischer und sozialer Aspekte immer stärker an Bedeutung und bildet die Grundlage für eine ressourcenschonende Landbewirtschaftung. Gegenstand dieser Arbeit ist die ökologische und ökonomische Bewertung von unterschiedlichen Verfahren zur Minimierung von Nährstoffverlusten im Stickstoff- und Phosphorkreislauf. In diesem Zusammenhang wurden folgende Fragestellungen untersucht: • Welchen Einfluss haben Boden, Applikationstechnik und Nitrifikationsinhibitor auf Stickstoffverluste (NH3 und N2O) und Nmin-Gehalte bei der Gülle- und Gärrestausbringung? • Können durch eine Gülleablage in zwei Bändern vertikal übereinander Stickstoffverluste (NH3 und N2O) reduziert und Erträge im Silomaisanbau gesteigert werden? • Wie können aus Klärschlammaschen P-Recyclingdüngemittel hergestellt werden, die in ihrer P-Löslichkeit, mineralischen Zusammensetzung und Ertragswirksamkeit mit Triplesuperphosphat (TSP) vergleichbar sind? Die Einflüsse unterschiedlicher Applikationstechniken (Schleppschlauch mit Einarbeitung und Injektion in 15 und 20 cm Bodentiefe) von verschiedenen Substraten (Gülle und Gärrest) auf unterschiedlichen Böden (Plaggenesch, Gley und Erd-Niedermoor) unter Anwendung eines Nitrifikationsinhibitors (3,4-Dimethyl-Pyrazol-Phosphat – DMPP) auf die Emissionsfreisetzung (NH3, N2O, CO2 und CH4) wurden in zwei Mikrokosmenversuchen untersucht. In einem Feldversuch wurden die im Mikrokosmenversuch gewonnenen Ergebnisse überprüft. Außerdem wurde in diesem Versuch erstmalig der Einfluss einer Gülleablage in zwei Bändern vertikal übereinander auf Stickstoffverluste und Ertragswirksamkeit im Silomaisanbau untersucht. In den Mikrokosmenversuchen mit ungestörten Bodensäulen wurde festgestellt, dass der Boden (Bodentextur, Bodenfeuchtigkeit, Bodenkohlenstoffgehalt) (P < 0,001), der Zusatz von einem Nitrifikationsinhibitor (P < 0,001) zu Gärrest und die Applikationstechnik (P < 0,01) einen Einfluss auf die N2O-Freisetzung haben können. Die Tiefe der Gülle- und Gärrestinjektion hatte nur bei dem untersuchten Erd-Niedermoorboden einen signifikanten Einfluss (P < 0,01) auf die Höhe der N2O-Emissionen. Bei den Böden mit einem niedrigen Kohlenstoffgehalt (Gley: 1,7 % Corg; Plaggenesch: 2,4 % Corg) und einem geringen Wassergehalt (Gley: 28 % H2O vol.; Plaggenesch: 21 % H2O vol.) hatte die Applikationstechnik einen geringen Einfluss auf die Freisetzung von N2O-Emissionen. Auf kohlenstoffreichen Böden war ein Unterschied (P < 0,5) zwischen den beiden Substraten Gülle und Gärrest auf die N2O-Freisetzung gegeben. Der Einsatz des Nitrifikationsinhibitors DMPP reduzierte die N2O-Emissionen im Mikrokosmenversuch durchschnittlich um 45 % (P < 0,001). Die Wirkung von DMPP (P < 0,001) war unabhängig von der Applikationstechnik und hatte einen statistisch größeren Einfluss auf die N2O-Freisetzung als die Applikationstechniken (P < 0,01). Zur weiteren Reduzierung von Stickstoffverlusten wurde im Feldversuch mit Silomais ein Premaister (Unterfußinjektor - Firma Kotte Landtechnik, Deutschland) so modifiziert, dass in zwei Bändern vertikal übereinander (10 und 20 cm) Gülle ausgebracht werden konnte. Das sollte die Nährstoffbedürfnisse von Mais in mehreren Wachstumsphasen berücksichtigen. Im Feldversuch wurden zwischen den unterschiedlichen Varianten [Schleppschlauch mit sofortiger Einarbeitung (Gülle und Gärrest), Injektion 15 cm (Gülle und Gärrest), Injektion 10 und 20 cm (Gülle), Injektion 15 cm mit DMPP (Gülle) und Kontrolle ohne Düngung und Bodenbearbeitung] hinsichtlich der durchschnittlichen N2O-Emissionen (52 - 153 µg N/h/m²) Unterschiede festgestellt, die aber statistisch nicht absicherbar waren. Die Ablage von Gülle in zwei Bändern übereinander führte tendenziell zu den höchsten N2O-Emissionen (153 µg N/h/m²). Durch die Ablage von zwei Güllebändern übereinander bildeten sich verstärkt „anoxic hot spots“, welche Nitrifikation und Denitrifikation förderten. Im Vergleich zur Gülleinjektion ohne DMPP (64 µg N/h/m²) konnte die Gülleinjektion mit DMPP (71 µg N/h/m²) N2O Emissionen nicht reduzieren. Im Vergleich zu allen gedüngten Varianten konnte DMPP die N2O-Emissionen um durchschnittlich 33 % reduzieren. Die freigesetzten NH3-Emissionen aller Varianten lagen unter der Bestimmungsgrenze. Die unterschiedlichen Applikationstechniken zeigten keinen Einfluss auf die Nmin-Gehalte. Die Nmin-Gehalte waren in den mit DMPP behandelten Varianten am höchsten. Der Nitrifikationsinhibitor DMPP reduzierte die Umwandlung von NH4-N zu NO3-N und erhöhte den Nmin-Gehalt im Boden um durchschnittlich 16 %. Zwischen den Erträgen (537 - 620 dt/ha FM und 197 - 225 dt/ha TM) und den Erntequalitäten der Versuchsvarianten konnten im Feldversuch keine signifikanten Unterschiede festgestellt werden. Ein Nitrifikationsinhibitor kann nach der Wirtschaftsdüngerapplikation die Umwandlung von NH4-N zu NO3-N verlangsamen und die Freisetzung von N2O-Emissionen reduzieren. Gegenüber der Schleppschlauchausbringung mit sofortiger Einarbeitung (141 €/ha) hat die Injektion (82 €/ha) eine höhere monetäre Vorzüglichkeit. Zur Steigerung der Verfahrenseffizienz bei der Gülle- und Gärrestapplikation ist auf Böden mit einem geringem Kohlenstoff- und Wassergehalt der Einsatz der Injektionstechnik (Injektion in 12 - 15 cm) kombiniert mit Nitrifikationsinhibitoren zu empfehlen. Auf Böden mit einem Kohlenstoffgehalt über 5 % und einer Feldkapazität von über 60 % sollte die Schleppschlauchapplikation kombiniert mit einem Nitrifikationsinhibitor eingesetzt werden. In einem zweiten Teil dieser Arbeit wurde das P-Recyclingpotential von thermochemisch aufbereiteten Klärschlammaschen untersucht. In einem Laborversuch wurden verschiedene Produkte aus der thermochemischen Klärschlammaufbereitung (Klärschlammasche + Na, Ca, Si und Klärschlammasche + Konverterschlacke) auf ihre P-Löslichkeitsformen (analog zur DüMV, ANONYM 2012) und auf ihre mineralische Zusammensetzung untersucht. Außerdem wurden die Produkte auf ihre Düngewirkung überprüft. Durch die thermochemische Behandlung von Klärschlammasche werden die enthaltenen schlecht pflanzenverfügbaren Phosphate (Ca3(PO4)2) in gut pflanzenverfügbare Calcium- und Natrium-Silico Phosphate (Na2Ca4(PO4)2SiO4 und Ca2SiO4 x 0,05Ca3(PO4)2) umgewandelt. Die unbehandelte Klärschlammasche hatte eine relative Neutralammoniumcitratlöslichkeit von 54 %. Mit ihrer NAC-Löslichkeit von über 85 % lagen die aufgeschlossenen Klärschlammaschen deutlich höher. In einem anschließenden Gefäßversuch mit Mais wurden verschiedene thermochemisch aufbereitete Klärschlammaschen (Klärschlammasche + Na, Ca, Si und Klärschlammasche + Konverterschlacke) im Vergleich zu einer nicht aufbereiteten Klärschlammasche und TSP, in drei Stufen, auf ihre Düngewirkung untersucht. Die Düngung mit thermochemisch aufbereiteteten Klärschlammaschen (45 - 55 g/Gefäß TM Ertrag) führte im Vergleich zur unbehandelten Variante (8,35 g/Gefäß TM Ertrag) zu signifikant (P < 0,05) höheren Erträgen. Die Ertragswirkung der thermochemisch aufbereiteten Klärschlammaschen ist mit der von TSP (48 g/Gefäß TM) vergleichbar. Die RAE der thermochemisch aufbereiteten Klärschlammaschen (102 %) liegt deutlich über der von unbehandelten Klärschlammaschen (21 %) und ist vergleichbar mit der von TSP (100 %). Die Marktpreise für thermochemisch aufbereitete Klärschlammaschen zur Nutzung als Düngemittel liegen zwischen 2,50 - 3,50 €/kg P (Aufschluss von Klärschlammasche mit Na, Ca und Si) und 2,15 €/kg P (Klärschlammasche + Konverterschlacke).

En Europe, la prairie occupe près de 40% de la surface agricole utile et fournit un ensemble de services environnementaux et agricoles, tout en constituant un réservoir de diversité végétale et animale. Cet écosystème herbacé, plurispécifique et multifonctionnel est un système biologique complexe qui fait interagir l’atmosphère, la végétation et le sol, via les cycles biogéochimiques, notamment ceux du carbone et de l’azote. Motivées par le maintien des biens et services des prairies face aux changements climatiques et atmosphériques, les recherches actuelles sur l’écosystème prairial s’attachent à étudier l’évolution des processus clés du système prairial (i .e. production, échanges gazeux, changements d’espèce) sous changement climatique complexe. Ce projet de thèse a pour objectif d’étudier in situ les impacts des principales composantes du changement climatique (température de l’air, précipitations, concentration atmosphérique en gaz carbonique) sur des prairies extensives de moyenne montagne. Nous cherchons à mettre en évidence les changements de structure et de fonctionnement de l’écosystème prairial sous l’influence d’un scénario de changement climatique prévu à l’horizon 2080 pour le centre de la France. Ce scénario (ACCACIA A2) prévoit une augmentation de 3.5°C des températures de l’air, une augmentation des concentrations atmosphériques en CO2 de 200 ppm et une réduction des précipitations estivales de 20 %. Nos résultats indiquent qu’à moyen terme (trois ans de traitements expérimentaux) le réchauffement a des effets néfastes sur la production annuelle du couvert végétal. L’effet bénéfique d’une élévation des teneurs en CO2 sur la production aérienne n’apparaît qu’à partir de la troisième année. La richesse spécifique (nombre d’espèces) et les indices de diversité taxonomique n’ont pas montré de variations significatives sous changement climatique. Cependant après trois années de réchauffement, l’abondance des graminées semble être altérée. Contrairement à la production, les traits sont plus affectés par la concentration en CO2 élevée que par le réchauffement. Après trois ans de traitements, des mesures d’échanges gazeux (CO2) à l’échelle du couvert végétal pendant la saison de croissance ont montré un effet négatif du réchauffement sur l’activité photosynthétique du couvert et une acclimatation de la photosynthèse au cours de la saison de croissance sous CO2 élevé. Ces tendances ont aussi été trouvées sur la photosynthèse foliaire d’une des espèces dominantes du couvert (Festuca arundinacea). L’effet négatif direct du réchauffement à l’échelle foliaire semble être associé à une diminution des sucres dans les limbes. L’acclimatation à l’enrichissement enCO2 à l’échelle foliaire, quant à elle, semble être indirectement dépendante du statu hydrique du sol. Notre étude a aussi porté sur l’analyse des échanges gazeux sol-atmosphère d’un des principaux gaz à effet de serre trace des prairies, l’oxyde nitreux (N2O). Malgré une forte variabilité inter- et intra- annuelle, les flux de N2O semblent être favorisés sous réchauffement. L’augmentation de la température affecte aussi positivement les taux de nitrification et leur pool microbien associé (AOB), et les rejets de N2O via dénitrification. De plus, les flux de N2O mesurés aux champs ont montré une corrélation plus forte à la taille des populations microbiennes (nitrifiantes et dénitrifiantes) en traitement réchauffé qu’en traitement témoin. En conclusion, la température semble être le facteur principal dans les réponses de cette prairie aux changements climatiques futurs. De plus, nos résultats suggèrent que le fonctionnement (production, émissions de N2O) des prairies extensives de moyenne montagne est plus vulnérable aux changements climatiques que la structure de la communauté végétale. / In France, the grassland ecosystem represents an important part of the total of agricultural landscape and provides important economic and ecological services. This multifunctional ecosystem is a complex biological system where atmosphere, plants and soil interact together,via the biogeochemical cycles (particularly carbon and nitrogen cycles). In order to maintain goods and services from grasslands in changing environmental conditions, current research on the grassland ecosystem focus on the evolution of key grassland processes (i.e. production,gaseous exchanges, biodiversity) under multiple and simultaneous climate change.This thesis addresses the impacts of the three main climate change drivers (air temperature, precipitation and atmospheric carbon dioxide concentrations) on an extensively-managed upland grassland in situ. We investigated changes in ecosystem function and structure under the influence of a projected climate scenario for 2080 for central France. This scenario (ACCACIA A2) comprises : air warming of 3.5°C, 20 % reduction of the summer precipitation and an increase of 200 ppm in atmospheric carbon dioxide (CO2).Our results indicate that in the medium term (after three years of experimental treatments), warming had negative effects on the annual aboveground production. Elevated CO2 had no significant effects on aboveground production initially, but positive effects on biomass from the third year onwards. Species richness and the indices of species diversity did not show significant differences in response to climate change, but warming was associated with a decline in grass abundance after three years. Contrary to biomass production, plant traits showed a stronger response to elevated CO2 than to warming. After three years of study, canopy-level photosynthesis showed a negative effect of warming but an acclimation to elevated CO2 during the growing season. This pattern was also found for leaf-level photosynthetic rates measured on a dominant grass species (Festuca arundinacea). For Festuca, the direct negative effect of warming was associated with a decrease in leaf fructan metabolism. In contrast, the photosynthetic acclimation under elevated CO2 observed in Festuca seemed closely linked to the indirect effect of soil water content. Our study also examined effects of climate change on one of the main trace greenhouse gases in grasslands, nitrous oxide (N2O). During our study, N2O fluxes showed significant inter-and intra-annual variability. Nevertheless, mean annual N2O fluxes increased in response to warming. Warming had a positive effect on nitrification rates, denitrification rates and the population size of nitrifying bacteria (AOB). Furthermore, field N2O fluxes showed a stronger correlation with the microbial population size in the warmed compared with the control treatment. Overall, warming seems to be the main factor driving ecosystem responses to projected climate change conditions for this cool, upland grassland. In addition, our results suggest that grassland function (aboveground production, N2O emissions) are more vulnerable to complex climate change than grassland community structure for our study system.

O cultivo de pinhão manso é indicado como uma opção multi-propósito já que além de ser utilizado como matéria-prima para produção de biodiesel, reduzindo as emissões de gases do efeito estufa (GEE) quando este biocombustível é utilizado em substituição aos combustíveis fósseis, também pode estocar C no solo. O objetivo geral deste trabalho foi avaliar o potencial de sequestro de C no solo em cultivos de pinhão manso, bem como as alterações na qualidade da matéria orgânica do solo (MOS). Para tanto, foram quantificados os estoques de C e N do solo e os fluxos de GEE em cultivos de pinhão manso. O cálculo das taxas de sequestro de C no solo foi efetuado pela diferença entre o acúmulo de C no solo e as emissões de GEE, expressos em C equivalente (C-eq). A qualidade da MOS foi avaliada por meio da análise isotópica, fracionamento físico, índice de manejo do C (IMC), grau de humificação (HFIL) e teores de C e N na biomassa microbiana. A conversão da vegetação nativa em agroecossistemas alterou a quantidade e composição da MOS nos biomas Cerrado, Mata Atlântica e Caatinga, especialmente nas camadas superficiais. O cultivo de pinhão manso manteve os teores e estoques de C e N do solo, independentemente do uso da terra anterior (pastagem, milho ou vegetação nativa), com tendência de aumento em função do tempo de cultivo da cultura. Adicionalmente, a análise isotópica do C e N demostrou que a partir de dois anos de cultivo do pinhão manso há mudanças na composição da MOS. As contribuições do C derivado dos resíduos vegetais do pinhão manso para o C total do solo atingiram 11,5% após 7 anos de cultivo, na camada 0-30 cm. O cultivo de pinhão manso aumentou os teores de C nas frações da MOS, o IMC e os teores de C e N da biomassa microbiana em função do tempo de implantação da cultura, o que evidencia o potencial de melhoria da qualidade da MOS desse sistema a longo prazo. O HFIL foi menor nas áreas de pinhão manso em relação à vegetação nativa, indicando que os incrementos nos teores de C nessas áreas estão associados ao aumento da matéria orgânica menos estável e que a preservação seletiva não é o principal mecanismo de acumulação de C em solos sob pinhão manso. Os fatores de emissão de N2O variaram de 0,21 a 0,46% para doses inferiores à 150 kg ha-1, sendo emitidos 0,0362 Mg ha-1 ano-1 de C-eq quando aplicada a dose média usual no cultivo de pinhão manso (75 kg ha-1 ano-1). O balanço anual entre o acúmulo de C no solo e a emissão dos GEE mostrou que o cultivo de pinhão manso por 7 anos produz saldo positivo, que significou um sequestro de 0,6 Mg ha-1 ano-1 em C-eq. O presente estudo é pioneiro no Brasil e os resultados gerados nesta pesquisa são base para a análise de ciclo de vida do pinhão manso como matéria prima para a produção de biodiesel. / Jatropha cultivation is pointed as a multipurpose option whether is used for biodiesel production reducing greenhouse gases (GHG) emissions when replaces the need for fossil fuels, and also for storing C in the soil. The overall objective of this work was to evaluate the C sequestration potential of soil cultivated with Jatropha, as well as the variations in soil organic matter (SOM) quality. Therefore, C and N stocks were determined and GHG fluxes were measured in Jatropha cultivation. The difference between results from soil C storage and GHG emissions were used to calculate the C sequestration rates, defined as the C-equivalent (C-eq). SOM quality was assessed by isotopic analysis, physical fractioning, C management index (CMI), humufication degree (HFIL) and microbial C and N content. Land use change from native vegetation to agroecosystems altered the amount and composition of soil organic matter located in biomes of Cerrado, Atlantic Forest and Caatinga, especially within the surface layers. Jatropha cultivation preserved soil N and C stocks and contents, regardless of previous land use management (pasture, maize or native vegetation), proning to increase with cultivation time. Additionally, the isotopic analysis of C and N showed changes in SOM after two years with Jatropha cultivation. After 7 years of cultivation, the contribution of carbon derived from Jatropha residues to the total amount of the element stored within the 0-30 cm layer of soil reached 11.5%. The Jatropha cultivation increased the C contents in SOM, the CMI and microbial C and N contents along with cultivation time, which highlights the potential of Jatropha cultivation to improve SOM quality in the long term. HFIL of the areas with Jatropha cultivation showed lower values compared to the native vegetation. This indicates the increments of C contents for the areas planted with Jatropha are associated to the increase of the less stable portion of SOM and that the selective preservation is not the main mechanism responsible for C accumulation in soils under Jatropha cultivation. The N2O emission factors ranged from 0.21 to 0.46% for the doses up to 150 kg ha-1. Considering the average N fertilization rates applied annually in comercial Jatropha cultivation (75 kg ha-1 yr-1), the crop is responsible for the emission of 0.0362 Mg ha-1 yr-1 of C-eq. Moreover, the annual balance between soil C storage and GHG emission indicated that Jatropha cultivation for 7 years is able to contribute to the carbon sequestration accounting for 0.6 Mg ha- 1 yr-1 of C-eq stored in the soil. This study is pioneer in Brazil and the results generated in this research are basis for life cycle analysis of the Jatropha as a feedstock for biodiesel production in Brazil.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-08-31T14:28:05Z No. of bitstreams: 1 Tese Renato Ribeiro-FINAL (FINAL)_BGQ.pdf: 2538261 bytes, checksum: 368478fea67bb3f88e3e4eebf8a854cd (MD5) / Made available in DSpace on 2017-08-31T14:28:05Z (GMT). No. of bitstreams: 1 Tese Renato Ribeiro-FINAL (FINAL)_BGQ.pdf: 2538261 bytes, checksum: 368478fea67bb3f88e3e4eebf8a854cd (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O óxido nitroso (N2O) possui um potencial de aquecimento global 310 vezes superior ao do dióxido de carbono (CO2). Além disso, o N2O é a principal fonte de óxido nítrico (NO) na estratosfera, sendo indiretamente responsável pelo consumo do ozônio (O3) estratosférico. Os resíduos de origem humana representam uma das fontes de N2O, e estima-se que sistemas de tratamento de esgotos podem contribuir com cerca de 10% do total das emissões antrópicas. Nas estações de tratamento de esgotos (ETEs), as emissões de N2O ocorrem naturalmente devido às transformações microbiológicas dos compostos de nitrogênio (N) através dos processos de nitrificação e desnitrificação. Entretanto, não existe um único mecanismo de emissão de N2O provenientes de ETEs, e suas vias de produção são dependentes do projeto da planta e também relacionadas às diferentes condições dos principais parâmetros operacionais, tais como carga orgânica afluente, concentração de oxigênio dissolvido (OD), taxa de aeração e idade do lodo, dentre outros. O objetivo principal da presente tese foi determinar a relação das diferentes condições operacionais, tais como variabilidade na carga orgânica afluente, diferentes idades do lodo e taxas de aeração, limitação das concentrações de OD e choques de carga orgânica e de N amoniacal, nas emissões de N2O provenientes de diferentes sistemas de tratamento de esgotos por lodos ativados (convencional e aeração prolongada) operados com remoção biológica de N (RBN) e não-RBN, em escalas de bancada e real. Três experimentos realizados in situ em uma ETE de lodos ativados convencional, mostraram a influência da carga de NT afluente, especialmente NH4 +, e da taxa de aeração na emissão de N2O do tanque de aeração. O excesso de aeração intensifica o processo físico de transferência do N2O do meio líquido para a atmosfera e, portanto, deve ser evitado. O monitoramento contínuo das emissões de N2O dos tanques de aeração de três ETEs com sistemas de lodos ativados e operadas com RBN e não-RBN mostraram que as altas emissões de N2O representam condições de excesso de aeração ou uma perda da conversão de NH4 + a NO3 -, com acúmulo de NO2 -. Uma preocupação adicional é o lançamento de lixiviados de aterros sanitários em sistemas de tratamento de esgotos. Condições de estresse, tais como choque de carga de N amoniacal, podem causar uma limitação nas concentrações de OD, acúmulo de NO2 - e, consequentemente, maiores emissões de N2O. Assim, as medições contínuas de N2O podem fornecer informações importantes sobre a adequação da taxa de aeração e da perda de eficiência da nitrificação completa. Sistemas de tratamento de esgotos que não operam com RBN respondem por maiores emissões de N2O quando comparados com aqueles que removem N. Entretanto, um dos maiores desafios das ETEs com RBN é o controle adequado dos parâmetros operacionais responsáveis pelos processos de nitrificação e desnitrificação completos. Diferentes condições experimentais realizadas em um sistema de lodos ativados, em escala de bancada, mostraram que idades do lodo reduzidas (5 dias) combinadas com baixas concentrações de OD (0,5 mg L-1) resultaram em menores eficiências de oxidação de NTK e, consequentemente, em uma insignificante taxa de acúmulo de NO2 -. Nesta condição, a nitrificação foi dificultada pela oxidação da matéria orgânica, com a maior parcela do N removida pela incorporação ao lodo excedente. Por outro lado, idades do lodo mais elevadas (10 dias) combinadas com o aumento da concentração de OD (1,0 mg L-1) resultaram no acúmulo de NO2 - e no aumento da eficiência de oxidação de NTK, o que representa uma condição ideal para oxidação da matéria orgânica e nitrificação. Nesta condição a maior parcela do N foi transferida para a atmosfera. Parte do N transferido para a atmosfera pode ser atribuído ao N2O, que variou de 0,3 a 5,6% da carga de NT afluente, com o maior valor associado a nitrificação parcial. Portanto, o controle adequado das concentrações de OD é um fator chave para evitar o acúmulo de NO2 -, e consequentemente, elevadas emissões de N2O. / Nitrous oxide (N2O) has a global warming potential 310 times greater than carbon dioxide (CO2). Moreover, N2O is the major source of nitric oxide (NO) in the stratosphere which implies that it is indirectly responsible for the consumption of stratospheric ozone (O3). Human waste is a source of N2O and it is estimated that wastewater treatment systems are thought to contribute with about 10% of total anthropogenic N2O emissions. In wastewater treatment plants (WWTPs), N2O emissions occur naturally due to the microbial transformations of nitrogen (N) compounds by the nitrification and denitrification processes. However, there is no single N2O emission mechanism from WWTPs and the pathways related to its production are dependent on the WWTP design and closely related to operating parameters, such as organic matter and total N (TN) loads, dissolved oxygen (DO) concentration, aeration rate and sludge retention time (SRT), among others. The main goal of the present doctoral thesis was to determine the relationship of different operating conditions, such as variable organic loading, different SRTs and air flow rates, limited DO concentrations and organic (and NH4 +) shock loading on N2O emissions in different activated sludge systems (conventional and extended aeration) operated with biological N removal (BNR) and non-BNR, in the laboratory and in full-scale processing. Three in situ experiments, conducted in a conventional activated sludge WWTP, showed the influence of the TN loading rate, especially NH4 +, and the aeration flow rate on the emission rate of N2O from the aeration tank. Excessive air flow intensified N2O transfer from the liquor to the atmosphere by air stripping, and therefore should be avoided. The continuous measurements of N2O emissions from the aeration tanks of three activated sludge WWTPs operated with BNR and non-BNR showed that high N2O emissions denote over-aeration conditions or a loss of NH4 + conversion to NO3 -, with accumulation of NO2 - concentrations. An additional concern is the observed propensity of WWTPs to receive landfill leachates in their wastewater systems. Stress conditions, such as NH4 + shock loading, can cause limited DO conditions, NO2 - accumulation and, consequently, higher N2O emissions. Thus, continuous measurements of N2O emissions can provide information on aeration adequacy and the efficiency of complete nitrification. Non-BNR WWTPs are subject to high N2O emissions, in contrast to BNR WWTP with controlled nitrification and denitrification processes. However, one of the major challenges for WWTPs with BNR is the adequate control of operating parameters responsible for complete nitrification and denitrification processes. Different experimental conditions performed in a lab-scale activated sludge system showed that short SRT (5 days) combined with very low DO levels (0.5 mg L-1) were responsible for lower TKN oxidation efficiencies and, consequently, negligible NO2 - accumulation rates. These results suggest that nitrification efficiency was hampered by the oxidation of organic matter, with a large part of TN removed by sludge waste process. As the SRT increased (from 5 to 10 days) and DO was set to 1.0 mg L-1, TKN oxidation rates and NO2 - accumulation reached their maxima, which are thought to be the optimal conditions for both organic matter oxidation and partial nitrification. Under these conditions, gas transfer to the atmosphere became the preferential route for TN removal instead of incorporation to the sludge waste. Part of the N transferred to the atmosphere is attributed to N2O, which varied from 0.3 to 5.6% of the influent TN load, with the highest value associated with partial nitrification. Therefore, the adequate control of DO concentrations is a key factor to avoid NO2 - accumulation and consequently high N2O emissions.