O Pantanal é a maior área úmida do planeta e considerada uma das maiores fontes naturais de gases de efeito estufa (GEE). A sub-região da Nhecolândia, um dos maiores ecossistemas do Pantanal, possui o sistema lêntico mais diverso, onde lagoas de água doce coexistem com salinas, apesar das condições climáticas regionais não explicarem totalmente esta alta salinidade. As salinas são permanentes e funcionam de maneira diversa, sendo assim, subdivididas em tipologias verde e preta. As salinas verdes e pretas diferem tanto pela composição e funcionamento biogeoquímico, quanto pela abundância de espécies extremófilas. Tal distinção pode afetar o balanço regional de GEE, e assim, reduzir a confiabilidade das estimativas regionais das emissões gasosas. As estimativas de emissões de GEE obtidas anteriormente no Pantanal representaram principalmente ecossistemas de água doce, desconsiderando, portanto, a transferência de massa a partir das lagoas salinas. As lagoas de água doce, porém, podem ser permanentes ou temporárias, dependo da intensidade das inundações anuais. Estas lagoas concentram grande quantidade de matéria orgânica e vegetação aquática que aumenta este aporte orgânico. Devido a diversidade química das águas superiores na Nhecolândia, buscou-se quantificar os fluxos de GEE em lagoas salinas dos tipos verde e preta, e lagoas de água doce. O monitoramento destes corpos d\'água ocorreram nas duas estações climáticas comuns do Pantanal, seca e úmida, quando as alterações climáticas e químicas das águas são marcantes. Deste modo, foi possível retratar o efeito das variáveis abióticas sobre o balanço de massa no sistema água-atmosfera da segunda maior sub-região pantaneira. Duas metodologias distintas foram utilizadas para indicar a variabilidade espacial entre lagoas análogas, como as salinas, e variações específicas em cada lagoa. Os resultados indicaram que houve grande variabilidade espaço-temporal na dinâmica dos GEE entre os ecossistemas estudados, de maneira que, uma mesma lagoa que atuou como fonte em uma estação, comportou-se como sumidouro em outro período. Houve intensa variabilidade espacial, ainda, entre salinas de mesma tipologia, quando no mesmo período, umas podem ser fonte e outras sumidouros para determinados gases. As maiores emissões de metano e gás carbônico ocorreram na lagoa de água doce, porém, salinas verdes apresentaram valores próximos na mesma estação. Isto aponta a necessidade de aumentar as amostragens diretas visando incorporar a variabilidade espacial e temporal aos modelos climáticos regionais. As medidas in situ podem, assim, caracterizar as contribuições individuais no sistema lêntico e aumentar a confiança nas estimativas de emissões gasosas atribuídas ao Pantanal. / The Pantanal is the largest wetland on the planet and considered one of the largest natural sources of greenhouse gases (GHG). The sub-region of Nhecolândia, one of the largest ecosystems in the Pantanal, has the most diverse lentic system, where freshwater lagoons coexist with saline, although regional climatic conditions do not fully explain this high salinity. The salinas are permanent and function in a different way, being thus subdivided into green and black typologies. The green and black salinas differ as much by the composition and biogeochemical functioning, as by the abundance of extremófilas species. Such a distinction may affect the regional GHG balance sheet, and thus reduce the reliability of regional estimates of gaseous emissions. Estimates of GHG emissions previously obtained in the Pantanal represented mainly freshwater ecosystems, thus disregarding the mass transfer from saline lagoons. Freshwater ponds, however, can be permanent or temporary depending on the intensity of annual floods. These ponds concentrate a great amount of organic matter and aquatic vegetation that increases this organic contribution. Due to the chemical diversity of the upper waters in Nhecolândia, it was sought to quantify GHG flows in saline lagoons of the green and black types, and freshwater lagoons. The monitoring of these bodies of water occurred in the two common wetland climate seasons, when the climatic and chemical changes of the waters are remarkable. In this way, it was possible to portray the effect of the abiotic variables on the mass balance in the water-atmosphere system of the second largest sub-region of the Pantanal. Two different methodologies were used to indicate the spatial variability between analogous lagoons, such as salinas, and specific variations in each lagoon. The results indicated that there was great space-time variability in the GHG dynamics among the studied ecosystems, so that the same lagoon that acted as a source in one season, behaved as a sink in another period. There was intense spatial variability, also, between salinas of the same typology, when in the same period, some can be source and other sinks for certain gases. The highest emissions of methane and carbon dioxide occurred in the freshwater lagoon, however, green salinas presented close values in the same season. This points to the need to increase direct sampling to incorporate spatial and temporal variability into regional climate models. In situ measurements can thus characterize individual contributions in the lentic system and increase confidence in the gaseous emissions estimates attributed to the Pantanal.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2018-02-27T15:18:48Z No. of bitstreams: 1 Guimaraes GP 2005.pdf: 1398079 bytes, checksum: 2001454348415a2dbc540e659a2f4498 (MD5) / Made available in DSpace on 2018-02-27T15:18:48Z (GMT). No. of bitstreams: 1 Guimaraes GP 2005.pdf: 1398079 bytes, checksum: 2001454348415a2dbc540e659a2f4498 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Em ambientes marinhos, a química do nitrogênio é controlada por reações redox, mediadas pelo fitoplâncton e por bactérias, que produzem gases trocados com a atmosfera devido ao desequilíbrio entre as concentrações do ar e do mar. Os dois principais gases de nitrogênio envolvidos neste processo são a amônia (NH3) e o óxido nitroso (N2O). O NH3 é a base dominante na atmosfera, possuindo grande importância como neutralizador dos ácidos presentes no ar. O N2O é um importante gás traço na atmosfera e absorve radiação infravermelha contribuindo para o efeito estufa, além de estar associado a diminuição de O3 na estratosfera. Na Baía de Guanabara cerca de 7,8 milhões de habitantes geram esgotos domésticos, que são lançados diretamente nas suas águas gerando elevadas concentrações de nitrogênio inorgânico, levando a acreditar que esta é uma importante fonte de NH3 e N2O para a atmosfera. Neste trabalho foi realizada uma estimativa preliminar dos fluxos de NH3 e N2O na interface ar-mar da Baía de Guanabara em dois tipos de abordagem: espacial e temporal. Para a abordagem espacial foram coletadas 37 amostras entre os dias 05 e 07 de abril de 2004. Para a abordagem temporal, foram coletadas amostras semanais em 10 praias da cidade do Rio de Janeiro, durante o período de julho de 2003 e fevereiro de 2004 (macrotemporal, n = 267), e amostras de 3 em 3 horas em um ponto central durante 9 a 12 de fevereiro de 2004 (microtemporal, n = 25). Em todas as análises a temperatura, salinidade e pH foram medidos in situ e o nitrogênio amoniacal analisado através do método do indofenol. Apenas na abordagem espacial foram analisados nitrito, nitrato (métodos espectrofotométricos) e N2O por cromatografia gasosa com ECD. Os fluxos foram calculados baseado no modelo de duas camadas (two-layer model) adotando concentrações atmosféricas de 1 e 5 μg m-3 para NH3 e de 325 ppb para N2O. Os fluxos de NH3 na interface ar-mar variaram de –31 a 3486 μg N m-2 h-1. Considerando as maiores concentrações na atmosfera (5 μg NH3 m-3), 92% dos fluxos na abordagem espacial, 68% na macrotemporal e 20% na microtemporal indicaram emissão de NH3 para a atmosfera. Os fluxos de N2O variaram entre -46 e 2123 ng N m-2 h-1 (média 306 ± 495 ng N m-2 h-1), dos quais 89% representaram emissão para a atmosfera. Foi verificada uma alta correlação do N2O com o nitrito (r=0,84) indicando que provavelmente o processo dominante de produção de N2O nas águas superficiais da Baía de Guanabara é a nitrificação. Todos os dados indicam uma maior contribuição orgânica no setor oeste da Baía de Gaunabara, contribuindo com altos fluxos de NH3 e N2O para a atmosfera. / In the marine environment, the chemistry of nitrogen is controlled by redox reactions, mediated by phytoplankton and bacteria, that produce gases exchanged with the atmosphere due to the desequilibrium between the concentrations of air and sea. The two main gases of nitrogen involved in this process are ammonia (NH3) and nitrous oxide (N2O). NH3 is the dominant base in the atmosphere and has great importance as neutralizer of the acids in the air. N2O is a trace gas that absorbs infrared radiation contributing to global warming and to ozone depletion in the stratosphere. Around Guanabara Bay about 7.8 million of habitants release domestic sewage directly in to the water elevating the concentrations of inorganic nitrogen, which leads us to believe that this is an important source of NH3 and N2O to atmosphere. A preliminary estimate of the fluxes of NH3 and N2O in the air-sea interface of Guanabara Bay were made using two approachs: spatial and temporal. For the spatial approach 37 samples were collected from 5 to 7 April 2004. For the temporal approach weekly samples were collected at 10 beaches of the city of Rio de Janeiro, during the period of July 2003 and February 2004 (macro temporal, n = 267), and samples in intervals of 3 hours in a central point from 9 to 12 February 2004 (micro temporal, n = 25). The temperature, salinity and pH were measured in situ and the ammoniacal nitrogen analyzed by the indophenol method. Only in the spatial approach were analyzed the nitrite, nitrate (spectrophotometer methods) and N2O by gaseous chromatography with ECD. The fluxes were calculated based on the two-lawyer model adopting atmospheric concentrations of 1 and 5 μg m-3 for NH3 and 325 ppb for N2O. The fluxes of NH3 in the air-sea interface varied from –31 to 3486 μg N m-2 h-1. Considering the greatest concentrations adopted in air (5 μg NH3 m-3), 92% of the fluxes in the spatial, 68% of macro temporal and 20% of micro temporal approaches indicated emission of NH3 to the atmosphere. The fluxes of N2O varied between –6 and 2123 ng N m-2 h-1, of which 89% indicated emission to the air. A high correlation of N2O with nitrite (r=0.84) was verified indicating that probably the dominant process of production of N2O in the surface waters of Guanabara Bay is nitrification. All data indicate a greater organic contribution in the West sector of Guanabara Bay, contributing with high fluxes of NH3 and N2O to the atmosphere.

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

This thesis links papers reporting field measurements, modelling studies and reviews of greenhouse gas (GHG) emissions and their abatement from agriculture, in particular from livestock production. The aims of the work were to: quantify GHG emissions from litter-based farmyard manures; evaluate means by which GHG emissions from agricultural production may be abated; assess synergies and conflicts between the abatement of other N pollutants on emissions of nitrous oxide (N2O); analyse two records of soil temperature from 1976-2010 from Wolverhampton (UK) and Vienna (Austria). Agricultural emissions of GHGs are not readily abated by ‘end of pipe’ technologies. Large decreases in agricultural GHG emissions may require changes in the production and consumption of food that could have unwelcome impacts on both consumers and producers. However, identifying and prioritizing both modes and locations of production, together with utilizing inputs, such as N fertilizer and livestock feeds, more efficiently can reduce GHG emissions while maintaining outputs. For example, GHG emissions from livestock production may be lessened by increasing the longevity of dairy cows, thereby decreasing the proportion of unproductive replacement animals in the dairy herd. Sourcing a larger proportion of calves from the dairy herd would decrease emissions of GHGs from beef production. The distance between the region of food production to that of consumption has relatively little impact on total GHG emissions per tonne of food product. Due to greater productivity or lesser energy inputs, importing some foods produced in other parts of the world may decrease GHG emissions per tonne compared with UK production, despite the additional emissions arising from long-distance transport. Manure application techniques to abate ammonia (NH3) emissions do not axiomatically increase emissions of N2O and may decrease them. Soil temperature measurements from 1976 to 2010 were consistent with the warming trends reported over the last 40 years.

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.

Nitrogen (N)-fixing trees can both mitigate climate change, by relieving N limitation of plant growth which promotes carbon dioxide (CO²) sequestration in plant biomass, and exacerbate climate change, by stimulating nitrification and denitrification which promotes nitrous oxide (N²O) emissions from soils. The balance between the negative radiative forcing (CO² sequestration in plant biomass) and positive radiative forcing (N²O emissions from soils) of N-fixing trees is unresolved. In this thesis I use a sequence of theoretical and empirical approaches to investigate the influence of N-fixing trees on CO² sequestration by forests and N²O emissions from forest soils, i.e., the net CO²-N²O effect of forests. The first chapter establishes a basis for the N²O effect of N-fixing trees with a meta-analysis, to accompany existing meta-analyses of the CO² effect of N-fixing trees. Chapter one demonstrates that N- fixing trees significantly increase N²O emissions from forest soils relative to non-fixing trees. The second chapter explores the controls and potential global importance of the net CO²-N²O effect of N-fixing trees using a theoretical ecosystem model. The third chapter explores the net CO²-N²O effect of N-fixing trees under manipulations of these controls with a field experiment paired with a modified version of the theoretical ecosystem model from the second chapter. Together, chapters two and three suggest that the net CO²-N²O effect of N-fixing trees is controlled by N limitation of plant growth and the extent to which N-fixing trees can regulate N fixation: N-fixing trees mitigate climate change relative to non-fixing trees under N limitation of plant growth, but N-fixing trees that cannot regulate N fixation exacerbate climate change relative to non-fixing trees under non-N limitation of plant growth. The fourth chapter represents the ecological mechanisms studied in chapters one, two and three in a land model: LM4.1-BNF is a novel representation of biological N fixation (BNF) and an updated representation of N cycling in the Geophysical Fluid Dynamics Laboratory Land Model 4.1 (LM4.1). LM4.1-BNF includes a mechanistic representation of asymbiotic BNF by soil microbes, the competitive dynamics between N-fixing and non-fixing plants, N limitation of plant growth, and N2O emissions from soils. Together these chapters elucidate the influence of N-fixing trees on the capacity of forests to mitigate and exacerbate climate change and establish a framework to analyse and project the trajectory of the net CO²-N²O effect of forests under global change.

Les sols agricoles représentent près de 66 % des émissions anthropiques de protoxyde d’azote (N₂O), 3ème gaz responsable de l’effet de serre additionnel. La variabilité des émissions mesurées au champ est élevée. La structure du sol impacte à la fois la production et le transport du N₂O dans le profil de sol. L’objectif de cette thèse était de comprendre le rôle de l’état structural du sol sur la variabilité spatiale des émissions de N₂O. La démarche utilisée associe deux types d’expérimentations en laboratoire - à l’échelle d’un bac de 0,3 m² x 0,1 m et sur une maquette de parcelle agricole de 10 m² x 0,3 m en sol nu - à un travail de modélisation intégrant des processus physiques, chimiques et biologiques dans le profil de sol et le ruissellement, le tout à une résolution temporelle fine. Ce travail a mis en évidence une hiérarchie entre les processus de production et de transport, qui évolue avec le temps et les conditions environnementales : dans des conditions favorables à la dénitrification, la production de N₂O augmente avec la masse volumique en lien avec une augmentation de la part de porosité remplie d’eau, jusqu’à une certaine limite. Le modèle déterministe a montré que la dynamique de la pluie et du ruissellement associé modifie l’intensité et la dynamique des émissions de N₂O, celles-ci étant plus tardives dans les zones avales recevant du ruissellement. Enfin, ce travail a confirmé la complexité du déterminisme des émissions de N₂O et a permis de souligner l’intérêt de caractériser la structure du sol et les émissions à une haute résolution spatiale pour améliorer la qualité des modèles prédictifs. / Agricultural soils account for 66 % of anthropogenic nitrous oxide emissions (N₂O), the 3rd greenhouse gas emitted from anthropogenic activities. N₂O emissions variability measured in-situ is quite high. Soil structure affects both N₂O production processes and N₂O movements through the soil profile. The main goal of this work was to understand the part of soil structure in soil N₂O spatial variability. Two kinds of laboratory experiments were designed: rainfall experiments on soil trays of 0.3 m² x 0.1 m and on a 10 m² x 0.3 m box with a slope. A modelling approach with a short time step was combined, involving representation of physical, chemical and biological soil processes as well as a representation of surface runoff.This work highlighted a hierarchy between N₂O production and N₂O transportation processes, which evolve with time and environmental conditions: under conditions that favor denitrification, N₂O production increases with soil bulk density due to an increase in the water-filled pore space, until a threshold limit. The deterministic modelling approach showed that rainfall dynamic and resulting runoff affect soil N₂O emissions, those emissions occurring later downslope. Finally, this work highlighted the complexity of soil N₂O emissions determinism and we pointed out that the description of soil structure at a high spatial resolution would be useful to improve modelling quality.

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付記する学位プログラム名: グローバル生存学大学院連携プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第21465号 / 農博第2308号 / 新制||農||1064(附属図書館) / 学位論文||H31||N5160(農学部図書室) / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 舟川 晋也, 教授 間藤 徹, 教授 縄田 栄治 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Bakgrund: Lustgas har konstaterats vara ett mycket bra alternativ för smärtlindring av barn vid kortvarig procedurrelaterad smärta. Lustgasen har snabbt insättande effekt och biverkningar av lustgas är få eller av mild karaktär. Lustgas påverkar miljön negativt men en del av detta kan avhjälpas med effektiva ventilationssystem. Sjukvårdspersonal som exponeras för lustgas regelbundet utsätts för hälsorisker, dessa risker är dock inte helt kartlagda i nuläget. Sjuksköterskor som administrerar lustgas ställs inför en komplex situation med många faktorer att ta hänsyn till. Lustgasens betydelse i vården har studerats ur ett patient-, hälso- och miljöperspektiv. Enligt vår kännedom saknas studier som fokuserat på specialistsjuksköterskans eller blivande specialistsjuksköterskors upplevelser av lustgasadministrering till barn. Syfte: Att undersöka specialistsjuksköterskors och sjuksköterskor under pågående specialistutbildnings upplevelser av att administrera lustgas till barn i samband med procedursmärta på akutmottagning. Metod: En kvalitativ deskriptiv intervjustudie med induktiv design tillämpades. Strukturerade intervjuer genomfördes med tio specialistsjuksköterskor och blivande specialistsjuksköterskor på ett medelstort sjukhus i Sverige. Intervjuerna transkriberades och analyserades därefter genom kvalitativ innehållsanalys. Resultat: Analysen resulterade i tre huvudkategorier; Sjuksköterskans strategier vid lustgasadministrering, Utmaningar i samband med lustgasadministrering och Lustgasens begränsningar och möjligheter. Vidare abstraherades 11 underkategorier. Övervägande positiva erfarenheter av lustgasadministrering till barn framkom under intervjuerna. I resultaten framkom att sjuksköterskan behöver kunna anpassa sig efter barnets förutsättningar. Även betydelsen av ett välfungerande teamarbete, hur arbetsmiljön påverkar lustgasadministrering och betydelsen av tydliga riktlinjer framträdde. Upplevelser av trötthet och det känslomässiga engagemanget vid lustgasadministrering beskrevs. Diskussion: Teamarbetets framgång kopplas till god kommunikation. Resultaten tyder på att hög arbetsbelastning påverkar hur väl riktlinjer följs och i förlängningen skulle detta kunna innebära att patientsäkerheten påverkas negativt. Lokala skillnader kan ha gått förlorade då studien utgår från ett sjukhus, skillnader mellan olika verksamheter skulle kunna ha bidragit med viktig information. För att belysa sjuksköterskors personliga erfarenheter användes strukturerade intervjuer. Det är möjligt att frågorna styrt svaren och att ämnen som inte togs upp kunnat ge värdefullt information. Slutsats: Sjuksköterskors upplevelser av att administrera lustgas är övervägande positiva och det finns en önskan om att utöka användandet av lustgas inom barnsjukvård. Välfungerande teamarbete och tydliga riktlinjer framträder som väsentligt för att framgångsrikt kunna administrera lustgas till barn inom akutsjukvård. Vidare forskning bör inkludera flera sjukhus för att identifiera viktig information om likheter och skillnader i användandet av lustgas samt jämföra upplevelserna hos dem som administrerar lustgasen.