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Réactions chimiques sur surfaces de platine et d'or à l'échelle atomique: approche théorique et expérimentale.Chau, Thoi-Dai 15 December 2004 (has links)
Dans ce travail nous avons étudié des réactions chimiques sur la surface de deux métaux : le platine et l'or, en utilisant la microscopie ionique à effet de champ électrique (FIM) et la spectrométrie de masse de désorption par champ pulsé (PFDMS). En complément de ces données expérimentales, nous apportons des résultats obtenus par la théorie de la fonctionnelle de la densité (DFT). La taille et la morphologie de nos échantillons font qu’ils sont de bons modèles de grains de phase active dans un catalyseur réel.
Sur le platine nous avons observé l'interaction du monoxyde d'azote. En présence d'un champ électrique, la dissociation du NO est promue, laissant sur la pointe une couche d'oxygène que l'on peut titrer par la suite avec du NO pour former du dioxyde d'azote.
L'interaction de l'hydrogène avec une pointe de platine est différente en fonction de la température. A basse température (<200 K), l’hydrogène met en image la pointe avec un assombrissement de petites régions de la pointe. A partir de 200 K, l'hydrogène induit une transformation de la pointe : les faces denses s'élargissent au détriment des faces rugueuses, avec une rangée d'atomes le long des lignes de zone [100] et le pôle central passe d’une forme circulaire à une forme carrée. L'hydrogène est supposé être à l'état atomique sur la surface; sous sa forme moléculaire, il ne contribue qu'à la mise en image. C’est sous sa forme atomique qu’il contribue aux transformations observées.
La réaction NO+H2 sur le platine conduit à l'observation d'instabilités cinétiques pour des pressions et températures données. Les régions d'amorçage ont été identifiées comme étant tout ensemble de sites de cran situé le long des lignes de zone [100]. L'observation de phénomènes oscillants n'est pas liée exclusivement à une morphologie de type polyédrique : il est possible d’observer ces instabilités cinétiques sur des pointes de rayon de courbure différent, ces pointes ne subissent pas nécessairement un changement de morphologie. L'analyse chimique au cours de la réaction a révélé la présence d'oxydes de surface ce qui nous a conduit à penser que la surface du catalyseur de platine doit être oxydée plutôt que de rester à l'état métallique. Une étape intermédiaire dans le mécanisme de site vacant a été proposée pour permettre de rendre compte de l'apparition de phénomènes oscillants. L’étape déterminante est la décomposition du monoxyde d’azote adsorbé à la surface. L’apport d’hydrogène atomique nécessaire à la formation d’eau n’est pas une étape lente, au contraire l’hydrogène semble être largement présent sous forme atomique. L’influence du champ électrique reste important, ce qui pourrait expliquer les différences de gammes de température auxquelles d’autres groupes et le nôtre observons des oscillations.
L'étude de l'interaction du CO seul sur l'or a été motivée par l'observation de la réaction CO+O2 sur pointe d'or. Sous nos conditions expérimentales, il est possible de former des mono- et dicarbonyles d’or sous forme cationique. En présence d'un champ électrique, la formation de carbonyles d'or est promue au niveau des sites de cran de la surface. Les résultats obtenus par DFT sont concordants avec les résultats expérimentaux.
A l'instar du Pt, nous avons étudié l'interaction du monoxyde d'azote sur pointe d'or. Nous avons observé la formation de protoxyde d'azote et d'un dimère de monoxyde d'azote. Le mécanisme de formation de ces espèces reste encore inconnu. Une couche d'oxygène adsorbée à la surface peut être titrée par du NO en formant du dioxyde d'azote.
En présence d'oxygène seul sur une pointe d'or sans champ électrique, les spectres de masse ne révèlent que la présence d'oxygène moléculaire. En présence d'un champ électrique, il est possible de détecter de l'oxygène atomique sans toutefois avoir la formation d'un oxyde d'or. Il est possible de former de l'ozone à partir d'une pointe recouverte d'oxygène atomique en présence d'oxygène moléculaire gazeux. Les calculs par DFT nous laissent à penser que la formation du cation O3+ ne se fait pas à la surface mais à proximité. Ils montrent entre autres que le champ électrique déstabilise l'oxygène atomique, ce qui pourrait le pousser vers des régions où l'effet du champ est le moins intense (la tige de la pointe).
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La dynamique spatio-temporelle des flux d’oxyde nitreux (N2O) des lacs, rivières, et étangs boréauxSoued, Cynthia 12 1900 (has links)
L’oxyde nitreux (N2O), un puissant gaz à effet de serre (GES) ayant plus de 300 fois le potentiel de réchauffement du dioxyde de carbone (CO2), est produit par des processus microbiens du cycle de l’azote (N). Bien que les eaux de surface continentales soient reconnues comme des sites actifs de transformations de l’azote, leur intégration dans les budgets globaux de N2O comporte de nombreuses incertitudes, dont l’absence des lacs dans ces modèles. Le biome boréal est caractérisé par une des plus grandes densités d’eaux douces au monde, pourtant aucune évaluation exhaustive des émissions aquatiques de N2O n’a à date été conduite dans cette région. Dans la présente étude, nous avons mesuré les concentrations de N2O à travers une large gamme de lacs, rivières, et étangs, dans quatre régions boréales du Québec (Canada), et nous avons calculé les flux eau-air résultants. Les flux nets fluctuent entre -23.1 et 177.9 μmol m-2 J-1, avec une grande variabilité inter-système, inter-régionale, et saisonnière. Étonnamment, 40% des systèmes échantillonnés agissaient en tant que puits de N2O durant l’été, et le réseau d’eaux de surfaces d’une des régions était un net consommateur de N2O. Les concentrations maximales de N2O ont été mesurées en hiver dû à l’accumulation de ce gaz sous la glace. Nous avons estimé que l’émission qui en résulte lors de la fonte des glaces représente 20% des émissions annuelles des eaux douces. Parmi les types d’eaux douces échantillonnées, les lacs sont les principaux responsables du flux aquatique net (jusqu’à 90%), et doivent donc être intégrés dans les budgets globaux de N2O. En se basant sur les données empiriques de la littérature, nous avons éstimé l’émission globale de N2O des eaux douces à 0.78 Tg N (N2O) an-1. Ce chiffre est influencé par les émissions des régions de hautes latitudes (tel que le biome boréal) dont les flux nets varient de positif à négatif constituant -9 à 27 % du total. / Nitrous oxide (N2O), a potent greenhouse gas with over 300 times the global warming potential of carbon dioxide (CO2), is produced during microbial nitrogen (N) cycling (Trogler 1999). Inland waters, known as active sites of N processing (Seitzinger et al. 2006., Harrison et al. 2008), are nevertheless poorly characterized in recent global N2O budgets (Nevison 2000, Intergovernmental Panel on Climate 2006), especially considering the absence of an estimate for lakes emissions. Although the boreal biome holds the highest density of freshwater on earth (Lehner and Döll 2004), no comprehensive evaluation of N2O emissions from boreal aquatic systems has ever been conducted. In this study, we measured N2O concentrations across a wide range of rivers, lakes, and ponds in four distinct boreal regions of Québec (Canada), and derived water surface-atmosphere N2O fluxes. Net fluxes ranged from -23.1 to 177.9 μmol m-2 d-1, with a large degree of variability across sampled systems, regions, and seasons. Over 40% of the 322 systems sampled acted as N2O sinks during the summer, with one region’s aquatic network being an overall net atmospheric N2O consumer. Seasonally, maximum N2O concentrations were measured during winter due to gas accumulation under the ice, resulting in an outgassing at ice thaw that accounts for approximately 20% of annual flux. Lakes were major drivers of the net freshwater regional flux (up to 90%), and must therefore be integrated in global aquatic N2O budgets. Based on empirical literature data, we estimated global freshwater N2O emissions to be 0.78 Tg N (N2O) yr-1. This number is subtantially influenced by fluxes from high latitude regions (including the boreal biome) which, being extremely variable, may contribute from -9 to 27 % of the total.
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Contribution à l'évaluation multicritère des systèmes de culture en protection intégrée contre les adventices : cas des émissions de protoxyde d'azote / Contribution to the multi-criteria performance assessment of integrated weed management cropping systems : case of nitrous oxide emissionsVermue, Anthony 24 February 2014 (has links)
Dans le cadre de l’évaluation multicritère des systèmes en protection intégrée contre les adventices (PIC-Adventices), cette étude a eu pour objectif d’étudier l’impact de la combinaison de pratiques alternatives à l’usage d’herbicides sur les émissions de N2O par les sols. L’étude a été conduite sur quatre systèmes de culture, un système de référence en agriculture raisonnée (S1) et trois systèmes PIC-Adventices (S2, S3, S5), sur le site expérimental Dijon-Epoisses (47°20'N, 5°2'E). La mise en place de dispositifs de mesure à haute résolution, alliant la méthode des chambres d’accumulation de gaz en surface du sol aux analyses de gaz par infrarouge, a permis d’estimer l’intensité des émissions de N2O pour les sols argilo-calcaires caractéristiques de la plaine dijonnaise, avec des flux moyens compris entre -6 et 257 g N-N2O ha-1 jour-1. Cette intensité s’est avérée étroitement liée à certains paramètres environnementaux (température, part de porosité occupée par l’eau, teneur en azote), et certaines pratiques agricoles, induisant des différences significatives entre les systèmes. Les émissions de N2O ont notamment été affectées par le mode de gestion des sols et la nature des cultures constituant la succession de chaque système. L’absence de travail du sol depuis 2008 dans le système S2 s’est traduite par une amplification des émissions de N2O d’un facteur multiplicatif d’au moins six par rapport aux autres systèmes pour l’année 2012. Par ailleurs, ces émissions équivalentes à 0.7 t C-CO2 ha-1 pourraient avoir compensé la séquestration de carbone additionnelle induite par le travail réduit du sol pendant la période de mesure. De la même manière, la dégradation des résidus de culture légumineuse, dans les systèmes S3 et S5 ont respectivement stimulé les émissions de N2O en 2011 et en 2012, en comparaison avec le système de référence S1. Par ailleurs, le suivi mensuel de la taille des communautés microbiennes du sol a également permis de mettre en évidence une variabilité temporelle liée aux pratiques culturales (travail du sol, récolte), en plus de la variabilité saisonnière. En revanche, dans cette étude les variations de taille des communautés microbiennes nitrifiantes et dénitrifiantes ne sont pas apparues comme un facteur d’explication de la variabilité des émissions de N2O, quel que soit le système. Enfin, l’approche par la modélisation des émissions de N2O sur les quatre systèmes, à l’aide des modèles NOE et DNDC, a permis d’identifier les principaux facteurs de régulation de ces émissions. De surcroît, le modèle NOE a bien identifié le système de culture S2, sans travail du sol, comme étant le système le plus émetteur de N2O, conformément aux observations de terrain. Cette étude renforce donc la pertinence de la modélisation pour estimer et analyser les émissions de N2O dans différents systèmes de culture. / In the context of the multicriteria evaluation of Integrated Weed Management (IWM) cropping systems, our study highlights the impacts of the combination of alternative agricultural practices to herbicide reliance on N2O emissions from soils. The study was located at the INRA experimental site of Dijon-Epoisses (47 ° 20'N, 5 ° 2'E) and considered 4 cropping systems, a reference system designed to maximize financial returns (S1) and three IWM systems (S2, S3, S5). The setup of high resolution measuring devices, combining the non-steady state chamber method with infrared gas analysis, allowed to estimate the intensity of N2O emissions from the calcareous clay soil, which is specific of Dijon plain, with average fluxes laying between -6 and 257 g N2O-N ha-1 day-1. The intensity of fluxes was closely related to environmental parameters (temperature, water filled pore space, inorganic N amount) and particular agricultural practices, leading to significant differences between systems. N2O emissions were notably affected by soil management and nature of crops. The conversion of S2 system to no-till in 2008 increased the N2O emissions, fluxes being at least 6 times more important than those emitted by the other cropping systems, during the year 2012. Moreover, these emissions, equivalent to 0.7 ha-1 C-CO2 ha-1, could have offset the soil additional carbon sequestration induced by reduced tillage during the studying period. Similarly, the degradation of legume crop residues in the S3 and S5 systems respectively enhanced N2O emissions in 2011 and 2012, by comparison with the S1 reference system. Elsewhere, the monthly monitoring of the soil microbial communities sizes has also helped to highlight temporal variability induced by the agricultural practices (tillage, harvest) as well as the seasonal variability. However, in this study the fluctuations of nitrifying and denitrifying communities sizes observed did not explain the variability of N2O emissions, whatever the considered cropping system. Finally, the modeling of N2O emitted from the 4 cropping systems, using NOE and DNDC models, allowed to identify the mains factors regulating the emissions. In addition, the NOE model accurately identified the S2 system, without tillage, as the most N2O emitter, in accordance with field observations. Thus, our study reinforces the relevance of modeling to estimate and explain N2O emissions in different cropping systems.
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Méthodes de méta-analyse pour l’estimation des émissions de N2O par les sols agricoles / Meta-analysis methods to estimate N2O emissions from agricultural soils.Philibert, Aurore 16 November 2012 (has links)
Le terme de méta-analyse désigne l'analyse statique d'un large ensemble de résultats provenant d'études individuelles pour un même sujet donné. Cette approche est de plus en plus étudiée dans différents domaines, notamment en agronomie. Dans cette discipline, une revue bibliographique réalisée dans le cadre de la thèse a cependant montré que les méta-analyses n'étaient pas toujours de bonne qualité. Les méta-analyses effectuées en agronomie étudient ainsi très rarement la robustesse de leurs conclusions aux données utilisées et aux méthodes statistiques. L'objectif de cette thèse est de démontrer et d'illustrer l'importance des analyses de sensibilité dans le cadre de la méta-analyse en s'appuyant sur l'exemple de l'estimation des émissions de N2O provenant des sols agricoles. L'estimation des émissions de protoxyde d'azote (N2O) est réalisée à l'échelle mondaile par le Groupe d'experts intergouvernemental sur l'évolution du climat (GIEC). Le N2O est un puissant gaz à effet de serre avec un pouvoir de réchauffement 298 fois plus puissant que le CO2 sur une période de 100 ans. Les émissions de N2O ont la particularité de présenter une forte variabilité spatiale et temporelle. Deux bases de données sont utilisées dans ce travail : la base de données de Rochette et Janzen (2005) et celle de Stehfest et Bouwman (2006). Elles recensent de nombreuses mesures d'émissions de N2O réparties dans le monde provenant d'études publiées et ont joué un rôle important lors des estimations d'émissions de N2O réalisées par le GIEC. Les résultats montrent l'intérêt des modèles à effets aléatoires pour estimer les émissions de NO2 issues de sols agricoles. Ils sont bien adaptés à la structure des données (observations répétées sur un même site pour différentes doses d'engrais, avec plusieurs sites considérés). Ils permettent de distinguer la variabilité inter-sites de la variabilité intra-site et d'estimer l'effet de la dose d'engrais azoté sur les émissions de NO2. Dans ce mémoire, l'analyse de la sensibilité des estimations à la forme de la relation "Emission de N2O / Dose d'engrais azoté" a montré qu'une relation exponentielle était plus adaptée. Il apparait ainsi souhaitable de remplacer le facteur d'émission constant du GIEC (1% d'émission quelque soit la dose d'engrais azoté) par un facteur variable qui augmenterait en fonction de la dose. Nous n'avons par contre pas identifié de différence importante entre les méthodes d'inférence fréquentiste et bayésienne. Deux approches ont été proposées pour inclure des variables de milieu et de pratiques culturales dans les estimations de N2O. La méthode Random Forest permet de gérer les données manquantes et présente les meilleures prédictions d'émission de N2O. Les modèles à effets aléatoires permettent eux de prendre en compte ces variables explicatives par le biais d'une ou plusieurs mesures d'émission de N2O. Cette méthode permet de prédire les émissions de N2O pour des doses non testées comme le cas non fertilisé en parcelles agricoles. Les résultats de cette méthode sont cependant sensibles au plan d'expérience utilisé localement pour mesurer les émissions de N2O. / The term meta-analysis refers to the statistical analysis of a large set of results coming from individual studies about the same topic. This approach is increasingly used in various areas, including agronomy. In this domain however, a bibliographic review conducted by this thesis, showed that meta-analyses were not always of good quality. Meta-analyses in agronomy very seldom study the robustness of their findings relative to data quality and statistical methods.The objective of this thesis is to demonstrate and illustrate the importance of sensitivity analysis in the context of meta-analysis and as an example this is based on the estimation of N2O emissions from agricultural soils. The estimation of emissions of nitrous oxide (N2O) is made at the worldwide level by the Intergovernmental Panel on Climate Change (IPCC). N2O is a potent greenhouse gas with a global warming power 298 times greater than the one of CO2 over a 100 year period. The key characteristics of N2O emissions are a significant spatial and time variability. Two databases are used for this work: the database of Rochette and Janzen (2005) and the one of Stehfest and Bouwman (2006). They collect numerous worldwide N2O emissions measurements from published studies and have played a significant role in the estimation of N2O emissions produced by the IPCC. The results show the value of random effects models in order to estimate N2O emissions from agricultural soils. They are well suited to the structure of the data (repeated observations on the same site for different doses of fertilizers, with several sites considered). They allow to differentiate the inter-site and intra-site variability and to estimate the effect of the rate of nitrogen fertilize on the N2O emissions. In this paper, the analysis of the sensitivity of the estimations to the shape of the relationship "Emission of N2O / N fertilizer dose" has shown that an exponential relationship would be the most appropriate. Therefore it would be appropriate to replace the constant emission factor of the IPCC (1% emission whatever the dose of nitrogen fertilizer) by a variable factor which would increase with the dose. On the other hand we did not identify significant differences between frequentist and Bayesian inference methods. Two approaches have been proposed to include environmental variables and cropping practices in the estimates of N2O. The first one using the Random Forest method allows managing missing data and provides the best N2O emissions predictions. The other one, based on random effects models allow to take into account these explanatory variables via one or several measurements of N2O. They allow predicting N2O emissions for non-tested doses in unfertilized farmer's field. However their results are sensitive to the experimental design used locally to measure N2O emissions.
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The role of biochar on greenhouse gas offsets, improvement of soil attributes and nutrient use efficiency in tropical soils / O papel do biochar nas emissões de gases do efeito estufa, melhoria de atributos do solo e eficiência de uso de nutrientes em solos tropicaisAbbruzzini, Thalita Fernanda 25 August 2015 (has links)
The solid product of pyrolysis, called \"biochar\" (BC) in the context of improving soil properties as part of agronomic or environmental management, also got into focus as a climate mitigation strategy. The researcher investigated the effects of BC on soil attributes, nitrogen (N) use and GHG emissions. In Chapter 1 the origin of BC was commented. In Chapter 2, BC from sugarcane straw was characterized, and its priming on native SC was evaluated with the treatments: (T1) Soil; (T2) BC; (T3) Soil + BC 10 Mg ha-1; (T4) Soil + BC 20 Mg ha-1; and (T5) Soil + BC 50 Mg ha-1. In Chapter 3, it was evaluated the combination of BC, filter cake (F) and vinasse (V), in relation to soil attributes and carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) emissions. The treatments were: (T1) Soil + FC + V; (T2) Soil + FC + V + BC 10 Mg ha-1; (T3) Soil + FC + V + BC 20 Mg ha-1; and (T4) Soil + FC + V + BC 50 Mg ha-1. In Chapter 4, the nitrogen (N) use efficiency was investigated in a pot trial under wheat using NH4[15N]O3 and rates of BC, with the treatments: (T1) Soil, with N, no BC; (T2) Soil, with N, BC 10 Mg ha-1; (T3) Soil, with N, BC 20 Mg ha-1; and (T4) Soil, with N, BC 50 Mg ha-1. BC had C and N contents higher compared to the feedstock. Total K, Mg and P also increased. The lowest CO2 fluxes were for BC, and CO2 from soil and soil + BC did not differ. The highest CO2 - C4 was in the first day, and there were no differences in the CO2 - C3. The BC presents characteristics to improve soil attributes. BC stability is an opportunity to reduce CO2 emissions. In Chapter 3, soil pH, P and base contents increased and Al3+ decreased with BC to sandy soil. Impacts of BC on the CEC were higher in sandy soil. Mineral N decreased with BC. Cumulative CO2 in T1 were higher in sandy and clayey soils than the control. T2 and T3 in sandy soil increased CO2 emissions, but T4 did not differ from T1. BC reduced N2O emissions from sandy and clayey soils relative to T1. BC with FC and V affected pH, CEC, P and base contents. However, those effects were higher in sandy soil. The BC supressed N2O from V and FC. In Chapter 4, BC decreased N2O from N fertilization compared to only N fertilizer. T4 had higher tillering and grain yield. Also, T2 to T4 had higher 100-grain weight and shoot. T3 and T4 had the highest N in grains. The application of BC to soil improves N availability and use efficiency, enhances grain yields and reduces N2O from N fertilization. This study opened encouraging perspectives to the evaluation of sugarcane straw BC to improve soil quality and mitigate GHG emissions. / O produto sólido da pirólise, denominado \"biochar\" (BC) no contexto da melhoria nos atributos do solo como parte do manejo agrícola e ambiental, também tem se destacado na mitigação das mudanças climáticas. O pesquisador investigou os efeitos do BC nos atributos do solo, uso do nitrogênio (N) e emissões de GEE. No Cap. 1 comentou-se a origem do BC. No Cap. 2, caracterizou-se o BC de palha de cana-de-açúcar e avaliou-se o potencial de decomposição do C do solo, com os tratamentos: (T1) Solo; (T2) BC; (T3) Solo + BC 10 Mg ha-1; (T4) Solo + BC 20 Mg ha-1 (T4); e (T5) Solo + BC 50 Mg ha-1. No Cap. 3, avaliou-se a combinação BC, torta de filtro (TF) e vinhaça (V) em atributos do solo e fluxos de dióxido de carbono (CO2), metano (CH4) e óxido nitroso (N2O) nos tratamentos: (T1) Solo + TF + V; (T2) Solo + TF + V + BC 10 Mg ha-1; (T3) Solo + TF + V + BC 20 Mg ha-1; e (T4) Solo + TF + V + BC 50 Mg ha-1. No Cap. 4 investigou-se a eficiência de uso do N num experimento em vasos com trigo usando NH4 [15N]O3 e doses de BC, com os tratamentos: (T1) Solo, com N, sem BC; (T2) Solo, com N, BC 10 Mg ha-1; (T3) Solo, com N, BC 20 Mg ha-1; e (T4) Solo, com N, BC 50 Mg ha-1. Os teores de C e N do BC foram maiores comparado à biomassa. K, Mg e P totais também aumentaram. Os menores fluxos de CO2 foram do BC. O CO2 do solo e solo + BC não diferiram. Observou-se maior CO2 - C4 no primeiro dia de incubação, porém sem diferenças no CO2 - C3. O BC apresenta características para melhorar atributos do solo e reduzir as emissões de CO2. No Cap. 3, pH, P e bases aumentaram e o Al3+ diminuíu com o BC. Os impactos do BC na CTC foram maiores em solo arenoso. O N mineral diminuíu com o BC. O CO2 acumulado no T1 foi maior nos solos arenoso e argiloso comparado ao controle. O T2 e T3 aumentaram o CO2 acumulado do arenoso relativo ao T1, enquanto T4 e T1 não diferiram. O BC reduziu as emissões de N2O pelos solos arenoso e argiloso comparado ao T1. O BC combinado à TF e V afetaram pH, CTC, P e bases do solo arenoso. O BC suprimiu o N2O de solos com V e TF. No Cap. 4, o BC diminuíu as emissões de N2O comparado ao fertilizante N apenas. T4 teve rendimento de grãos superior ao T1. T2 a T4 apresentaram maior peso de 100 grãos e biomassa aérea. T3 e T4 tiveram maior N em grãos. O BC melhora o uso do N, a produção de grãos e reduz o N2O de fertilizante N, abrindo perspectivas para a avaliação do BC de palha de cana-de-açúcar na melhoria da qualidade do solo e mitigar das emissões de GEE.
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Emissão de gases de efeito estufa do solo devido à remoção de quantidades de palha de cana-de-açúcar e à adubação nitrogenada / Greenhouse gas emission due to sugarcane straw removal and nitrogen fertilizationVasconcelos, Ana Luisa Soares de 02 December 2016 (has links)
A palha de cana-de-açúcar tem sido uma importante matéria prima para aumentar a produção de bioenergia no Brasil. Porém a dinâmica das emissões de gases de efeito estufa no campo devido à prática de remoção de palha ainda não é totalmente compreendida. O objetivo deste trabalho foi quantificar as emissões de GEE do solo devido à remoção da palha de cana-de-açúcar com e sem adição de nitrogênio. Foram realizados dois experimentos com câmaras amostrais de gás mantidas em condições naturais com quatro tratamentos: sem palha, 3, 6 e 12 Mg ha-1, os quais equivalem as intensidades de 100, 75, 50 e 0% de remoção. O primeiro foi conduzido por 180 dias sem adição de N e o segundo experimento conduzido por 100 dias, foi adicionado 80 kg ha-1 de N no sulfato de amônio e 32 kg ha-1 de N na vinhaça. Conjuntamente ao experimento 1, foi conduzido um ensaio de decomposição com as mesmas quantidades de palha limitadas por caixas plásticas sem fundo (0,3 x 0,5 m). No Experimento 1 a presença de palha aumentou 35 - 45% os fluxos acumulados N2O e CO2 em relação ao solo descoberto. O influxo de CH4 aumentou 40% na presença total de palha (12 Mg ha-1) em relação ao sem palha. O fator de emissão de N2O encontrado para a palha em decomposição foi de 0,02%. No Experimento 2 ocorreu uma intensificação das emissões devido à adubação nitrogenada, com isso as emissões em razão das quantidades de palhas não foram significantes. O fator de emissão médio foi de 0,42%. Os resultados indicam que a palha, sem N, possui um efeito na emissão de GEE e, que para manter o estoque de C do solo, é necessário a manutenção de pelo menos 6 Mg ha-1 para compensar as perdas de CO2 por respiração. Este trabalho contribuirá para os cálculos de pegada de carbono do bioetanol e na decisão da usina sobre a intensidade de remoção de palha de cana-de-açúcar para a produção de energia e etanol 2G / Sugarcane straw has been point out as an important feedstock to increase bioenergy production in Brazil However, the field greenhouse gas (GHG) emission dynamic due straw removing management is not completely understood yet. Two experiments were conducted with gas sampling chambers that was kept under natural conditions with four treatments: bare soil, 3, 6 and 12 Mg ha-1, which is approximately the equivalent of the 100, 75, 50 and 0 % intensities of removing. The first was conducted for 180 days without the N addition and the second experiment was conducted for 100 day and its was added 80 kg ha-1 N in ammonium sulfate and 32 kg ha-1 N in the vinasse. Parallely to the experiment 1, a decomposing trial was conducted with the same straw amounts in a side limited bottomless plastic boxes (0.3 x 0.5 m). In Experiment 1, the presence of straw increased 35-45% the N2O and CO2 accumulated flux compared to the bare soil. While the influx of CH4 increased by 40% in the maximum straw amount (12 Mg ha-1) compared to zero. The N2O emission factor found for the straw decomposition was 0.02%. In Experiment 2 occurred an intensification of emissions due to nitrogen fertilization which raised the average emission factor for 0.42%. Thus emission due straw quantities were not significant. The results indicate that the straw without N has an effect of GHG emissions, and in order to maintain the C stock in soil is need keep at least 6 Mg ha-1 of straw to compensate for the loss of CO2 thru respiration. This work will contribute to the bioethanol carbon footprint calculation and in the grower decision taking of straw removing intensity for energy and 2G ethanol
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Fisiologia, bioquímica e conservação de bananas e goiabas sob altas concentrações de O2 combinadas com CO2 e N2O / Physiology, biochemistry and conservation of bananas and guavas at high concentrations of O2 combined with CO2 and N2OCerqueira, Thales Sandoval 06 July 2012 (has links)
Atmosferas com altas concentrações de O2, bem como atmosferas enriquecidas com N2O têm sido sugeridas como alternativas para as atmosferas com baixo O2 e alto CO2. O armazenamento de frutos em atmosferas com alto CO2 por um longo período pode ocasionar desordens fisiológicas. Além disso, existe pouca informação na literatura sobre os efeitos de altas concentrações de O2 no metabolismo oxidativo em frutos. O N2O é um gás de ocorrência natural, não tóxico descrito como um potente antagonista à produção e à ação do etileno. Este trabalho teve como objetivo estudar a influência da atmosfera controlada com altas concentrações de O2 associadas ou não a CO2 e N2O sobre a fisiologia, o metabolismo oxidativo e o comportamento pós-colheita de bananas e goiabas. Bananas Nanicão e goiabas Kumagai foram submetidas aos tratamentos com atmosfera controlada em sistema de fluxo contínuo. Os frutos foram dispostos em câmaras sob o fluxo de 200 mL min-1. Todos os tratamentos foram mantidos em câmara com temperatura controlada de 22°C. A umidade em torno dos frutos foi mantida em 95%UR. Os frutos foram avaliados quanto à qualidade, produção de CO2, etileno e atividade enzimática. O alto O2 acelerou o início da senescência em ambos os frutos. Porém, foram observadas diferenças entre a banana e a goiaba, sendo que na banana o pico climatérico e o processo de amadurecimento foram antecipados. Na goiaba, o efeito marcante foi a perda da cor verde da casca. Provavelmente, as respostas observadas estão diretamente relacionadas à influência do oxigênio no metabolismo do etileno e as capacidades antioxidantes da banana e goiaba. Quando o alto O2 foi associado ao CO2 e ao N2O também foi verificada antecipação do início da senescência, porém foram verificadas diferenças entre os tratamentos com CO2 e aqueles com N2O. O alto O2 associado ao CO2 evitou a ocorrência de processos fermentativos mesmo nas concentrações mais elevadas de CO2. Com relação ao N2O, a associação deste gás ao alto O2 não reteve o amadurecimento. Por outro lado, sua associação ao baixo O2 permitiu aumento na vida pós-colheita de ambos os frutos, sem a ocorrência de processos fermentativos. Em relação ao metabolismo oxidativo a banana com alto O2 desencadeou acúmulo de oxigênio reativo com conseqüente alteração na atividade das enzimas oxidativas, diferindo da goiaba na qual os teores de oxigênio reativo se mantiveram baixos durante todo armazenamento. Isso ocorre, provavelmente devido às diferenças na capacidade antioxidante entre estas frutas a qual é consideravelmente maior na goiaba. / Atmospheres with high O2 levels and N2O enriched atmospheres have been suggested as an alternative to the atmospheres of low O2 and high CO2. Fruit storage under atmospheres with high CO2 for a long period may develop physiological disorders. In addition, there is not enough information about the effects of high O2 concentrations on fruits oxidative metabolism. N2O is a gas present on nature, non-toxic described as a powerful antagonist to production and action of ethylene. This work aimed to study the influence of controlled atmosphere with high O2 concentrations, associated or not to CO2 and N2O on the physiology, oxidative metabolism and post-harvest behavior of bananas and guavas. Bananas Nanicão and guava Kumagai were treated under continuous flow system. The fruits were placed into chambers under flow of 200 mL min-1. All treatments were maintained in a chamber with controlled temperature of 22°C. The humidity around the fruits was kept at 95% UR. It was quality evaluated CO2 and ethylene production and enzyme activity. The high O2 accelerated the onset of senescence in both fruits. However, differences were observed between the banana and guava, banana anticipated the occurrence of the climacteric peak by changing all the variables related to maturity. The main effect observed over guavas was the loss of peel green color. Probably, the observed responses are related to oxygen effect on ethylene and antioxidant capacity of banana and guava. When the O2 was associated with high CO2 and N2O was also observed an anticipation of the beginning of senescence, but differences were observed between CO2 and N2O treatments. The high O2 associated with CO2 prevented the occurrence of fermentative processes even at the highest concentrations of CO2. The N2O associations with high O2 do not increase postharvest life too. On the other hand, the N2O associations with low O2 allow delay ripening process. In relation to oxidative metabolism at high O2 banana triggered accumulation of reactive oxygen and consequent change in the activity of enzymes involved, differing from guava in which the levels remained low throughout storage. This is probably due to differences in the antioxidant activity of these fruits and which is considerably higher in guava. Keywords: High oxygen; Nitrous oxide;
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Emissões de N2O pela parte aérea de plantas de milho (Zea mays L.) / Nitrous oxide emissions from the above ground part of maize plants (Zea mays L.)Ferrão, Gregori da Encarnação 08 August 2013 (has links)
O óxido nitroso (N2O) é um gás traço, considerado um dos principais causadores do aquecimento global. Em solos agrícolas, a aplicação de fertilizantes nitrogenados, necessários às culturas, é a principal responsável pela formação deste gás. Internacionalmente, a metodologia mais utilizada e aceita para quantificar os fluxos totais de uma área baseia-se na alteração de concentração no interior de câmeras estáticas instaladas sobre o solo. Entretanto, diversos trabalhos sugerem que as plantas também são agentes desta dinâmica de fluxos entre o solo e a atmosfera, um fator não contabilizado na quase totalidade das pesquisas. O objetivo deste trabalho de pesquisa foi quantificar as emissões de N2O em plantas de milho simultaneamente aos fluxos provenientes do solo ao longo de um ciclo de cultivo, assim, agregar este montante potencial de emissão nas estimativas do sistema solo-planta-atmosfera. O experimento foi conduzido em delineamento inteiramente casualizado, sendo que seis Câmaras de Crescimento e Coleta (CCC\'s) comportaram as plantas de milho e três CCC\'s permaneceram sem plantas (testemunhas). Durante a coleta das amostras a atmosfera no interior das câmaras foi mantida a 28ºC ± 1 °C, a umidade relativa abaixo do ponto de saturação e a concentração de dióxido de carbono (CO2) entre 300 e 400 ppmv. As medidas de N2O provenientes da parte aérea e do solo foram determinadas durante todo o ciclo da cultura do milho (i. e. 105 dias). O fluxo de N-N2O proveniente do solo variou de 10,37 a 693,85 ´mü´g m-2solo h-1. Para a parte aérea das plantas de milho, os fluxos de N-N2O variaram de 65,47 a 1444,92 ´mü´g m-2folha h-1. Os resultados mostraram uma estreita correlação entre as respostas nas emissões provenientes do solo e parte aérea após a aplicação do fertilizante nitrogenado em cobertura, indicando não somente a influencia do conteúdo de N2O do solo, mas também a influência da dimensão da aérea foliar das plantas no momento de disponibilidade deste N2O no solo. O fator de emissão total (solo + parte aérea) calculado em função N-fertilizante aplicado foi de 8,2%. Ao longo do período amostral, cada planta acumulou uma emissão superior a 8000 ´mü´g N-N2O. Os resultados explicitam que, ao negligenciar esta via emissora, pode-se estar subestimando o fluxo total de N2O emitido por uma área sob cultivo em mais de 20% / Nitrous oxide (N2O) is a trace gas, considered a major cause of global warming. In agricultural soils the application of nitrogen fertilizer needed for crops, is the main responsible for the formation of this gas. Internationally, the most used and accepted method to measure total flow from one area is based on the change of concentration into static chambers installed on the soil surface. However, several studies suggest that plants are also active members of this dynamic flux between soil and atmosphere, a factor not accounted for in almost all surveys. Thus, the aim of this research was to simultaneously quantify N2O emissions from maize plants and soil over a crop cycle and thus aggregate this potential amount of emission in the estimates of the soil-plant-atmosphere system. The experiment was conducted in a completely randomized design with six Growth and Sampling Chambers (CCC) containing plants and three Chambers without plants (controls). During sampling period the atmosphere inside the chambers was maintained at 28 ° C ± 1 ° C, relative humidity below the saturation point and the concentration of carbon dioxide (CO2) between 300 and 400 ppmv. Measurements of N2O from shoot and soil were made throughout the life cycle of maize (i.e. 105 days). The flux of N2O-N from soil ranged from 10.37 to 693.85 ´mü´g m-2 soil h-1. For the shoots of maize, N2O-N flux ranged from 65.47 to 1444.92 ´mü´g m-2 leaf h-1. The results showed a close correlation between the responses from soil and shoot emissions after the application of nitrogen fertilizer as topdressing, indicating not only the influence of the content of N2O in soil, but also the influence the leaf size of the plants when N2O was available in the soil. The total emission factor (soil + shoot) calculated according to total N in the applied fertilizer was 8.2%. Over the sample period, each plant accumulated more than 8000 ´mü´g N-N2O emissions. The results of this research indicates that ignoring this way of N2O release can lead to an underestimation of almost 20% of the total N2O flux emitted by an area under cultivation
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Comentários à Resolução CFO 051/04 do Coselho Federal de Odontologia que regulamenta a aplicação da analgesia relativa ou sedação consciente com a mistura de oxigênio e óxido nitroso no Brasil / Commentaries on the Resolução CFO 51/04 from the Conselho Federal de Odontologia that regulates the use of relative analgesia or conscious sedation with the mixture of oxygen and nitrous oxide in BrazilFerrari, Mario André Maximilian Couto 19 July 2005 (has links)
Durante muitos anos a sedação consciente com a mistura de oxigênio e óxido nitroso foi utilizada por cirurgiões-dentistas em vários países do mundo. Já no Brasil, essa utilização só foi regulamentada com a edição da resolução do Conselho Federal de Odontologia CFO 51/04 (CFO, 2004b). Como todo instrumento de regulamentação, este também deve ser analisado para que possa ser melhor entendido. Assim, o presente estudo teceu comentários acerca dos aspectos integrantes de tal resolução, procurando destacar a importância e a relevância de cada um deles. Tal avaliação reveste-se de grande importância, pois a organização dos cursos que habilitarão os cirurgiões-dentistas a aplicar a sedação consciente com a mistura de oxigênio e óxido nitroso terá que cumprir os requerimentos presentes na citada resolução. Ressalte-se que não se pretendeu esgotar o assunto, até mesmo porque isso seria impossível, mas suscitar o interesse dos pesquisadores no desenvolvimento de investigações mais aprofundadas sobre a matéria. / For many years the conscious sedation with nitrous oxide and oxygen has been used in various countries in the world. This usage in Brazil has only been regulated with the present Resolução do Conselho Federal de Odontologia CFO 51/04. As any other regulating instrument, this also needs analysis for its complete understanding. In this study every aspect of the Conselho´s Resolution were analyzed, trying to underline their importance and relevance of each one of them. This evaluation becomes of great importance because it is based on its requirements that the courses for the habilitation of dentists who intend to use the technique of conscious sedation with nitrous oxide and oxygen will be developed and ruled. This study intends to be one of the tools that will be used to fully understand this resolution.
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Avaliação agronômica e fluxo de gases do efeito estufa a partir de solo tratado com resíduos e cultivado com mamona (Ricinus communis L.) em área de reforma de canavial / Agronomic evaluation and greenhouse gas flow from soil treated with residues and cultivated with castor bean (Ricinus communis L.) in a reform area of sugar caneChiaradia, Jonas Jacob 09 February 2006 (has links)
A aplicação de resíduos em solos agrícolas pode alterar significativamente a dinâmica do ciclo dos elementos no solo, conseqüentemente modificando sua fertilidade, a nutrição das plantas e os fluxos de gases do solo para a atmosfera. A possibilidade de produção de biocombustíveis a partir de óleos vegetais e com a atenção especial dada a cultura da mamona faz nesse momento com que o cultivo desta oleaginosa ressurja nacionalmente como cultura de interesse. Além disso, em áreas agrícolas próximas a grandes centros urbanos, a utilização agrícola de resíduos na agricultura é uma prática já empregada, porém ainda, sem o total conhecimento dos processos envolvidos em relação ao comportamento desses materiais no ambiente e seu real comportamento como fonte de nutrientes para as culturas. Em função do exposto, o presente trabalho foi realizado com o objetivo de avaliar os efeitos de três resíduos, contendo diferentes formas de N, na fertilidade do solo e nutrição mineral da mamona cultivada em área de reforma de canavial, bem como também quantificar os fluxos de gases do efeito estufa (CO2, CH4 e N2O) em função da aplicação de doses de um lodo de esgoto ou fertilização mineral no solo, antes do plantio da mamona. Assim, foram conduzidos dois experimentos a campo no ano agrícola de 2004-2005. No primeiro avaliou-se a contribuição de resíduos como fonte de N para a cultura da mamona e foi conduzido sob um Argissolo Vermelho-Amarelo distrófico. A dose de nitrogênio referencial foi de 75 kg ha-1 e as quantidades aplicadas de cada resíduo foram calculadas em função do conteúdo e disponibilidade do N nestes. Os dados obtidos mostram que os resíduos de origem orgânica (lodo de esgoto e Citrofer) constituíram-se numa fonte eficiente de N e para as doses equivalentes ou maiores que a referência, a produtividade da mamona foi igual ou superior a adubação mineral. Com relação a outros componentes de produção, o tamanho do racemo e nº de frutos para os tratamentos que receberam a aplicação de N via resíduos orgânicos ou a adubação mineral, não diferiram estatisticamente, mas foram superiores aos demais. O N foi o nutriente que mais limitou o desenvolvimento e produtividade da mamona. No segundo experimento avaliou-se a emissão dos gases CO2, CH4 e N2O na mesma área onde foi realizado o primeiro experimento, porém, foram avaliados os tratamentos que receberam adubação mineral e lodo de esgoto em três doses. Tanto a adição de lodo de esgoto como a adubação mineral alteraram os fluxos de CO2, N2O e CH4. Quando a quantidade de N aplicada via lodo de esgoto foi igual ao tratamento que recebeu adubação mineral, parece não haver diferenças entre as emissões de CO2 desses tratamentos. Para o N2O, quando se faz a comparação entre os tratamentos que foram concebidos para disponibilizar cerca de 75 kg N ha-1, observa-se que os valores de emissão de N2O na maioria das amostragens foram semelhantes. O tratamento que recebeu o dobro da dose de N via lodo de esgoto apresentou emissões de N2O superiores ao tratamento controle e adubação mineral. Com relação à emissão de metano para a atmosfera, não houve diferenças significativas entre os tratamentos. / The application of residues in agricultural soils can significantly change the dynamic of the element cycles into the soil, changing consequently its fertility, the plant nutrition and the soil gas fluxes to the atmosphere. The possibility of bio-fuel production from vegetable oils and the special care given to the castor bean at this time, make interest to this crop to re-start its cultivation in all country. Beside that, agricultural area near big urban centers, the use of residues in crop production is common and it is already incorporated, but there is still lack of knowledge of the process involved in relation to the behavior of these residues in the environment and as a source of nutrients for the crops. Taken in consideration what was written above, the present work was made aiming to evaluate the effect of three residues having different forms of nitrogen in the soil fertility and mineral nutrition of castor bean cultivated in a reform area of sugar cane, and also to quantify the gas fluxes of greenhouse effect (CO2, CH4 and N2O) in relation to the applied dose of sewage sludge or mineral fertilization of the soil before the castor bean plantation. Two experiments were carried out in the field in the agricultural year of 2004-2005. In the first it was evaluated the residues contribution as nitrogen source to the castor bean crop and it was conducted under one Ultisol (Argisolo Vermelho Amarelo distrófico) soil. The reference dose for nitrogen was 75 Kg ha-1 and the applied quantities of each residue were calculated in function of the content and the availability of N into the residues. The data have shown that the residues of organic origin (sewage sludge and Citrofer) constitute in an efficient source of N and for the equivalent dose or grater than the reference dose, the castor bean productivity was similar or higher than the mineral fertilization. In relation to the other parameters of production, the size of raceme and the number of fruits for the treatments that received N application via organic residues or mineral fertilization, did not differ statistically, but they were higher than the other treatments. The N was the nutrient that limited more the development and the productivity of castor bean. In the second experiment, it was evaluated the CO2, CH4 and N2O gas emission in the same area of the first experiment, but with treatments that received mineral fertilization and sewage sludge in three doses. The sewage sludge and the mineral fertilization changed the gas flow of CO2, CH4 and N2O. When the applied quantity of N via sewage sludge was equal to the mineral fertilization treatment seems that there was no difference between the CO2 emissions. For the N2O, when it was compared the treatments responsible to fulfill about 75 Kg ha-1 of N, it was observed that the values of N2O emission were similar for the great part of samples. The treatment that received the double dose of N via sewage sludge presented N2O emission higher than the control and the mineral fertilization treatments. All the treatments presented no difference for the methane emission to the atmosphere.
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