O Brasil ocupa uma posição de destaque na produção e exportação mundial de carne bovina. No entanto, devido a parcela de contribuição dos ruminantes nas emissões de metano no país, a pecuária brasileira vem sofrendo contínua pressão das comunidades internacionais; e possivelmente, no futuro, tais emissões, possam ser motivo para a criação de barreiras para a exportação mundial de nossa carne. Neste contexto, o presente estudo teve o objetivo de avaliar o efeito dos taninos como alternativa a moduladores químicos de fermentação ruminal sobre as emissões de metano da microbiota de bovinos de corte. Para isso, foram realizados quatro experimentos. No primeiro estudo, foi avaliado o efeito dos taninos condensados (TC) das espécies Flemingia macrophylla, Leucaena leucocephala, Stylosanthes guianensis, Gliricidia sepium, Cratylia argentea, Cajanus cajan, Desmodium ovalifolium, Macrotiloma axilare, Desmodium paniculatum e Lespedeza procumbens em presença ou não de polietileno glicol (PEG), sobre os parâmetros ruminais através da técnica de produção de gases in vitro. Foram mensurados a produção de metano, a concentrações de amônia e de ácidos graxos de cadeia curta (AGCC), quantificações microbianas e cinética de degradação ruminal. As espécies L. leucocephala, D. paniculatum e L. procumbens reduziram a produção de metano in vitro. A população de Ruminococcus flavefaciens, arqueias metanogênicas e protozoários foi reduzida, enquanto que o número total de bactérias ruminais e Fibrobacter succinogenes foi elevado. No segundo experimento, foram mensurados consumo, digestibilidade, parâmetros ruminais, quantificação microbiana e emissão de metano em bovinos fistulados Nelore consumindo dietas contendo 0%, 1,25% e 2,5% de TC de extrato de acácia. A suplementação com taninos reduziu tanto o consumo como as emissões de metano diárias por animal. Os TC suprimiram diretamente a comunidade de arqueias metanogênicas e alteraram beneficamente as populações ruminais de F. succinogenes, R. flavefaciens e bactérias totais. No terceiro experimento, dejetos dos bovinos obtidos no ensaio in vivo foram acondicionados em biodigestores de bancada para avaliação do efeito das fezes ricas em taninos sobre a produção de biogás e metano. O estudo mostrou que os taninos não tiveram efeito negativo sobre a produção do biogás a partir dos dejetos dos bovinos. No quarto experimento, foi realizado ensaio em casa de vegetação para a avaliação do efeito das fezes ricas em taninos condensados sobre a dinâmica da população microbiana do solo. Os taninos aumentaram a entrada de N fecal e alteraram a ciclagem de nutrientes e a dinâmica microbiana do solo. Nosso estudo mostrou que os taninos podem ser uma promissora alternativa nutricional a moduladores químicos na redução da metanogênese de bovinos de corte, contribuindo positivamente na relação solo-planta-animal e colaborando na sustentabilidade da pecuária em sistemas tropicais. / Brazil occupies a prominent position in cattle beef production and export in the world. However, due to the ruminant\'s contribution to methane emissions in the country, Brazilian livestock farming has been suffering continuous pressure from international communities; and possibly in the future, such emissions, may be grounds for creating barriers to the worldwide export of our meat. In this context, the present study aimed to evaluate the effect of tannins on the methane emissions of rumen beef cattle microbiota as an alternative to chemical rumen modulators. For this, four experiments were performed. In the first assay, condensed tannins (CT) from Flemingia macrophylla, Leucaena leucocephala, Stylosanthes guianensis, Gliricidia sepium, Cratylia argentea, Cajanus cajan, Desmodium ovalifolium, Macrotiloma axilare, Desmodium paniculatum and Lespedeza procumbens in the presence or not of polyethylene glycol (PEG) on the ruminal parameters in the in vitro gas production technique was evaluated. Methane production, concentrations of ammonia and short chain fatty acids (AGCC), microbial quantification and kinetics of ruminal degradation were measured. The species L. leucocephala, D. paniculatum and L. procumbens reduced the production of methane in vitro. The populations of Ruminococcus flavefaciens, methanogenic archeas and protozoa were reduced, while total number of ruminal bacteria and Fibrobacter succinogenes was increased. In the second experiment, intake, digestibility, ruminal parameters, microbial quantification and methane emission were evaluated in Nelore fistulated cattle consuming diets containing 0%, 1,25% and 2,5% TC of acacia extract. Tannin supplementation reduced both daily intake and methane emissions per animal. CT directly suppressed methanogenic archeas community and beneficially altered ruminal populations of F. succinogenes, R. flavefaciens and total bacteria. In the third experiment, bovine manure from the in vivo assay was stored in bench scale biodigesters to assess the effect of tannin-rich feces on the production of biogas and methane. The study showed that tannins had no negative effect on the biogas production from the bovine manure. In the fourth experiment, a greenhouse experiment was carried out to evaluate the effect of tannin-rich feces on the dynamics of soil microbial population. Tannins increased fecal N intake and altered nutrient cycling and soil microbial dynamics. Our study showed that tannins might be a promising nutritional alternative to chemical modulators in the reduction of methanogenesis of beef cattle, contributing positively to the soil-plant-animal relationship and collaborating on the sustainability of livestock farming in tropical systems.

The aim of this thesis was to investigate contrasting pasture management strategies on the foraging behaviour, pasture production, carcass characteristics, herbage intake, faecal gas emissions and methane emission by sheep grazing Italian ryegrass (Lolium multiflorum) pastures. The experiment was carried out in 2014 and 2015. The experimental design was a randomized complete block with four replicates and two grazing strategy treatments (traditional rotational stocking method – RT meaning pre- and post-grazing target heights of 25 and 5 cm, respectively and, “rotatinuous stocking” – RN with pre- and post-grazing target heights of 18 and 11 cm, respectively). The grazing management was based on a 1-day strip-grazing regime. Male castrated sheep were used. The actual average sward heights for the RN treatment were 17.9 and 11.1 cm (pre- and post-grazing, respectively) and 27.1 and 7.8 cm for the RT (pre- and post-grazing, respectively). The stocking period in 2014 was 146 and 140 days (RN and RT, respectively) and in 2015 it was 155 and 146 days (RN and RT, respectively). The diurnal animal activities (grazing, ruminating and resting time) did not differ between treatments, with average of 439.6, 166.9 and 85.0 minutes, respectively. The bite rate, feeding station per min and steps per min were greater at the RN than the RT treatment. Grazing time and bite rate were greater in the afternoon than morning in both treatments. Therefore, the daily herbage intake by sheep grazing Italian ryegrass was greater for the RN than the RT treatment (CHAPTER II). The herbage production in the RN was 28% higher than the RT treatment. Individual average daily gain and live weight gain per hectare were greater in the RN than the RT treatment (CHAPTER III). RN treatment presented greater final live weight, carcass and commercial cut weights from grazing sheep than RT treatment (CHAPTER IV). RN treatment had a faecal chemical quality greater than RT treatment, resulting in a greater daily nitrogen excretion per animal and greater faecal CH4 and N2O emissions (CHAPTER VI). The “rotatinuous stocking” (RN) was the better grazing management strategy for mitigation of CH4 emissions by sheep grazing Italian ryegrass, emitting 64% less CH4 per unit area and 170% less CH4 per unit of animal product than the traditional rotational stocking method (RT) (CHAPTER V).

The present dissertation covers three research topics on catalytic environmental emissions control, including (1) aging and regeneration mechanisms of Rh- and Pd- model three-way catalysts (TWC) for gasoline automotive emission control, (2) catalytic methane emissions abatement from natural gas vehicles, and (3) scale-up of CO₂ capture and methanation using dual functional catalytic materials. The study resulted in two peer-reviewed publications, two future papers and one patent application which is currently under review. Modern TWC use supported two separate catalyst layers on a monolith containing one Pd and the other Rh for the emissions control of CO, HC and NOₓ. The rhodium (Rh) metallic component (active for NOₓ reduction) experiences the most severe oxidative thermal deactivation (forming inactive Rh³⁺) during fuel cutoff, an engine mode (e.g., at downhill coasting) used for enhancing fuel economy. In a subsequent switch to a slightly fuel rich condition, in situ catalyst regeneration is accomplished by the reduction of the Rh³⁺ with H₂ generated through steam reforming catalyzed by residual Rh⁰ sites. The present thesis reports the effects of the deactivation and regeneration processes on the activity, stability and structural properties of 0.5% Rh/Al₂O₃ and 0.5% Rh/Ce_xO_y-ZrO₂ (CZO) as model catalysts. Both materials are used to varying extents in modern TWC. A very brief introduction of three-way catalysis and system considerations will be presented. During simulated fuel cutoff, catalyst deactivation is accelerated with increasing aging temperature from 800 °C to 1050 °C. Rh on a CZO support experiences less deactivation and faster regeneration than Rh on Al₂O₃. Catalyst characterization techniques including BET surface area, CO chemisorption, temperature programmed reduction, and x-ray photoelectron spectroscopy, transmission electron microscopy, scanning-electron microscopy, and x-ray diffraction measurements were applied to examine the role of metal-support interactions in each catalyst system. For Rh/Al₂O₃, strong metal-support interactions leading to the formation of a stable rhodium aluminate (Rh(AlO₂)_y) complex dominates during fuel cutoff, resulting in more difficult catalyst regeneration (reduction). For Rh/CZO, Rh sites were partially oxidized to Rh₂O₃ and were relatively easy to be reduced to active Rh⁰ during regeneration. Moderate Pd and support sintering of Pd-Ce_xO_y is experienced upon aging, but with a minimal effect on the catalyst activity. Cooling in air, following aging, was not able to reverse the metallic Pd sintering by re-dispersing to PdO. Unlike the aged Rh-TWCs, reduction via in situ steam reforming (SR) of exhaust HCs was not effective in reversing the deactivation of aged Pd/Al₂O₃, but did show a slight recovery of the Pd activity when CZO was the carrier. The Pd⁺/Pd⁰ and Ce³⁺/Ce⁴⁺ couples in Pd/CZO are reported to promote the catalytic SR by improving the redox efficiency during the regeneration, while no such promoting effect was observed for Pd/Al₂O₃. A suggestion is made for improving the catalyst performance. The use of natural gas for vehicle applications is growing in popularity due to advanced fracking technology. Exhaust methane has been excluded from regulations since it does not participate in photochemical reactions. New vehicle environmental regulations are expected for controlling methane emissions given their contribution to the greenhouse gas effects. Methane is extremely resistant to oxidation when the natural gas-fueled engine operates in the stoichiometric mode with a supported Rh-Pd three-way catalyst (TWC). Furthermore, vehicles will still operate with fuel cutoff (for enhanced fuel economy), resulting in thermal oxidative deactivation (1050 °C) of the Rh metal in TWC to inactive Rh³⁺, resulting in a loss of both NOₓ and methane abatement activity. When the engine returns to the slightly rich mode, H₂ generated by methane steam reforming does not readily occur to reduce and regenerate the Rh. We report a solution to methane emissions abatement by catalytic reforming of an injected aqueous solution of ethanol into the simulated exhaust stream in TWC mode, which generates sufficient H₂ to regenerate especially Rh by reducing Rh³⁺ to its metallic active state. Conventional CO₂ capture and sequestration (CCS) in aqueous alkaline solutions is a very energy-intensive process with relative unstable performance and low efficiency especially for power plant effluents, and therefore there is a need for new approaches to control green house gas emissions of CO₂. Here we report on progress with an advanced technology involving CO₂ adsorption from flue gas and synthetic natural gas production, via methanation, both performed at the same temperature with the addition of renewable H₂ and by using a dual functional material (DFM). The stored H₂ used is produced by water electrolysis during those times when solar, wind, and other alternative energies generate excess power out of phase with the direct use of the electricity. The DFM is composed of nano-dispersed CaO (or Na₂CO₃) and Ru metal supported on γAl₂O₃ carrier, respectively functioning as the CO₂ adsorbent and methanation catalyst. The present paper focuses on a laboratory scale-up study by using a simulated flue gas and 5%Ru,10%CaO/Al₂O₃ and 5% Ru,10%Na₂CO₃/Al₂O₃ DFM samples. The effects of DFM preparation methods, Al₂O₃ carrier materials (with different shapes and properties), and adsorption and methanation conditions (feed compositions, flow rates, reaction temperatures) on the DFM performance were examined. Samples were prepared using chloride precursor salts and showed stable performance under pseudo scale-up conditions, with SASOL TH100 Al₂O₃ (with the highest BET surface area and pore volume/radius among the support materials) exhibiting the best performance. Compared to Ru-CaO, Ru-Na₂CO₃ based DFM materials showed improved CO₂ utilization and methanation production. Reaction conditions were explored to find optimized CO₂ adsorption and methanation.

This dissertation describes methods developed for analysis of the New York City energy system. The analysis specifically aims to consider the built environment and its' impacts on greenhouse gas (GHG) emissions. Several contributions to the urban energy systems literature were made. First, estimates of annual energy intensities of the New York building stock were derived using a statistical analysis that leveraged energy consumption and tax assessor data collected by the Office of the Mayor. These estimates provided the basis for an assessment of the spatial distribution of building energy consumption. The energy consumption estimates were then leveraged to estimate the potential for combined heat and power (CHP) systems in New York City at both the building and microgrid scales. In aggregate, given the 2009 non-baseload GHG emissions factors for electricity production, these systems could reduce citywide GHG emissions by 10%. The operational characteristics of CHP systems were explored further considering different prime movers, climates, and GHG emissions factors. A combination of mixed integer linear programing and controlled random search algorithms were the methods used to determine the optimal capacity and operating strategies for the CHP systems under the various scenarios. Lastly a multi-regional unit commitment model of electricity and GHG emissions production for New York State was developed using data collected from several publicly available sources. The model was used to estimate average and marginal GHG emissions factors for New York State and New York City. The analysis found that marginal GHG emissions factors could reduce by 30% to 370 g CO₂e/kWh in the next 10 years.

This doctoral research provides an advanced molecular approach for the investigation of microbial structure and function in response to operational conditions of biological nitrogen removal (BNR) processes, including those leading to direct production of a major greenhouse gas, nitrous oxide (N₂O). The wastewater treatment sector is estimated to account with 3% of total anthropogenic N₂O emissions. Nevertheless, the contribution from wastewater treatment plants (WWTPs) is considered underestimated due to several limitations on the estimation methodology approach suggested by the Intergovernmental Panel on Climate Change (IPCC). Although for the past years efforts have been made to characterize the production of N₂O from these systems, there are still several limitations on fundamental knowledge and operational applications. Those include lack of information of N₂O production pathways associated with control of aeration, supplemental organic carbon sources and adaptation of the microbial community to the repeated operational conditions, among others. The components of this thesis, lab-scale investigations and full-scale monitoring of N₂O production pathways and emissions in conjunction with meta-omics approach, have a combined role in addressing such limitations. Lab-scale experiments imposing short-term anoxic-aerobic cycling on partial- and full-nitrification based processes were conducted to investigate the microbial response to N₂O production. Interestingly, it was determined that full-nitrification systems could be a higher contributor to N₂O production and emissions than partial-nitrification. While it has been reported in the literature a higher contribution from the latter when the microbial community is not subjected to oxygen cycling conditions. Following the knowledge obtained with a single anoxic-aerobic cycle imposed to nitrifying communities, long-term adaptation of the microbial community to continued anoxic-aerobic cycling and its impact on N₂O production were investigated through a meta-omics approach. Long-term studies are particularly significant regarding engineered systems, where the microorganisms are continually subjected to cycling conditions again and again. A microbial adaptation at the RNA level was identified on both autotroph and heterotroph organisms. The transcripts of the metabolic pathways related to NO and N₂O production (nir, nor) and consumption (nor, nos) were initially induced followed by a gradual decline, leading to a parallel reduction in gaseous emissions over time. Other pathways not typically interrogated in conjunction with the nitrogen metabolism, such as electron transport chain and carbon fixation were also investigated and revealed a mechanism to overcome the imbalance in electron flow and generation of proton motive force (increased transcription of terminal oxidase genes, cco and cox) to uphold carbon fixation during continued cycling. The second part of this thesis focuses on full-scale WWTPs, where it is crucial to determine specific nuances of the systems’ dynamics and of the different types of treatment that may contribute to increased production and emissions of N₂O. For that purpose, two distinct BNR systems not usually considered and studied in terms of N₂O production and emissions were chosen. First, a separate centrate treatment (SCT) process employing glycerol as the supplemental carbon source was monitored. Significantly, this system was found to have one of the highest levels of N₂O production and emission report thus far. Glycerol revealed to foster a microbial community (i.e. Burkholderiales, Rhodobacterales and Sphingomonadales) that stores internal carbon and promote partial denitrification, leading to accumulation of nitrite and N₂O [7-11]. Second, both fixed- and moving-bed biofilm BNR systems were investigated. The overall N₂O emission fractions for the Integrated Fixed-Film Activated Sludge (IFAS)(0.09 – 1.1% infl-TKN) and denitrification filters (0.11 – 1.4% infl-TN) were similar to the reported emissions from suspended growth activated sludge systems [4-6]. For the IFAS system, aqueous and gaseous N₂O profiles paralleled the diurnal variability on influent nitrogen load. The production of N₂O was significantly correlated with ammonia concentration (p<0.05, r=0.91), suggesting the production through hydroxylamine oxidation pathway. Denitrification filters displayed a very peculiar pattern on N₂O emissions associated with intermittent operational cycles (i.e. nitrogen release cycle and backwash). These intrinsic operations of the denitrification filters contributed to transient oxygen conditions and nearly the entire N₂O emissions through gaseous stripping and production by inhibition of denitrification. Similarly to suspended growth systems, process design and operations demonstrated to also play an important role in N₂O emissions from attached growth processes. Finally, aeration strategies for energy efficient conventional nitrification based on the microbial community development and its associated performance was investigated in lab-scale. It was demonstrated that using the same air supply rate, continuous and intermittent aeration resulted in completely different microbial structure. Consequently, distinct kinetics and nitrification performance were observed. The aeration rate could be minimized (resulting in reduction in energy consumption) for high ammonia removal efficiency and lower N₂O emissions, as long as the process is designed accordingly to the microbial ecology developed in such conditions. In sum, the microbial structure, function and connection of metabolic pathways of complex engineered microbial communities as applicable to BNR systems and its operations were investigated in detail. From an engineering perspective, this dissertation provides an advancement on the molecular approach to characterize structure and function of microbial responses to engineered operations beyond the business-as-usual target genes, which can eventually result in better design and control of engineered BNR processes. This study offers more than an improved scientific understanding of the complex microbial environment and direct engineering applications. It connects sanitation with water quality and the greenhouse gas effect by prioritizing concurrent enhanced biological nitrogen removal and mitigation of N₂O production and emission. Ultimately the implications of the result presented herein can provide economical, environmental, health benefits for the society.

Este trabalho tem por objetivo avaliar a viabilidade técnica de processos de separação de gás carbônico em correntes de gases de combustão. Neste sentido, a separação por meio de membranas e por criogenia são avaliadas por meio de simulação de sistemas. As propostas envolvendo membranas avaliam arranjos de membranas em série, os quais são otimizados para condições de maior fluxo permeado e maior beneficio econômico. A corrente de alimentação é de 5 kmol/s e as respectivas frações molares de CO2 e N2 que compõem esta corrente são 0,15 e 0,85. Os resultados obtidos da otimização, para um arranjo de três membranas em série de polyimida de 9000 m² de área superficial, foram uma corrente de permeado de 443,1 mol/s de CO2 a 41,6%, correspondendo a aproximadamente 59% do CO2 da corrente de alimentação. Já com um arranjo de 6 membranas de 9000 m², onde a função objetivo é o maior lucro, foi selecionado o material kapton e a quantidade de CO2 separada é 161,12 mol/s, cuja concentração na mistura é de 79%, e a função objetivo tem um valor de 24.405,30 €/ano. Na outra parte do trabalho, propõe-se e avalia-se um ciclo para o aproveitamento da disponibilidade térmica na regasificação do gás natural líquido, para liquefação de CO2. Obtém-se como resultando em CO2 líquido com fração molar igual a 94%. Este processo consta de uma corrente proveniente da combustão completa de 1 mol/s de metano, contendo 1 mol/s de CO2 e 7,52 mol/s de N2. Esta corrente é comprimida e resfriada até atingir a pressão de 4000 kPa e 25 °C, posteriormente uma membrana enriquece a corrente de gases de combustão, que novamente é comprimida e resfriada até se obter a condensação e separação do CO2. Realiza-se o cálculo de equilíbrio líquido-vapor da mistura utilizando as equações de Peng-Robinson e a regra de mistura de Van der Waals no software VRTherm. A vazão molar do CO2 líquido obtida é de 0,3207 mol/s na concentração declarada. A intensidade energética do processo é de 1,135 kWh/kg de CO2 liquefeito. / The objective of this work is to evaluate the technical feasibility of carbon dioxide separation processes of flue gases streams. In this way, separation processes due membrane and cryogenics are evaluated by system simulation. The systems using membranes evaluates setup of those membranes in series, these setups are optimized for the largest permeate molar flow and the largest economic profit. The feed stream is a 5 kmol/s CO2 – N2 mixture, with molar fraction of 0.15 and 0.85 respectively. The result obtained from the optimization for a setup of three polyimide membranes of 9000 m² is a permeate stream of 443.1 mol/s with CO2 at 41.6%, corresponding to aproximadely 59% of the CO2 contained in the feed stream. When a setup of six 9000 m² membranes is analyzed using an objective function that results in the largest profit, kapton was selected as the material for the membranes. The quantity of CO2 captured is 161.12 mol/s, at 79% of concentration in the mixture, and the objective function has a value of 24,405.30 €/year. The second part of this work, proposes and evaluates a cycle that takes the thermal availability of the regasification of liquid natural gas in advantage for CO2 liquefaction. The product of the cycle is liquid CO2, with a molar fraction of 0.94. The process is fed with a stream that comes from the stoichiometric combustion of 1 mol/s of methane, that stream is composed by 1 mol/s of CO2 and 7.52 mol/s of N2. The stream is then compressed up to the pressure of 4000 kPa and cooled down to 25 °C. After that a membrane concentrates the CO2 in one stream, which is again compressed and cooled down until the condensation of CO2 is achieved. Calculations of liquid – vapor are performed with the Peng- Robinson’s equations and the Van der Waals mixture rule using the software VRTherm. The molar flow rate of liquid CO2 obtained is of 0.3207 mol/s in the concentration mentioned before. The energy intensity of the process is of 1.135 kWh/kg of liquid CO2.

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-03T16:31:46Z No. of bitstreams: 1 _Dissertação-1.pdf: 1765644 bytes, checksum: 7e195b49bdd27dff996d76e75bbb6210 (MD5) / Made available in DSpace on 2017-10-03T16:31:46Z (GMT). No. of bitstreams: 1 _Dissertação-1.pdf: 1765644 bytes, checksum: 7e195b49bdd27dff996d76e75bbb6210 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / O aquecimento global provocado por gases como CO2, N2O e o CH4 resultantes de atividades agrícolas e por solos alagados tem motivado inúmeros estudos em diversos países, procurando quantificar a contribuição de diferentes sistemas na emissão desses gases. Os objetivos desse estudo foram elucidar o mecanismo de produção do gás do efeito estufa, óxido nitroso (N2O) em uma área de floresta secundária baixa localizada em Manguariba - Rio de Janeiro e determinar se estas emissões ocorrem acompanhadas por processos de nitrificação ou desnitrificação. Para que isso fosse possível, foram realizadas quatro campanhas de amostragens seguidas de experimentos de incubação do solo em laboratório e análises químicas deste solo antes e após as incubações. Medidas de variação de pressão em câmaras sob condições controladas de temperatura foram realizadas empregando-se um manômetro tubo em “U” em quatro experimentos e um barômetro/sensor/datalogger em outros dois experimentos. As concentrações de N2O, bem como as de CH4 no solo, foram determinadas antes e após as incubações por cromatografia gasosa. Na primeira campanha de amostragem foram coletadas também amostras de água em um curso de água que pode ser uma fonte de nitrogênio para este solo, pois em época de chuvas a água poluída com esgoto doméstico, deste riacho chega até os pontos de amostragem. Foram determinadas as concentrações de amônio e nitrato em amostras do solo, antes e após incubações, e na água do riacho. Através dos dados gerados pelas análises químicas determinamos as taxas líquidas de nitrificação, mineralização/assimilação ocorridas durante o período de incubação do solo e correlacionamos essas taxas com a produção de óxido nitroso. A nitrificação a uma taxa constante se mostrou dominante no experimento onde houve a maior produção de N2O. Nos demais experimentos a nitrificação permaneceu dominante, porém seguida por desnitrificação em outros dois experimentos, nos quais a produção do gás foi muito pequena e até mesmo nula, indicando a redução do óxido nitroso a N2. A desnitrificação ocorreu de forma dominante em apenas um dos experimentos e possivelmente foi seguida por nitrificação, pois houve uma pequena produção de N2O durante esta incubação. / The global warming caused by greenhouse gases like CO2, CH4 and N2O resulting from agricultural activities and flooded soils has motivated numerous studies in many countries, seeking to quantify the contribution of different systems on greenhouse gas emissions. The objectives of this study were to elucidate the mechanism of production of greenhouse gas, nitrous oxide (N2O) in a secondary forest area located in downtown Manguariba (Rio de Janeiro) and determines if these emissions occur accompanied by processes of nitrification and denitrification. To make this possible, there were four sampling campaigns followed by incubation experiments of soil in the laboratory and chemical analyses of soil before and after incubations. Measures of barometric pressure variation in PVC chambers under controlled temperature were carried out using a variation of a pressure gauge manometer tube into "U" for four incubation experiments and a sensor which measures the pressure variation barometer / sensor / datalogger (Baro Diver) during the third and fourth experiments. N2O concentrations were determined by gas chromatography. In the first year of sampling, samples of water were taken from a tributary of the Rio Guandu, which can be a source of sewage pollution for this soil, because in the rainy season the water in this tributary reaches the sampling points. Chemical analysis was performed for determination of NH4 + and for analysis of nitrate ions. Data generated by the chemical analysis determined the rate of net nitrification, mineralization / assimilation which occurred during the incubation periods and correlated these rates with the production of nitrous oxide. Nitrification at a constant rate proved to be dominant in the experiment where there was a greater production of N2O. In other experiments, however, nitrification remained dominant followed by denitrification in two other experiments, in which gas production was very small and even zero, indicating the reduction of nitrous oxide to N2. Denitrification was very dominant in only one experiment and was followed by nitrification possibly because there was a small N2O production during this incubation. The experiment with the barometer / sensor / datalogger (Baro Diver) was carried out to confirm what would be the dominant process along these incubations. With this sensor we observed nitrification-dominant production of nitrous oxide. There were no correlations between the flow of N2O emitting in situ and flow generated during the incubation periods. We also observed that the effluent water from the Rio Guandu sample showed high concentrations of nitrate and ammonia and can be considered as a source of inorganic N to this soil

Atualmente a questão das mudanças climáticas causada por gases do efeito estufa (GEE), desperta grande interesse. Diante dos possíveis impactos que tais mudanças podem causar, buscam-se alternativas visando diminuir as emissões desses gases associadas a atividades antrópicas. Entre essas alternativas está a utilização de biocombustíveis, que no caso do Brasil é representado pelo etanol proveniente da cana-de-açúcar. Existe um debate sobre a magnitude da redução de emissões de GEE que tal opção de combustível representa. Fatores como mudança do uso da terra e fluxos de óxido nitroso (N2O) e metano (CH4) nas plantações de cana-de-açúcar, ainda estão sendo estudados. O propósito deste trabalho foi avaliar, com auxílio de modelagem computacional e sistemas de informações geográficas (SIG), as emissões de GEE associadas ao cultivo da cana-de-açúcar no estado de São Paulo, nos anos de 2003 e 2010, comparando os resultados com os obtidos a partir das diretrizes do \"Intergovernmental Panel on Climate Change\" (IPCC). Também foi avaliada a influência nos resultados quando os dois métodos são utilizados em diferentes escalas espaciais. O programa computacional de emissões utilizado foi o \"Denitrification Decomposition\" - DNDC. Inicialmente foram comparados valores de emissão simulados pelo programa com valores de um experimento com medição contínua desses gases numa plantação de cana-deaçúcar na região de Quensland - Austrália. Os resultados da simulação foram quantitativamente semelhantes aos obtidos no experimento no caso dos fluxos de N2O, e qualitativamente satisfatórios com relação aos fluxos CH4. As estimativas estaduais de emissões de N2O, obtidas através do programa DNDC foram significativamente maiores do que as obtidas pelas diretrizes do IPCC, em todas as escalas consideradas. Também foram observadas variações significativas entre as estimativas nas diversas escalas espaciais quando utilizado o programa computacional, o mesmo não sendo verificado quando utilizados os algoritmos do IPCC. Em ambos os casos também se notou um aumento na estimativa de emissões de N2O para o ano de 2010 em relação a 2003. A simulação computacional indicou que os fluxos de N2O e CH4 na cultura da cana-de-açúcar, são influenciados pelo tipo de solo e condições climáticas, sendo que tais fatores não são levados em consideração quando as estimativas são baseadas nos algoritmos do IPCC. / Currently the climate change issue caused by greenhouse gases (GHG) attracts great interest. Given the potential impacts that such changes might cause, option aiming to reduce emissions of these gases associated with anthropogenic activities are currently being sought. Among these options is the use of biofuels, which in the case of Brazil is represented by sugarcane ethanol. There is a debate about the magnitude of GHG emission reduction that this option represents. Issues like land use change and fluxes of nitrous oxide (N2O) and methane (CH4) on sugarcane plantations are still being investigated. The purpose of this work is to evaluate, with the assistance of computational modeling and geographic information systems (GIS), greenhouse gases emissions associated with the cultivation of sugarcane in the state of São Paulo, in the years 2003 e 2010, comparing the results with the ones obtained by the International Panel on Climate Change (IPCC) guidelines. The influence on the results when both methods are used at different spatial scales was also evaluated. The computer program used to simulate GHG emissions was the \"Denitrification Decomposition\" - DNDC. Initially, emissions values simulated by the computer program were compared with values obtained in an experiment with continuous measurements of such gases in a plantation of sugarcane in the region of Queensland-Australia. The simulation results were quantitatively similar to those obtained in the experiment in the case of N2O fluxes, and of a satisfactory quality with respect to CH4 fluxes. The statewide estimates for N2O emissions, obtained through the DNDC program were significantly greater than the ones obtained by the IPCC guidelines, at all scales considered. Significant variations between estimates were also observed at different spatial scales when using the computer program, the same thing was not observed when using IPCC algorithms. In both cases it was also notice an increase on the estimates of N2O emissions for the year 2010 compared to 2003. The computer simulation indicated that the flows of N2O and CH4 in sugarcane crops are influenced by soil types and climatic conditions, and these factors are not taken into account when estimates are based on the IPCC algorithms.

Os aspectos ambientais vêm ganhando importância para a gestão de grandes, e até mesmo, de pequenas empresas, que passaram a adotar práticas sustentáveis para atender às legislações governamentais, além de buscar eventuais retornos econômicos e mercadológicos. Assim, considerando este cenário, este estudo tem como foco a análise da emissão de gases de efeito estufa, partindo da premissa de que para minimizar esta emissão é necessário examinar todos os processos de extração, produção e transporte ocorridos ao longo da cadeia de suprimentos. Nesse sentido, este estudo tem como objetivo principal o desenvolvimento de uma metodologia para redução da emissão de tais gases em uma cadeia de suprimentos, utilizando tecnologias da automação e de informação. Para verificar sua efetividade, tal metodologia foi aplicada em uma cadeia de suprimentos de etanol, que teve suas emissões estimadas, avaliadas e aperfeiçoadas por meio do uso de um Sistema Inteligente de Navegação, que pretendia diminuir as distâncias rodadas e o consumo de combustível dos veículos usados na distribuição do produto. Os resultados obtidos nas simulações realizadas expõem a possibilidade de reduzir, em um cenário otimista, até 13,42% das emissões da cadeia analisada. / Environmental aspects are gaining importance for the management of big and small organizations. These have adopted environmental practices to meet government laws and to pursue economic and market returns. So, considering this scenario, this study focuses on the analysis of the emission of greenhouse gases, on the premise that to minimize this issue is necessary to examine all processes of extraction, production and transportation occurring along the supply chain. In this sense, this thesis has as main objective the development of a methodology that seeks to reduce the emission of greenhouse gases in a supply chain, using for this technologies of automation and information. To evaluate its effectiveness, the methodology is applied in an ethanol supply chain located in Brazil, which has its emissions estimated, evaluated and possibly optimized through the use of an intelligent navigation system during the distribution process. This technology intends to assist the vehicle\'s driver to find routes that minimize the distance traveled and to maintain an optimal speed set by the manufacturer to reduce the consumption of energy. The results obtained in the simulations show that the implementation of the methodology can reduce, in an optimistic scenario, up to 13.42 % of the greenhouse gases emissions of the ethanol SC analyzed.

Dentre os ecossistemas terrestres, o solo constitui um dos principais reservatórios de carbono (C). As práticas de preparo agrícola alteram esse compartimento, acelerando o processo de oxidação da matéria orgânica do solo, o que favorece a emissão de gases do efeito estufa. O presente trabalho foi desenvolvido em um experimento de longa duração localizado na Fundação ABC em Ponta Grossa (PR) sob diferentes sistemas de manejo do solo: plantio convencional (PC), preparo mínimo (PM), plantio direto (PD) e plantio direto escarificado (PDE), dispostos em blocos ao acaso. Os objetivos foram, determinar: a) os estoques de C e nitrogênio (N) do solo; b) a quantidade e qualidade dos resíduos culturais; e c) quantificar as trocas gasosas de CO2 e N2O entre o solo-atmosfera. As amostragens foram realizadas de outubro de 2003 a novembro de 2004 na sucessão aveia branca/soja/trigo. Os estoques de C e N do solo foram determinados após a colheita das culturas e não apresentaram diferença estatística entre épocas de cultivo e tratamentos. O PD apresentou os maiores estoques médios de C e N, e o PC os menores valores. As taxas de seqüestro de C, na camada 0-20 cm nos tratamentos estudados em comparação ao PC (15 anos de implantação), foram de: 0,55; 0,66 e 0,46 Mg ha-1ano-1 para PM, PD e PDE, respectivamente. As massas secas e os estoques de C e N dos resíduos culturais foram maiores na época da colheita das culturas, e superiores nos tratamentos PD e PDE. Os teores de C dos resíduos não tiveram diferença estatística entre as médias dos tratamentos. Os resíduos de soja apresentaram, em todos os tratamentos, maior teor de N e menor de hemicelulose. As variações no Quociente holocelulose/lignocelulose (QCL), Índices ligno-celulósico (ILC) e de decomponibilidade (ID) foram pequenas, evidenciando pouca variação entre os resíduos da rotação. As médias diárias das emissões de CO2 do solo variaram de 24 a 248 mg m-2 h-1 aumento progressivo, de novembro/03 (semeadura da soja) a fevereiro/04, devido ao crescimento das raízes que incrementou a taxa de respiração do solo. Não foi observada correlação significativa entre as emissões de CO2 e N2O com o ciclo diário da temperatura. As médias anuais de emissão de CO2 e N2O foram iguais nos horários 8:00, 12:00h e 17:00h. Os fluxos de N2O variaram de 3 a 53 &#181;g m-2, e a maior freqüência observada com saturação de água no solo em torno de 60%, após as adubações nitrogenadas em junho/2004 no PC e PM e em julho/2004 no PD e PDE. O revolvimento do solo pela gradagem e incorporação dos resíduos culturais no PC e PM, não alteraram significativamente as emissões de CO2 e N2O. Os tratamentos estudados não apresentaram diferença nas médias anuais de emissão de CO2 e N2O do solo. Dentre todas as variáveis estudadas, comparando os tratamentos PC, PM, PD e PDE, o PD destacou-se por apresentar maior estoques de C e N no solo em relação aos demais tratamentos. / Between the terrestrial ecosystems, the soil is one of the most important pools of carbon (C). Agricultural tillage practices alter the contents of this element, accelerating the process of organic matter oxidation, inducing greenhouse gases emissions. The present research was carried out in a long-term experiment located at Fundação ABC in Ponta Grossa (Paraná State, Brazil) under different soil management systems: conventional (CT), minimum (MT), no-till (NT) and no-till harrowed (NTH), randomly displayed in blocks. The objectives were to determine: a) soil C and nitrogen (N) stocks; b) quantity and quality crop residues; c) quantify the CO2 and N2O gasses fluxes from the soil to the atmosphere. Sampling activities were performed between October 2003 and November 2004 in the succession white oat/soybean/wheat. Soil C and N stocks were determined after the crops were harvested and showed the same distribution of soil C and N for all treatments, no significant statistically difference among cultural seasons and treatments was observed. NT system presented the highest mean soil C and N stock values, and the CT had the smaller values. Soil C sequestration rates in the 0-20 cm, in the treatments in comparison with the CT with 15 years of adoption, were 0,55; 0,66 and 0,46 Mg ha-1year-1 for MT, NT and NTH, respectively. Dry matter and C and N stocks of crop residues were higher in the harvest season, and presented high values for NT and NTH. Carbon contents in crop residues were maintained in the same magnitude and showed no significant statistically difference. Soybean residues just presented, in all treatments, higher N concentration and smaller hemicelulose contents. The holocelulose/lignocelulose quotient (HLQ), ligno-celulosico (LCI) and decomposition (DI) indexes were small, evidencing in this work, little variation between the crop residues analised. The soil CO2 CO2 daily average emissions varied from 24 to 248 mg m-2 h-1 and presented a progressive increase of November/03 (sow of the soy) to February/04, indicating that the soil respiration passed to be constituted of the organism soil and root plants. Correlation was not observed between the emissions of CO2 and N2O with the daily cycle of the temperature. The same annual averages of emission of CO2 and N2O were observed in the schedules 8:00, 12:00 and 17:00 hours. The N2O flow varied from 3 to 53 g m-2, and the largest frequency observed with water filled pore space around 60 %, and after the nitrogen fertilization in June 2004 in CT and MT and in July 2004 in NT and NTH. Soil tillage with plow and incorporation of the cultural residues in CT and MT, didn&#39;t alter the emissions of CO2 and N2O significantly. The studied treatments didn\'t present difference in the annual averages of emission of CO2 and N2O of the soil during 2003 and 2004 years. Between the studied variables, comparing the treatments CT, MT, NT and NTH, NT system stranded out from the other treatments by present higher soil C and N stocks.