O objetivo global deste trabalho foi fornecer subsídios para melhor compreender como as políticas públicas voltadas às emissões veiculares, incluindo o uso de etanol combustível, podem afetar a composição química da atmosfera. O peróxido de hidrogênio (H2O2) é um dos oxidantes mais importantes presentes na troposfera, podendo participar de reações com uma variedade de compostos orgânicos e inorgânicos. Neste trabalho, a determinação de H2O2, etanol, acetaldeído e outras espécies orgânicas e inorgânicas, foi realizada na fase gasosa, água de chuva e em águas superficiais. Foi utilizado de forma pioneira o método fluorimétrico baseado na formação do fluoróforo 2,7-diclorofluoresceína para determinar H2O2 em amostras de águas naturais (LD = 2 nmol L-1 e LQ = 7 nmol L-1). Enquanto outros métodos demandam a análise imediata da amostra, neste caso, o fluoróforo permanece estável por cerca de 48 h, facilitando as análises e o trabalho de campo. A concentração de H2O2 na água de chuva de Ribeirão Preto coletada de 2014 a 2017 variou entre 5,8 e 96 mol L1, com média ponderada pelo volume (MPV) de 28,9 ± 1,3 µmol L-1 (n = 88). Foi observado que a radiação solar foi um parâmetro mais importante na formação de H2O2 do que no seu consumo. Enquanto as concentrações MPV de sulfato (pH < 5) e nitrato na água de chuva decresceram em torno de 35% em 2017 com relação a 2014, as concentrações de H2O2 praticamente dobraram no mesmo período. A correlação negativa entre essas espécies evidencia que as políticas nacionais destinadas a reduzir as emissões veiculares podem alterar a capacidade oxidativa da atmosfera. As concentrações de H2O2, etanol e acetaldeído na fase gasosa em Ribeirão Preto (RP) e São Paulo (SP) foram determinadas, utilizando de forma pioneira no Brasil, o método de coleta do condensado. As concentrações de etanol na atmosfera de RP (15,0 ± 6,6 ppbv, n = 19) e SP (22,0 ± 9,4 ppbv, n = 10) foram relativamente próximas, apesar da frota veicular de SP ser ~ 16 vezes maior. Essas concentrações de etanol são cerca de 21 vezes maiores que aquelas relatadas nos Estados Unidos devido ao elevado uso de etanol combustível no Brasil. As médias das concentrações de H2O2 e acetaldeído na atmosfera foram, respectivamente, de 2,10 ± 1,46 e 16,3 ± 6,0 ppbv em RP; e 1,29 ± 0,62 e 14,4 ± 5,4 ppbv em SP. A avalição diurna mostrou que enquanto a concentração de H2O2 aumentou com a radiação solar, a concentração de etanol diminuiu numa taxa próxima da produção de acetaldeído. Esses resultados indicam que o H2O2 pode ser um oxidante importante de etanol a acetaldeído em fase gasosa, sendo este último de elevada toxicidade para o ser humano. Os fluxos na interface ar-água nos locais estudados em RP e SP mostram que o corpo dágua funcionou como um sumidouro de H2O2. Já o fluxo de etanol foi variável, isto é, ora invasivo e ora evasivo, com evidências de uma importante produção fotoquímica dessa espécie no meio aquático. / The main objective of this work was to provide insights to better understand how the public policies focused on vehicular emissions, including the use of ethanol fuel, can affect the chemical composition of the atmosphere. Hydrogen peroxide (H2O2) is one of the most important oxidants in the troposphere and it can participate in reactions with a variety of organic and inorganic compounds. In this work, determination of H2O2, ethanol, acetaldehyde and other organic and inorganic species was carried out in the gas phase, rainwater and surface water. The fluorimetric method based on the formation of the 2, 7-dichlorofluorescein fluorophore was applied for the first time to determine H2O2 in natural water samples (LOD = 2 nmol L-1 and LOQ = 7 nmol L-1). While other methods require the immediate analysis of the sample, in this case, the fluorophore remains stable for about 48 h, facilitating the analyzes and fieldwork. H2O2 concentrations in rainwater of Ribeirão Preto collected between 2014 and 2017 ranged from 5.8 to 96 mol L-1, with a volume-weighted mean (VWM) of 28.9 ± 1.3 mol L-1 (n = 88). The solar radiation was observed to be a more important parameter in the formation of H2O2 than in its consumption. While the VWM concentrations of sulfate (pH <5) and nitrate in rainwater declined by approximately 35% in 2017 compared to 2014, H2O2 concentrations virtually doubled over the same period. The negative correlation between these species shows that national policies aimed at reducing vehicle emissions may modify the oxidizing capacity of the atmosphere. Gas phase H2O2, ethanol and acetaldehyde concentrations in Ribeirão Preto (RP) and São Paulo (SP) were determined using, for the first time in Brazil, the method of condensate collection. Ethanol concentrations in the atmosphere of RP (15.0 ± 6.6 ppbv, n = 19) and SP (22.0 ± 9.4 ppbv, n = 10) were relatively close, although the SP vehicle fleet is ~ 16 times higher. These ethanol concentrations are about 21 times higher than those reported in the United States due to the high use of ethanol fuel in Brazil. The mean concentrations of H2O2 and acetaldehyde in the atmosphere were, respectively, 2.10 ± 1.46 and 16.3 ± 6.0 ppbv in RP; and 1.29 ± 0.62 and 14.4 ± 5.4 ppbv in SP. Daytime variation showed that while H2O2 concentration increased with solar radiation, ethanol concentration decreased at a rate close to the one of acetaldehyde production. These results indicate that H2O2 may be an important oxidant of ethanol to acetaldehyde in the gas phase, the latter being highly toxic to humans. Fluxes in the air-water interface at the studied sites in RP and SP show that the water body worked as an H2O2 sink. On the other hand, ethanol fluxes were variable, i.e., sometimes invasive and sometimes evasive, with evidence of an important photochemical production of this species in the aquatic environment.

O objetivo principal desta tese foi o de se desenvolver uma biocélula a combustível enzimática em microfluídica, utilizando a glicose como combustível e o oxigênio como oxidante. Foram utilizadas as enzimas Glicose Oxidase ou Glicose Desidrogenase em um bioânodo, de forma a promover reações bioeletrocatalíticas de oxidação da glicose e as enzimas Lacase ou Bilirrubina Oxidase, de forma a promover reações bioeletrocatalíticas de redução do oxigênio molecular. O trabalho se procedeu por tentativas de imobilizar estas enzimas, de forma a promover o mecanismo de transferência eletrônica direta com um eletrodo. Nas situações as quais isso não foi possível, foram utilizados mediadores eletrônicos, de forma a promover o mecanismo de transferência eletrônica mediada. O melhor par de sistemas de bioeletrodos e mediadores foi escolhido para serem aplicados em uma biocélula a combustível. O trabalho se procedeu em adaptar este par de bioeletrodos desenvolvidos para um sistema de microfluídica em papel, sendo ambos biocátodo e bioânodo em papel. Como as condições de concentração de combustível e de cofatores foram otimizadas para o bioânodo, foi necessário trabalhar com os biocátodos, de forma a apresentar as características de um biocátodo respirador, para melhor utilizar o oxigênio presente no ar e a apresentar um desempenho tão bom quanto o dos bioânodos. A biocélula a combustível em papel possibilitou a geração de energia elétrica por até 18 dias, utilizando uma resistência de 1.7 k&Omega;, nas condições experimentais ideais. De forma a provar o conceito da tecnologia para aplicações reais, a biocélula a combustível em papel foi demonstrada a ter a capacidade de geração de energia elétrica suficiente para fazer um relógio funcionar por pelo menos 36 horas, utilizando a bebida isotônica Gatorade&reg;, como combustível. / The main objective of this thesis is to develop a microfluidic biofuel cell using glucose as the fuel and oxygen as the oxidant. The enzymes Glucose Oxidase or Glucose Dehydrogenase were used in a bioanode to promove the bioelectrocatalytic oxidation of glucose and the enzymes Laccase or Bilirubin Oxidase to promove the bioelectrocatalytic reduction of the molecular oxygen. The work was conducted by attempts to immobilize these enzymes in order to promote the mechanism of direct electron transfer with the electrode. For the situations where this was not observed, mediators were used in a way to promote the mechanism of mediated electron transfer. The best pair of bioelectrodes and mediatores was chosen to be applied in a biofuel cell. The work was carried out to adapt this par of developed bioelectrodes to a paper based microfluidic system, using both biocathode and bioanode in a paper-like design. As the conditions for concentration of fuel and cofactors were optimized for the bioanode, it was necessary to work on these biocathodes so as to have the characteristics of an air-breathing biocathode for a better use of the oxygen present in the air and to work with a performance as good as the bioanode. The paper based biofuel cell enabled the generation of electricity for up to 18 days using a resistance of 1.7 k&Omega; within the optimum experimental conditions. In order to prove the concept of this technology for real applications, the paper based biofuel cell was demonstrated to have the capacity for generation of enough electrical energy to power up a clock for at least 36 hours using the isotonic drink Gatored&reg; as fuel.

Earth is exposed to an amount of energy that is fixed organically via photosynthesis and stored as fossil fuels, which are currently the major energy sources of humanity. Since Arrhenius concluded that carbon dioxide emissions from fossil fuels could lead to a climate warming, studies have sought ways to reduce human contribution on the environment to mitigate possible negative impacts on climate. The increasing world population is an obstacle for the efforts to reduce CO2 emissions and other greenhouse gases (GHG), because it demands more energy for transportation, electricity and heating. Among several renewable energy sources, biomass for fuels stands out, such as sugarcane ethanol in Brazil. Using biomass for fuels may help reducing the pressure on fossil fuels, besides, fixing organic carbon already emitted, contributing to mitigate problems of climate change and global warming. Thus, this study aims to analyse carbon cycles of mitigating emissions from fossil fuels with biofuel based on useful energy (exergy) content to determine the equivalent area required. Previous studies of life cycle assessment in sugarcane and eucalyptus were used to obtain carbon- and energy-flow data. These data were applied to estimate the available exergy to the final user through different routes of biofuel production, including current and evolving technologies. Exergy assessment demonstrated that on average, each Mg of biomass produced, led to a change of 3.02 GJ on sugarcane scenarios and 5.93 GJ on eucalyptus scenarios. Reducing sugarcane straw moisture from 50% to 30% increased the exergy output in 13.32 GJ ha-1, an increase of 0.67 GJ ha-1 for each 1% of moisture reduce. Eucalyptus to firewood, reducing moisture from 20% to 15% had an increase of 7.52 GJ ha-1 in the exergy output, representing 1.50 GJ ha-1 of increase for each 1%. This kind of assessment brings a new point of view in carbon mitigation, looking for its functionality. Biofuel use implications in environmental, social and economic aspects were also studied through a hybrid input-output life cycle assessment (IO-LCA) showing differences between the occupation of land use and two different ways of sugarcane production. The IO-LCA showed, in areas of land use change from pasture to sugarcane, energy consumption is increased by 3.7 times, employment is reduced by 5.4 times, and GHG emissions are reduced to only 2% of original emissions for each unit of R$ of final demand changed Most of the employment is generated by the sugarcane supply chain sector. Comparing sugarcane produced by the mills, it originates more direct full time jobs and probably in a more formal job market than sugarcane produced by farm suppliers. Farm suppliers use less energy and release less GHG than mills sugarcane production. / A energia à qual o planeta é exposto é fixada organicamente via fotossíntese e estocado na forma de combustíveis fósseis, atualmente, as maiores fontes energéticas da humanidade. Desde que Arrhenius concluiu que emissões de CO2 decorrentes de combustíveis fósseis, poderiam levar a um aquecimento do clima, até os dias atuais, estudos buscam formas de reduzir os impactos antrópicos de forma a atenuar possíveis problemas climáticos. Os esforços para a redução de emissões de CO2 e outros gases de efeito estufa (GEE) têm como obstáculo uma população mundial crescente, que demanda cada vez mais energia para transporte, eletricidade e calor. Dentre as possibilidades de uso de fontes renováveis de energia, a biomassa é uma que se destaca em alguns países, como no caso do uso de etanol de cana-de-açúcar no Brasil. O uso de biomassa para a produção de combustíveis auxilia na redução da pressão para o uso de mais combustíveis fósseis e fixa organicamente o carbono emitido, contribuindo duplamente para a mitigação de problemas com mudanças climáticas e aquecimento global. O presente trabalho analisa os ciclos de carbono em biocombustível, correlacionando-os com sua energia útil (exergia) valorando a equivalência em área para a produção da exergia equivalente de combustíveis fósseis através de uma nova metodologia de avaliação de mitigação. Foram utilizados trabalhos existentes de análise de ciclo de vida em cana-de-açúcar e eucalipto para obtenção dos dados de inventário e fluxos de carbono e energia. Realizaram-se cálculos de exergia disponível ao usuário final com diferentes rotas de produção de biocombustível, abrangendo tecnologias atuais e em desenvolvimento. Na avaliação exergética, reduzir a humidade da palha da cana de 50% a 30% aumentou a exergia disponível em 13,32 GJ ha-1, 0,67 GJ ha-1 para cada 1% de redução na humidade. No caso do eucalipto para combustão, reduzindo-se a umidade de 20% a 15% houve um aumento de 7,52 GJ ha-1, 1,50 GJ ha-1 para cada 1% de umidade. Em média, cada Mg de biomassa produzida aumentou 3,02 GJ em cenários de cana de açúcar e 5,93 GJ em cenários de eucalipto. Este conceito traz uma nova perspectiva na mitigação de carbono, avaliando-o por sua funcionalidade. Também foram estudadas as implicações do uso de biocombustíveis em aspectos ambientais, sociais e econômicos em uma análise híbrida de ciclo de vida e insumo-produto (ACV-IP) evidenciando diferenças entre ocupação do uso de solo e duas maneiras de produção de cana-de-açúcar. A ACV-IP demonstrou que, em áreas de mudança do uso do solo de pastagem para cana de açúcar, o consumo de energia aumenta em 3,7 vezes, o emprego é reduzido em 5,4 vezes, e as emissões de GEE são reduzidas à apenas 2% das emissões originais para cada unidade de R$ de alteração na demanda final. A maior parte do emprego é gerado pelo setor da cadeia de suprimentos de produção de cana. A cana produzida pelas usinas origina mais empregos diretos do que a cana produzida por fornecedores agrícolas. Fornecedores usam menos energia e emitem menos GEE do que a produção de cana por usinas.

In order to satisfy the global requirement for transport fuel sustainably, renewable liquid biofuels must be developed. Currently, two biofuels dominate the market; bioethanol for spark ignition and biodiesel for compression ignition engines. However, both fuels exhibit technical issues such as low energy density, poor low temperature performance and poor stability. In addition, bioethanol and biodiesel sourced from first generation feedstocks use arable land in competition with food production, and can only meet a fraction of the current demand. To address these issues it is vital that biofuels be developed from truly sustainable sources, such as lignocellulosic waste resources, and possess improved physical properties. To improve and control the physical properties of a fuel for specific application, one must be able to tailor the products formed in its production process. All studies within this thesis, therefore, have the aim of assessing the fuels produced for their variability in physical property, or the aim of directing the process considered to specific fuel molecules. In Chapter 2, spent coffee grounds from a range of geographical locations, bean types and brewing processes were assessed as a potential feedstock for biodiesel production. While the lipid yield was comparable to that of conventional biodiesel sources, the fatty acid profile remained constant irrespective of the coffee source. Despite this lack of variation, the fuel properties varied widely, presumably due to a range of alternative biomolecules present in the lipid. Though coffee biodiesel was produced from a waste product, the fuel properties were found to be akin to palm oil biodiesel, with a high viscosity and pour point. The blend level would therefore be restricted. In Chapter 3 the coffee lipid, as well as a range of microbial oils potentially derived from renewable sources were transformed into a novel aviation and road transport fuel through cross-metathesis with ethene. Hoveyda-Grubbs 2nd generation catalyst was found to be the most suitable, achieving 41% terminal bond selectivity under optimum conditions. Metathesis yielded three fractions: an alkene hydrocarbon fraction suitable for aviation, a shorter chain triglyceride fraction that upon transesterification produced a short chain biodiesel fuel, and a multifunctional volatile alkene fraction that could potentially have application in the polymer industry. Though there was variation for the road transport fuel fraction due to the presence of long chain saturates, the compounds fell within the US standard for biodiesel. The aviation fraction lowered the viscosity, increased the energy density, and remained soluble with Jet A-1 down to the required freezing point. Oleaginous organisms generally only produce a maximum of 40% lipid, leaving a large portion of fermentable biomass. In Chapter 4, a variety of ethyl and butyl esters of organic acids – potentially obtainable from fermentation – were assessed for their suitability as fuels in comparison to bioethanol. One product, butyl butyrate, was deemed suitable as a Jet A-1 replacement while four products, diethyl succinate, dibutyl succinate, dibutyl fumarate and dibutyl malonate, were considered as potential blending agents for diesel. Diethyl succinate, being the most economically viable of the four, was chosen for an on-engine test using a 20 vol% blend of DES (DES 20) on a chassis dynamometer under pseudo-steady state conditions. DES20 was found to cause an increase in fuel demand and NOx emissions, and a decrease in exhaust temperature, wheel force, and CO emissions. While fermentation is generally directed to one product, producing unimolecular fuels, they do not convert the entirety of the biomass available. An alternative chemical transformation is pyrolysis. In Chapter 5, zeolite-catalysed fast pyrolysis of a model compound representative of the ketonic portion of biomass pyrolysis vapour – mesityl oxide – was carried out. The aim of this study was to understand the mechanistic changes that occur, which could lead to improved bio-oil yields and more directed fuel properties of the pyrolysis oil. While HZSM-5 and Cu ZSM-5 showed no activity for hydrogenation and little activity for oligomerisation, Pd ZSM-5 led to near-complete selective hydrogenation of mesityl oxide to methyl isobutyl ketone, though this reduced at higher temperatures. At lower temperature (150-250 °C), a small amount of useful oligomerisation was observed, which could potentially lead to a selective pyrolysis oligomerisation reaction pathway.

As biocélulas a combustível proporcionam meios de se obter energia de maneira mais sustentável, limpa e renovável e apresentam grande potencial para serem usadas como fontes de energia alternativas para dispositivos eletrônicos de baixa demanda energética. Esta dissertação investiga a bioeletro-oxidação de etanol pela enzima Álcool Desidrogenase (ADH) empregando-se bioânodos com polimerização simultânea do mediador (poli - verde de metileno) e polímero condutor (polipirrol). Uma vez preparado o bioânodo foram realizados estudos para verificar a oxidação do cofator (NADH), formação do produto da bio-oxidação de etanol, estabilidade e também estudos visando aumentar a eficiência energética gerada empregando nanotubos de carbono para aumento de área eletroquímicamente ativa e melhor comunicação com os sítios ativos das enzimas. Foi também preparada uma biocélula completa sem membrana polimérica visando diminuir resistência de transferência de prótons do sistema, com a configuração final constituída de ADH/NAD+, etanol, Lacase/O2 com e sem MWCNT. O bioânodo se mostrou relativamente estável, apresentando um decaimento médio de 36% do valor inicial da densidade de potência após 20 semanas de estocagem. Quando operado em condição contínua (tempo = 4h, E (V)= ½ PCA), o decaimento foi de 39% e de 66% em 12 horas de operação. Os valores de densidade de potência foram melhorados com a adição de MWCNTs sobre o suporte de C antes da eletropolimerização do filme simultâneo, em pH 8,9, obteve-se 275 + 12 ?W cm-2. A eletrólise para este sistema mostrou a formação de acetaldeído com conversão de 18% de etanol. Para a biocélula completa, os melhores resultados foram com a presença de MWCNTs no bioânodo, obtendo-se uma potência de 12,5 +0,9 ?W cm-2. Os resultados obtidos são bastante promissores comparado com a literatura atual e mostram que esse sistema pode ser empregado para construção de BFC. / Biofuel cells provide the means to obtain energy in a more sustainable, clean, and renewable way and have great potential as alternative energy sources for low-energy electronic devices. This dissertation investigates ethanol bioelectrooxidation by the enzyme Alcohol Dehydrogenase (ADH) at bioanodes with simultaneous polymerization of the mediator (polymethylene green) and conductive polymer (polypyrrole). After preparing the bioanode, we investigated cofactor (NADH) oxidation, the ethanol biooxidation product,and bioanode stability. We also conducted studies to increase the generated energy efficiency by using carbon nanotubes to augment the electrochemically active area and to improve communication with the enzyme active sites. We also prepared a complete biofuel cell without polymer membrane to decrease the system proton transfer resistance: the final configuration consisted of ADH / NAD +, ethanol, Laccase , and O2 with or without MWCNTs. The bioanode was relatively stable. The mean decay was 36% of the initial power density after 20 weeks of storage. When the bioanode was operated in continuous condition (time = 4h, E (V) = ½ PCA), the decay was 39% and 66% in 12 hours of operation. The power density values increased upon addition of MWCNTs to the C-support before simultaneous film electropolymerization at pH 8.9, to give 275 + 12 ?W cm-2. Under electrolysis conditions, this system produced acetaldehyde and converted 18% of ethanol. For the complete biofuel cell, the best results were with the presence of MWCNTs in the bioanode, which provided a power of 12.5 +0.9 ?W cm-2. The results obtained here are quite promising if compared to the current literature and show that this system can be used to construct a BFC.

Land use change is a major driver of species loss worldwide, the extent and intensity of agricultural land use poses particular pressures for biodiversity and the ecosystem services it provides. In recent years, agroecosystems have seen the introduction of 2nd generation bioenergy crops in order to tackle anthropogenic climate change, providing a renewable alternative to fossil fuels. In this thesis I study the impact of cultivating two commercial perennial energy crops (PECs), Miscanthus x giganteus and willow short-rotation coppice, when compared to the cereal crops they replace. I investigate processes relevant to the provisioning of pollination and decomposition services and explore patterns of soil element bioaccessibility alongside analyses of the similarity and diversity of soil bacterial communities. When compared to cereals, I find a consistent increase in pollinator (hoverfly, bumblebee and butterfly/moth) wildflower visitation in the margins of willow but not Miscanthus. In Miscanthus, opposing trends arose for different pollinator taxa: butterflies/moths were more frequent flower visitors in Miscanthus margins than cereal margins, while hoverfly flower visits were most frequent in cereal margins. Furthermore, the availability of margin wildflowers was enhanced in willow but not Miscanthus and the seed set of margin phytometers was similar between Miscanthus and cereals. Cultivation of willow, in particular, may therefore yield local conservation benefits for both wildflowers and pollinators. However, there was no evidence for enhancement of pollinator activity in cereals adjacent to either PEC, indicating that the strategic cultivation of these crops is unlikely to enhance pollinator service provision in the wider agri-environment. For investigated soil elements, bioaccessibility in PECs did not differ significantly to cereal controls, and denaturing gradient gel electrophoresis (DGGE) revealed no difference in the diversity of bacterial communities. Similarly, DGGE fingerprint patterns did not indicate the development of crop specific assemblages, demonstrating that the mobility of soil elements and structure of bacterial communities were principally determined by factors other than the identity of the crop cultivated. Investigation of meso-microfaunal decomposition rates in Miscanthus using litter bags demonstrated an impact on decomposition processes, with a significant increase in winter decomposition rates in the PEC when compared to cereals.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2017-07-21T11:00:40Z No. of bitstreams: 2 Dissertação - William Rodrigues Martins - 2016.pdf: 595784 bytes, checksum: 3a2ef59ef753e50f8bafcc9b780fa57f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-07-21T11:01:10Z (GMT) No. of bitstreams: 2 Dissertação - William Rodrigues Martins - 2016.pdf: 595784 bytes, checksum: 3a2ef59ef753e50f8bafcc9b780fa57f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-07-21T11:01:10Z (GMT). No. of bitstreams: 2 Dissertação - William Rodrigues Martins - 2016.pdf: 595784 bytes, checksum: 3a2ef59ef753e50f8bafcc9b780fa57f (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-03-01 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The objective of this work was to verify the volumetric production per area, the growth in height and diameter at breast height (DBH) in hybrid of Eucalyptus urophylla x E. grandis W. Hill., in reduced different planting spacings in southwest Goiás. The work was implemented in the Experimental Farm of the Federal University of Goiás, Regional Jataí (UFG / REJ), town of Jataí-GO, following the assumptions of completely randomized design, with three hybrids, two treatments for hybrid treatments and three replications, totaling 18 plots with 50 seedlings per plot. The hybrids were AEC1528, I144 and GG100 and the evaluated spacings were 3.0 m x 0.5 m and 3.0 m x 1.0 m. At 33 months of age tree were collected for the volume analysis, growth in height and diameter. The spacing of 3.0 m x 0.5 m in energy forests, affect the individual growth for both diameter and height, as to volume. The differentiation of hybrids was in height and production, where I144 hybrid gained greater prominence. The greatest expression in volume production, for wood with bark, not bark and bark volume was observed for 3.0 m x 0.5 m spacing. / Objetivou-se com este trabalho verificar a produção volumétrica por unidade de área, o crescimento em altura e diâmetro a altura do peito (DAP) em povoamentos de híbridos de Eucalyptus urophylla x E. grandis W. Hill., em diferentes espaçamentos reduzidos de plantio no sudoeste goiano. O trabalho foi implantado na Fazenda Experimental da Universidade Federal de Goiás, Regional Jataí (UFG/REJ), Município de Jataí-GO, seguindo os pressupostos do delineamento inteiramente casualizado, com seis tratamentos, e três repetições, totalizando 18 parcelas, com plantio de 50 mudas por parcela. Os híbridos avaliados foram o AEC1528, I144 e GG100 e os espaçamentos avaliados foram 3,0 m x 0,5 m e 3,0 m x 1,0 m. Assim observou-se aos 33 meses de idade que os crescimentos em diâmetro e altura são diretamente afetados pelo adensamento das plantas, e consequentemente com a redução da área útil disponível para cada planta. Os espaçamentos de 3,0 m x 0,5 em florestas energéticas afetam o incremento individual, tanto para diâmetro e altura, quanto para volume. A diferenciação dos híbridos ocorreu para o incremento em altura e produção, onde o híbrido I144 destacou-se. A maior expressão na produção volumétrica, para a madeira com casca, sem casca e o volume de casca foi observada para o espaçamento 3,0 m x 0,5 m.

A cana-de-açúcar e uma das principais atividades econômicas do Brasil, tanto em termos de balança comercial, como de geração de empregos. O álcool (etanol) obtido da cana-de-açúcar e um combustível menos poluente, pois, contem oxigênio na sua composição e utilizado nos veículos movidos a etanol, na composição da gasolina automotiva e nos veículos ex. A queima do etanol produz 25% menos monóxido de carbono e 35% menos oxido de nitrogênio que a gasolina. Desta forma, as nações preocupadas em diminuir seus nesses de poluição atmosférica têm considerado como uma importante solução viável, a adoção do etanol como combustível automotivo . O objetivo deste trabalho foi apresentar propostas para a melhoria da qualidade e produtividade do setor, focado no desempenho dos processos e produtos, atraves de métodos estatísticos. Foi utilizada a metodologia \"Lean Seis Sigma\" aplicada no processo produtivo do etanol, em uma usina de açúcar e de álcool, visando acelerar a velocidade do processo, através da redução do desperdício e da variabilidade. A aplicação da metodologia \"Lean Seis Sigma\" foi realizada com o uso do modelo DMAIC (Dene, Measure, Analyze, Improve, Control). A ferramenta utilizada para descrever a relação entre as variáveis de saída (Y) e as variáveis de entrada (X) foi a regressão linear múltipla, fazendo uso dos métodos de seleção de variáveis. O mapeamento do processo produtivo do etanol possibilitou a identificação das etapas que agregam e não agregam valor ao processo. Os resultados mostraram uma redução significativa no \\Lead Time\" (tempo do processo) e a identificação das principais variáveis envolvidas no processo produtivo do etanol / The sugarcane is one of the most important economic businesses in Brazil, in both terms of trade balance and job opportunity. Alcohol (ethanol), obtained from sugarcane, is a fuel cleaner, because it contains oxygen in its composition and is used in vehicles powered by ethanol, on the composition of automotive gasoline and ex-fuel vehicles. Ethanol burning produces 25% less carbon monoxide and 35% less nitrogen oxide than gasoline. Thus, the nations that concern on reducing their levels of air pollution consider it as an important and available solution to be adopted as an automotive fuel. So, this trial aimed at making some proposals for improving quality and productivity of this sector, focused on the performance of processes and products, according to some statistical methods. The studied methodology was Lean Six Sigma, applied in the production process of ethanol, in a sugar and alcohol Plant in order to speed up its process by reducing waste and variability. The Lean Six Sigma methodology was carried out using the DMAIC model (Dene, Measure, Analyze, Improve and Control). The multiple linear regression tool described the relationship among the output variables (Y) and the input variables (X), associated to the methods of variable selection. The mapping of ethanol production process enabled the identication of steps that add, and does not add value to the process. The results showed a signicant reduction in the Lead Time as well as to identify the main variables involved in the production process of ethanol.

Parmi les technologies basées sur H2 comme vecteur d’énergie, les biopiles à combustibles utilisant des enzymes comme biocatalyseurs spécifiques et efficaces au lieu des catalyseurs au platine apparaissent comme des alternatives émergentes. L’objectif de cette thèse est de comprendre les paramètres gouvernant l’immobilisation fonctionnelle sur des interfaces nanostructurées d'enzymes spécifiques de l’oxydation de H2 et de la réduction d’O2 en vue de désigner une biopile H2/O2 performante.Divers nanomatériaux sont caractérisés, nanoparticules d’or (AuNP) et nanotubes de carbone (CNT), présentant différentes tailles et chimie de surface, aptes à développer des ratios importants surface/volume, autorisant une augmentation du nombre de molécules enzymatiques incorporées et donc une augmentation des courants catalytiques. L’immobilisation des enzymes sur AuNP a permis de discriminer entre l’augmentation de surface ou un effet nano sur l’efficacité catalytique. L’étude intégrée sur CNT, avec les charges de l’interface électrochimique, les charges et moments dipolaires des enzymes considérées, a permis de démontrer que les interactions électrostatiques contrôlent le processus de transfert d’électrons. Cette étude montre que les bases moléculaires pour une immobilisation efficace des enzymes, obtenues sur monocouches est applicables aux réseaux 3D.La détermination des nanostructures optimales pour les réactions enzymatiques est étudiée pour un changement d’échelle. Ainsi des feutres de carbone sont fonctionnalisés avec les nanostructures adaptées, pour au final développer la première biopile H2/O2 capable d’alimenter un multicapteur et un système de communication sans fil. / Among the technologies based on H2 as an energy carrier, biofuel cells that use specific and effective enzymes as biocatalysts instead of platinum catalysts appear as emerging alternative. The objective of this thesis is to understand the parameters governing the functional immobilization of specific enzymes for H2 oxidation and O2 reduction reactions on nanostructured interfaces, aimed to design a performant H2 / O2 biofuel cell.Gold nanoparticles (AuNP) and carbon nanotubes (CNT) having different sizes and surface chemistry are characterized. These nanomaterials develop important ratios surface / volume ratio, allow an increment in the number of enzyme molecules immobilized and therefore an increase catalytic currents. The immobilization of enzymes on AuNP allowed the discrimination between the increase in surface area and a nanomaterial effect on catalytic efficiency. The study on CNT integrates the charge of the electrochemical interface, dipole moments and the surface charge of enzymes. It demonstrated that electrostatic interactions control the electron transfer process. This study shows that the molecular basis for effective immobilization of enzymes, obtained on monolayers is applicable to 3D networks.The determination of the best parameters for enzymatic reactions, allows the development of an optimized 3-D volumetric interface based on carbon felt. We finally design for the first time a H2/O2 biofuel cell able to generate enough electric power to feed a complete wireless communication device.

Ces dernières années, nous assistons à une prise de conscience généralisée de l'importance des impacts de notre mode de vie sur l'environnement, particulièrement en ce qui concerne le réchauffement global. L'objectif des politiques environnementales actuelles est le passage à des productions et des consommations durables qui passent par l'amélioration des performances énergétiques et environnementales des processus de production. De manière à réaliser cet objectif, la méthode de l'analyse du cycle de vie constitue à l'heure actuelle la méthode d'évaluation environnementale la plus largement utilisée. Cette méthode est ici appliquée dans le cadre de la production d'énergie renouvelable (électricité, chaleur, énergie motrice d'un véhicule) à partir de la biomasse d'origine agricole et forestière. Trois filières sont envisagées: la biométhanisation par fermentation d'effluents d'élevage et de cultures énergétiques, le bois énergie, et les biocarburants liquides purs et en mélange (5 % en volume) avec des carburants classiques (huile de colza, ester méthylique d'huile de colza, éthanol, éthyl tertio butyl éther). Il est prouvé que les énergies renouvelables participent à la réduction des impacts sur le réchauffement global et sur la diminution des ressources fossiles. Le présent travail apporte des éléments originaux sur plusieurs points. Outre ces deux aspects et au travers de trois méthodes d'analyse (CML 2 BASELINE 2000, ECOINDICATEUR 99 et IMPACT 2002+), d'autres catégories d'impact sont analysées de manière à fournir une information la plus complète possible sur la charge environnementale des filières étudiées. Les productions d'énergie des différentes filières considérées sont comparées avec des filières classiques utilisant des ressources fossiles pour un ensemble de charges environnementales en concordance avec la méthodologie de l'analyse du cycle de vie. Les méthodes d'analyse d'impact évoquées ci-dessus sont introduites successivement pour les comparaisons de chacune des filières avec les filières classiques. Afin de vérifier si le résultat environnemental obtenu est robuste à la méthode d'analyse d'impact, les trois filières utilisant la biomasse sont comparées entre elles avec les trois méthodes d'analyse d'impact. Compte tenu des résultats d'analyse d'impact, nous analysons si l'incertitude globale sur le résultat permet de considérer que les productions énergétiques comparées sont significativement différentes d'un point de vue environnemental. Les résultats montrent de manière générale, que les filières biométhanisation, bois énergie et biocarburants sont plus intéressantes que les filières classiques d'un point de vue environnemental global. L'application des trois méthodes d'analyse d'impact a permis de montrer que le choix d'une méthode n'est pas anodin et que les résultats peuvent être sensiblement différents en utilisant l'une ou l'autre des méthodes. La comparaison entre elles des trois filières montre que, pour des valorisations énergétiques analogues (production de chaleur en chaudière par exemple), la production énergétique par la filière biométhanisation est plus intéressante que la valorisation de l'huile (scores environnementaux de la production de chaleur en chaudière par la méthode IMPACT 2002+: 4,15.10-6 pt pour la chaudière au biogaz et 8,55.10-6 pt pour la chaudière fonctionnant à l'huile de colza). Le niveau de classement de la production énergétique de bois va dépendre des hypothèses retenues sur la gestion des cendres et sur le contrôle ou non des émissions. Les résultats d'analyses d'incertitude réalisées systématiquement montrent que l'incertitude globale est dans certains cas importante et ne permet pas de différencier de manière significative les systèmes de produits. Les différentes informations présentées dans cette étude constituent cependant autant d'éléments d'analyse objectifs dans le cadre d'un processus de décision qui concernerait le développement futur des filières étudiées./ Last few years, we attend a generalized awakening of our way of life influence to environmental impacts, particularly with regard to the global warming. The goal of the current environmental policies is the conversion to sustainable consumption and productions, making necessary the improvement of energy and environmental performance. To carry out this goal, the life cycle assessment is at present, the most largely used environmental assessment method. This method is applied in this study within the framework of the renewable energy (electricity, heat, mechanical energy in a vehicule) production from agricultural and wood biomass. Three reactor systems are considered: The co-fermentation of breeding effluents and energy crops, the wood fuels, the neat and blended (5 % volume) biofuels with fossil fuels. The biofuels considered are: rapeseed oil, rapeseed oil methyl ester, ethanol from wheat and sugar beet and ETBE (ethyl tertio butyl ether). It is proven that renewable energies take part in the global warming mitigation and in the reduction of the fossil resources depletion. The present work brings original elements on several points. In addition to these two impact categories and through three assessment methods (CML 2 BASELINE 2000, ECOINDICATOR 99 and IMPACT 2002+) we approach other impact categories in order to provide the most complete information on the environmental load of the studied reactor systems. The energy productions of the various reactor systems considered are compared with conventional reactor systems using fossil fuels for a whole of environmental loads, in agreement with the life cycle assessment methodology. The impact assessment methods cited above are introduced successively for each reactor system comparison with the traditional ones. In order to check if the environmental result obtained is robust with the impact assessment method, the three reactor systems using biomass are compared between each other with the three impact assessment methods and the results are analyzed. Taking into account the impact assessment results, we analyze if the global uncertainty on the result makes it possible to consider that the compared energy productions are significantly different from an environmental point of view. The impact assessment results show in a general way, that the reactor systems considered are more interesting from a global environmental point of view than the traditional ones. The application of the three impact assessment methods shows that it does matter which method one choose and that the results can be sensitive to the method used. The three reactor systems comparison shows that for similar energy development (heat production in a boiler for example), the energy production by using biogas from fermentation is more interesting than the energy production from rapeseed oil (IMPACT 2002+ scores for boiler heat production: 4,15.10-6 pt for the biogas boiler and 8,55.10-6 pt for the rapeseed oil boiler). The classification of wood energy production will depend on the assumptions retained on ashes management and on the emissions control. The results of uncertainty analysis carried out systematically show that the global uncertainty is in some cases important and does not allow to differentiate significantly the compared product systems. The various information highlighted in this study however constitutes as many objective elements of analysis within the framework of a decision-making process which would relate to the future development of the studied reactor systems.