Desde o primeiro choque do petróleo, em 1973, os países têm despendido esforços para reduzir sua dependência pelo produto, produzido principalmente em regiões politicamente instáveis. Os Estados Unidos são os maiores consumidores mundiais do combustível, e cerca de 70% são destinados ao transporte. Desde o final da década de 70, o governo americano tem incentivado o uso de etanol como substituto parcial da gasolina. No entanto, o crescimento do biocombustível levantou polêmicas porque a matéria-prima utilizada na sua produção no país é o milho, o que poderia estar afetando a oferta do grão para a produção de alimentos. Dessa forma, foi aprovado em 2007 o RFS2, uma legislação que prevê o consumo mandatório de volumes crescentes de etanol até 2022, mas limita a produção a partir de milho. Os investimentos em pesquisas de combustíveis alternativos passaram a se focar no desenvolvimento de etanol de segunda geração, que utiliza material celulósico como matéria-prima. Sua viabilidade técnica já foi confirmada, mas ainda são necessárias melhorias no processo de produção para que o produto possa ser ofertado em escala comercial. Por outro lado, o Brasil tem uma indústria de etanol madura e também tem feito pesquisas na tecnologia de segunda geração. Se bem sucedida, o país tem planos de exportar o excedente de produção, e os Estados Unidos são um mercado de interesse. O objetivo desta dissertação é auxiliar na avaliação das necessidades de os Estados Unidos importarem etanol de outros países, o que pode criar uma oportunidade para o Brasil. Para isso, foi utilizada a abordagem lógico-intuitiva de construção de cenários - voltada a aspectos qualitativos - para estudar o mercado de etanol combustível nos Estados Unidos até o ano de 2022. A coleta de informações foi feita por meio da revisão bibliográfica, focada em artigos internacionais. A política energética americana e a evolução da tecnologia de segunda geração de etanol foram identificadas como as principais incertezas que devem moldar o futuro do mercado em estudo. A partir delas, foram gerados quatro cenários, nomeados como \"Filho pródigo\", \"Pais esperançosos\", \"Filho independente\" e \"Filho preterido\". Concluiu-se que, enquanto o governo americano continuar incentivando o consumo de etanol, haverá boas oportunidades de exportação do biocombustível brasileiro. Os maiores volumes são esperados em \"Pais esperançosos\". Por outro lado, caso outras alternativas energéticas sejam priorizadas, nossas exportações podem reduzir substancialmente, e o volume comercializado dependerá do preço do nosso produto em relação ao deles e à gasolina. / Since the first oil shock in 1973, countries have made efforts to reduce their dependence on the product, mainly produced in politically unstable regions. The United States is the world\'s largest consumer of the fuel, and about 70 % is allocated to transport. Since the late 70s, the U.S. government has encouraged the use of ethanol as a partial substitute for gasoline. However, the growth of the biofuel arose controversy because the raw material used for the domestic production is corn, which could be affecting the supply of the grain for food production. Thus, it was approved in 2007 the RFS2, a legislation that requires mandatory use of increasing volumes of ethanol until 2022, but limits production from corn. Investments in alternative fuels research started to focus on the development of second generation ethanol, which uses cellulosic material as feedstock. Its technical feasibility has been confirmed, but improvements are still needed in the production process so that the product can be offered on a commercial scale. On the other hand, Brazil has a mature ethanol industry and is also doing research on second-generation technology. If successful, the country plans to export the surplus production, and the United States is a market of interest. The objective of this thesis is to assist the assessment of the United States needs to import ethanol from other countries, which may create an opportunity for Brazil. The logical-intuitive approach of scenario building - focused on qualitative aspects - was used to study the market for fuel ethanol in the United States until the year 2022. Data collection was done through literature review, focused on international articles. The U.S. energy policy and developments in the technology of second generation ethanol were identified as the major uncertainties that are shaping the future of the market under study. Four scenarios were generated from these two uncertainties and named as \"Prodigal Son\", \"Hopeful parents\", \"Independent Son\" and \"Deprecated Son\". It was concluded that while the U.S. government continues to encourage the consumption of ethanol, there are good opportunities to export the Brazilian biofuel. The largest volumes are expected in \"Hopeful parents\". On the other hand, if other energy alternatives are prioritized, our exports can reduce substantially, and sales volume will depend on the price of our product relative to theirs and gasoline.

This study presents an experimental investigation into the effects of running biodiesel fuel blends on conventional diesel engines. Bio fuels provide a way to produce fuels without redesigning any of the engine technology present today, yet allowing for green house emissions to decrease. Bio-diesel is one of these types of emerging bio-fuels, which has an immediate alternative fuel aspect to it, while providing a decrease in green house emissions, as well as a solution to recycling used Waste Vegetable Oils which are other wise disposed. This study shows how by blending bio-diesel with petroleum diesel at intervals of B5, B10, B15, and B20 decrease green house emissions can significantly while maintaining similar performance output and efficiency with respect to 100% petroleum diesel. / by Sergio Bastiani. / Thesis (M.S.C.S.)--Florida Atlantic University, 2008. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2008. Mode of access: World Wide Web.

O problema da poluição do ar se constitui em uma das mais graves ameaças à qualidade de vida de homens, animais, vegetais e a todo ambiente. O aumento da concentração de poluentes atmosféricos é gerado devido à crescente urbanização e ao aumento da frota de veículos automotores, principalmente. As emissões causadas por veículos carregam diversas substâncias tóxicas como: monóxido de carbono (CO), óxidos de nitrogênio (NOx), compostos orgânicos voláteis (COV), hidrocarbonetos policíclicos aromáticos (HPA) e outros que produzem vários efeitos negativos sobre a saúde. Tendo em vista essa situação, o objetivo deste trabalho foi a análise de gases poluentes emitidos por motores por Cromatografia Gasosa de Alta Resolução (CGAR). Foram analisados compostos orgânicos voláteis (benzeno, tolueno, etilbenzeno, o-xileno, m-xileno e p-xileno) nas emissões de motores empregando diesel de petróleo como combustível, B10 e etanol. Para estes combustíveis, compararam-se os teores dessas emissões (substâncias poluentes) variando-se alguns parâmetros dos motores. Também, foram feitas determinações dessas substâncias tóxicas nas emissões de motores empregando etanol como combustível. Nas emissões deste tipo de motor variando-se os parâmetros qualidade da mistura e rotação detectou-se benzeno na concentração 0,129 &#177 0,021, 0,124 &#177 0,020 e 0,132 &#177 0,007 &#956g/mL (mistura rica, estequiométrica e pobre, respectivamente); 0,134 &#177 0,017, 0,129 &#177 0,007 e 0,133 &#177 0,044 &#956g/mL (1700 rpm, 2200 rpm e 2700 rpm, respectivamente) que podem ser provenientes do óleo lubrificante. Em geral, para o motor de ignição por compressão, comparando-se as emissões tanto por diesel de petróleo como com mistura B10 observou-se uma redução significativa nas emissões dos poluentes aromáticos quando se emprega a mistura B10. Principalmente, para o benzeno, notou-se diminuição nas concentrações de até 24,5%. Apesar de ter obtido um valor de concentração abaixo de 1 &#956g/mL tanto na utilização do diesel quanto na de B10, esta redução é extremamente significante, por ser o benzeno, um composto carcinogênico. Além disso, a adição de biodiesel ao diesel mostrou-se eficiente na redução das emissões de poluentes. / Air pollution\'s is one of the most serious environment problems concerning human animals and vegetables life. The increase of concentration of atmospheric pollutants is generated mainly due to increasing urbanization and the increase on the number of motor vehicles. The emissions caused by vehicles contain several toxic substances as: carbon monoxide (CO), nitrogen oxides (NOx), volatile organic compounds (VOC), polycyclic aromatic hydrocarbons (PAH) and others substances ending quite negative effect on health. Considering this situation, this study described the procedures of analysis of pollutant gases emitted by engines, such as volatile organic compounds (benzene, toluene, ethilbenzene, o-xylene, m-xylene and p-xylene) by using High Resolution Gas Chromatography (HRGC) applied to diesel, B10 mixture, and ethanol emissions analysis. Considering the use of diesel and B10 as fuel, a comparative studies has been performed for fossil fuel (diesel) and biodiesel by varying some parameters of the engines. Also, determination of these toxic substances in the emissions of engines had been made using ethanol as fuel. In the emissions of this type of engine varying the parameters as mixture quality and rotation had been detected benzene at concentration values 0,129 &#177 0,021, 0,124 &#177 0,020 e 0,132 &#177 0,007 &#956g/mL (rich, stoichiometry and lean mixture); 0,134 &#177 0,017, 0,129 &#177 0,007 e 0,133 &#177 0,044 &#956g/mL (1700 rpm, 2200 rpm and 2700 rpm, respectively) that can be proceeding from the lubricant oil. In general, for CI engine burning diesel or B10 mixture it has been observed drastically reduction in the emissions of the aromatic compounds by using B10. Especially for benzene the reduction of concentrations occurs on the level of about 24.5%. Although, it has obtained a concentration value below 1 &#956g/mL as much as in the using diesel and B10, this reduction is, extremely significant, to being benzene a carcinogenic compound. Moreover, the addition of biodiesel to the diesel has been showed efficient in the reduction of the pollutants emissions.

Chosen as one of six Generation‒IV nuclear-reactor concepts, SuperCritical Water-cooled Reactors (SCWRs) are expected to have high thermal efficiencies within the range of 45 ‒ 50% owing to reactor‘s high outlet temperatures. A generic pressure-channel (or pressure-tube)SCWR operates at a pressure of 25 MPa with inlet- and outlet-coolant temperatures of 350°C and 625°C. Consequently, the sheath and fuel centerline temperatures are higher in SCWRs than those of the current nuclear reactors. Previous studies have shown that the sheath and fuel centerline temperatures could exceed the design and industry accepted limits of 850°C and 1850°C, respectively. These studies correspond to UO2 enclosed in a 43-element fuel bundle at an average thermal power per channel of 8.5 MWth. Additionally, these high operating conditions in the range of 350 - 625°C lead to high heat losses from the coolant to the moderator, which in turn reduces the overall thermal efficiency of the Nuclear Power Plant (NPP). Therefore, there is a need for alternative fuels or fuel bundles for future use in SCWRs. Hence, it is also necessary to determine the amount of heat losses from a number of fuel-channel designs for SCWRs. The objectives of this study are to investigate the possibility of using alternative fuels and to determine the heat losses from a fuel-channel design at SCWR conditions. The investigated fuels are categorized as low thermal-conductivity (e.g., UO2, MOX, and ThO2), high thermal-conductivity (e.g., UC, UC2, UN), and enhanced thermal-conductivity (e.g., UO2‒SiC, UO2‒C, and UO2‒BeO) fuels. Additionally, the examined fuel channel is the High Efficiency Channel (HEC), which has been designed by the Atomic Energy of Canada Limited (AECL) for the proposed CANDU SCWR. In order to achieve the objectives of this study, a steady-state one-dimensional heat-transfer analysis was conducted. The MATLAB© and NIST REFPROP© software were used for programming and retrieving thermophysical properties of a light-water coolant, respectively. The fuel centerline temperature was calculated for the fuel channels with the maximum thermal power, i.e., +15% above average channel power. Results of this analysis showed that the fuel centerline temperatures of low thermal-conductivity fuels exceed the industry limit; therefore, either a fuel with a higher thermal conductivity should be used or the fuel bundle geometry must be modified. Among the high thermal-conductivity fuels, UC has been shown to be a candidate for future use in SCWRs. However, the chemical compatibility of UC with water at high operating temperatures of SCWRs remains ambiguous. Therefore, further studies are required before selecting UC. In regards to enhanced thermal-conductivity fuels, UO2‒BeO is the most suitable candidate; however, its mechanical and neutronic properties must be thoroughly studied before any decision is made with regards to the selection of a fuel. In regards to the heat losses from the examined fuel channel, the heat loss was between 70 kW and 110 kW per fuel channel based on an average thermal power per channel of 8.5 MWth and a moderator pressure of 0.1 MPa at 80°C. A sensitivity analysis of the fuel channel shows that the heat loss can be reduced by increasing the operating pressure of the moderator, which in turn allows for increasing the operating temperature of the moderator. Higher operating temperatures of the moderator result in smaller temperature differences between the coolant and the moderator, which leads to lower heat losses. Therefore, either the thickness of the insulator or the pressure of the moderator should be increased in order to reduce the heat losses from the fuel channel. / UOIT

Alternative fuels are becoming important due to diminishing fossil fuel reserves and the environmental hazards associated with exhaust gases. Biodiesel is an attractive alternative fuel because it is environmentally friendly and can be synthesized from edible/non-edible oils. Though several methods are available for synthesis, transesterification is the preferred route for biodiesel synthesis. The current techniques for transesterification of the oils to biodiesel are based on acid/alkali catalysis. However, these methods do not work for oils with high free fatty acid content and also require an additional downstream step for separation of catalyst from the product. In this work, we investigate the synthesis of biodiesel by two techniques: in supercritical methanol and ethanol without any catalyst; in supercritical carbon dioxide using enzyme as catalyst. In the first technique, the transesterification of refined grade edible oil like sunflower oil, palm oil and groundnut oil, and crude non-edible oils like Pongamia pinnata and Jatropha curcas was investigated in supercritical methanol and ethanol without using any catalyst from 200 oC to 400 oC at 200 bar. The variables affecting the conversion during transesterification, such as molar ratio of alcohol to oil, temperature and time were investigated in supercritical methanol and ethanol. The conversion to biodiesel increased from 30-40% at a molar ratio of 10 to 80-85% at a molar ratio of 45 to 50. Very high conversions (96-97%) were obtained in supercritical methanol and ethanol within 30 minutes at 350 oC. The kinetics of the reaction was modeled, the rate coefficients and activation energies were determined. As an enzymatic transesterification in organic solvents is mass transfer limited, supercritical fluids are found to be a better alternative because of their gas like diffusivity. Among potentially interesting solvents for enzymatic synthesis, carbon dioxide is the most obvious choice in supercritical fluids, because it is non-toxic, nonflammable and easily available. Because the products and the enzyme do not dissolve in carbon dioxide at room conditions, separation can easily be achieved by reduction of pressure Thus, the enzymatic transesterification for production of biodiesel in supercritical fluids under mild conditions is of commercial interest. Therefore, biodiesel was synthesized using immobilized enzyme (Lipase, Novozym-435) in supercritical carbon dioxide. The effect of reaction variables like temperature, molar ratio, enzyme loading and kinetics of the reaction was investigated. The conversion to biodiesel was found to be lower in supercritical carbon dioxide than that in supercritical alcohol.

The first chapter of this dissertation examines welfare impacts of a combination of subsidies to alternative fuels (AFs) and alternative fuel vehicles (AFVs), and how they compare to gasoline taxes. The particular AF examined here is ethanol that is produced from agricultural products in a small open economy. The model in this paper characterizes a country or state where gasoline is the major source of fuel for automobiles, but that also produces and consumes ethanol as an AF. Gasoline combustion is polluting and its use equals the total amount of emissions produced. Thus, a gasoline tax here is the same as an emissions tax and is the most direct environmental instrument. However, increasing gasoline taxes for pollution purposes is often politically not feasible. Thus, this paper studies how closely subsidies to alternative fuels (AFs) and alternative fuel vehicles (AFVs) emulate abatement behavior from a unit gasoline tax in a simple three sector general equilibrium model, and in the presence of pre-existing labor taxes. The model can also be used to track the effects of each policy on outputs, exports, and fuel use. The analytical results of the model are then calibrated to data from the largest ethanol producing state in the U.S., namely Illinois. The paper finds that subsidies can achieve up to 64 percent of the welfare gains from the gasoline tax, if the uncompensated wage elasticity is low enough or the elasticities of substitution between the transportation goods is high enough. The second chapter estimates behavior of households who jointly make discrete decisions about vehicle ownership and continuous decisions about miles driven. The paper uses seven years of data from 1995-2001 for the 35 states and union territories of India. The estimated parameters will be used to calculate elasticities of each different type of vehicle for percentage changes in petrol price per unit distance travelled and in vehicle taxes. The paper also computes income and price elasticities for petrol consumption. Two types of vehicles predominant in India are cars and two-wheelers such as motorcycles, mopeds, and scooters. The latter type of vehicle is more fuel efficient than the former. However, patterns of vehicle ownership across the country reflect a growing number of cars relative to motorcycles. This paper investigates the impact alternative policies such as taxes on petrol or on cars have on efficient methods of vehicle emission abatement in India. In particular, the chapter estimates the effect of each such policy on vehicle choice and driving behavior, and how they in turn affect emissions. The main results are summarized as follows: First, continuous choice own-price elasticities are higher for 4w relative to 2w, given age, and for older vehicles relative to newer ones, within each category. Second, discrete choice own-price elasticities with respect to capital cost are higher for 2w relative to 4w. Moreover, older vehicles of each type are more sensitive to higher vehicle prices relative to their newer counterparts. Third, income elasticities for discrete vehicle choices are all positive and greater than unity. Thus, higher income encourages purchase of newer vehicles of each type. Moreover, usage of vehicles rises with income, conditional on the particular vehicle choice. Finally, the paper conducts simulations that alter the price per kilometer by adding either an additional gas tax, a distance tax or an emissions tax. Results show that a distance tax reduces vehicle kilometers traveled the most, followed by an emissions tax and lastly by the gas tax. However, local emissions are reduced the most by an emissions tax, followed by a distance tax and then by a gasoline tax. Even though it would be ideal to compare the results obtained in this paper to results generated using a micro-level data set, the estimates presented here are indicative of whether a distance tax or a gasoline tax is more effective for emissions abatement in India. The third chapter of this dissertation evaluates how information asymmetry in private automobile markets affects programs to accelerate vehicle retirement, also known as scrappage programs. We use a dynamic framework where agents have heterogenous preference for car quality. Cars can either be new, or used. While all new cars have the same quality, used cars can be of high- or low-quality. The quality of a car is perfectly correlated with emissions. The goal of a scrappage program is to induce car owners to voluntarily scrap low-quality used cars. One key result is that in the presence of adverse selection a subsidy that maintains an active resale market unambiguously makes all types of consumers better off. However, if this option of implementing the subsidy does not exist, then the only other way to induce effective scrappage in our framework is to shut down the used car market. Welfare implications suggest that it might be better not to do anything rather than have a scrappage program such as the latter. / text

This thesis develops the notion of the bioenergy transition as the long-term transformation of biomass from a local resource into a global commodity. An historical assessment is combined with interdisciplinary analysis that focuses especially on liquid biofuels and highlights the environmentally innovative case of bioethanol. The bioenergy transition is investigated from several different perspectives: technical-economic, socio-economic, socio-technical and political-economic. Linkages across different levels from household to global are analysed in relation to the effectiveness of bioenergy policies. In addition to studies at household and national levels, a North-South perspective is taken by including two major regions: the European Union (EU) and the Southern African Development Community (SADC). The relation of EU biofuels policy to international climate and trade regimes is assessed to show how regional-global linkages affect policy design and implementation. Household bioenergy markets in developing countries are poorly articulated and difficult to link to other sectors; a detailed choice model in Ethiopia showed that product-specific factors should be evaluated to inform design of programmes and policies. Municipal and sub-national markets for bioenergy have been successfully linked to national policies to coordinate supply and demand in Brazil and Sweden. Regional market development for biofuels has great potential in southern Africa but regional-national linkages currently remain unexploited. National level efforts remain quite important in terms of energy security and environmental innovation, as evidenced in Brazil, Malawi and Sweden. Biofuels sustainability criteria in the EU Renewable Energy Directive (EU-RED) were evaluated in relation to the international climate and trade regimes and were found to shift some costs onto developing countries. One of the mechanisms for assuring biofuels sustainability is bilateral agreements, which remain untested but potentially effective. Cross-level linkages were often unexploited in the cases studied; national approaches cannot easily capture complementarities across sectors and scales in biophysical and economic terms. Linking biofuels markets across different levels from household to global through regional development policies and specialised governance mechanisms could help to steer the bioenergy transition towards sustainability. / <p>QC 20141112</p>

Hydrogen Assisted Jet Ignition (HAJI) is an advanced ignition process that allows ignition of ultra-lean mixtures in an otherwise standard gasoline fuelled spark ignition engine. Under typical operating conditions, a small amount of H2 (~ 2 % ofthe main fuel energy or roughly the equivalent of 1 g/km of H2) is injected just before ignition in the region of the spark plug. By locating the spark plug in a small prechamber (less than 1 % of the clearance volume) and by employing a H2 rich mixture, the content of the prechamber is plentiful in the active species that form radicals H and OH on decomposition and has a relatively high energy level compared to the lean main chamber contents. Thus, the vigorous jets of chemically active combustion products that issue through orifices, which connect to the main chamber, burn the main charge rapidly and with almost no combustion variability (less than 2% coefficient of variation in IMEP even at λ = 2.5). / The benefits from the low temperature combustion at λ = 2 and leaner are that almost zero NOx is formed and there is an improvement in thermal efficiency. Efficiency improvements are a result of the elimination of dissociation, such as CO2 to CO, which normally occurs at high temperatures, together with reduced throttling losses to maintain the same road power. It is even possible to run the engine in an entirely unthrottled mode, but at λ = 5. / Although only a small amount of H2 is required for the HAJI process, it is difficult to both refuel H2 and store it onboard. In order to overcome these obstacles, the viability of a variety of more convenient fuels was experimentally assessed based on criteria such as combustion stability, lean limit and emission levels. The prechamber fuels tested were liquefied petroleum gas (LPG), natural gas, reformed gasoline and carbon monoxide. Additionally, LPG was employed as the main fuel in conjunction with H2 or LPG in the prechamber. Furthermore, the effects of HAJI operation under sufficient exhaust gas recirculation to allow stoichiometric fuel-air supply, thus permitting three-way catalyst application were also examined. / In addition to experiments, prechamber and main chamber flame propagation modeling was completed to examine the effects of each prechamber fuel on the ignition of the main fuel, which consisted of either LPG or gasoline. The modeling and experimental results offered similar trends, with the modeling results giving insight into the physiochemical process by which main fuel combustion is initiated in the HAJI process. / Both the modeling and experimental results indicate that the level of ignition enhancement provided by HAJI is highly dependent on the generation of chemical species and not solely on the energy content of the prechamber fuel. Although H2 was found to be the most effective fuel, in a study of a very light load condition (70 kPa MAP) especially when running in the ultra-lean region, the alternative fuels were effective at running between λ = 2-2.5 with almost zero NOx formation. These lean limits are about twice the value possible with spark ignition (λ = 1.25) in this engine at similar load conditions. In addition, the LPG results are very encouraging as they offer the possibility of a HAJI like system where a commercially available fuel is used as both the main and prechamber fuel, while providing thermal efficiency improvements over stoichiometric operation and meeting current NOx emission standards.

[pt] As pesquisas sobre carbono negro (BC) vêm ganhando grande importância nos últimos anos, não somente devido a sua capacidade de atuar como traçador histórico de processos de combustão em uma determinada região, mas também devido a sua capacidade de sorver contaminantes hidrofóbicos de ambientes aquosos. Buscou-se estudar a geocronologia de dois subprodutos provenientes de processos de combustão (BC e HPAs - hidrocarbonetos policíclicos aromáticos), que podem ter origem tanto de queima de biomassa quanto de combustíveis fósseis em um testemunho sedimentar coletado da região noroeste da Baía de Guanabara. Foram avaliadas suas possíveis relações, entre si e com o teor de carbono orgânico presente no sedimento. Avaliaram-se também as possíveis fontes dos HPAs presentes nas amostras, traçando um histórico de queima da região, caracterizada por um acentuado trafego veicular e poluição crônica por diversos compostos. O testemunho foi seccionados em intervalos de 2 cm, onde foram utilizados os segmentos entre 0-72 cm somando totalizando 30 amostras. A metodologia analítica utilizada para a determinação do BC foi a CTO-375, baseada na retirada da matéria orgânica (não-BC) por combustão na presença de oxigênio em excesso, restando somente a fração mais refratária composta pelo BC. Embora a variação percentual de BC tenha apresentado uma média de 0,36 (+-) 0,08 % p.s. ao longo do testemunho, foi observado que o mesmo compõe uma fração significativa do carbono orgânico total (TOC) desta região chegando a representar até 18% p.s. do TOC. A razão C/N possibilitou mostrar que grande parte de matéria orgânica presente neste local é proveniente de origem marinha. O método utilizado para a determinação da concentração dos HPAs foi o EPA 3540C, baseado na extração dos analitos da matriz, a purificação dos extratos através da remoção de interferentes. Através das razões diagnósticas e da análise de componentes principais (PCA) foi possível traçar uma transição das principais fontes de HPAs neste ambiente, mostrando a predominância de HPAs pirogênicos nas amostras mais antigas, para uma maior contaminação petrogênica nas amostras mais recentes. Ainda foi possível comprovar a afinidade de HPAs pirogênicos à presença de BC. Análises de microscopia eletrônica de varredura (SEM) contribuíram para uma maior compreensão das características morfológicas do sedimento, mostrando este ser rico em material amorfo e diatomáceas cêntricas. Esta análise também possibilitou a identificação visual da partícula de BC, porém, a falta de um pré-tratamento nas amostras dificultou o seu reconhecimento. Foram realizadas análises de ressonância magnética nuclear (CP/MAS (13)C NMR) visando possibilidades futuras de determinação de BC por esta técnica. As análises de NMR mostraram que o elevado teor de carbono aromático presente na amostra ambiental, relacionado principalmente a presença de lignina, interfere no sinal de NMR para a determinação de BC, sendo necessária a sua oxidação. Análises de CP/MAS-NQS (13)C NMR possibilitaram a separação das frações de BC, mostrando um teor acentuado de carbonos não-substituídos, sugerindo maior aporte de BC proveniente de queima ao longo do testemunho. Na amostra mais superficial, percebeu-se maior presença de carbonos quaternários, indicando o aumento no aporte de BC oriundo de combustão de combustíveis fósseis. / [en] Researches about black carbon (BC) have been gaining importance in recent years, not only because of its ability to act as a tracer of historical combustion processes in a given region, but also for its ability to adsorb hydrophobic contaminants in aqueous environments. In a sediment core collected from the northwestern region of Guanabara Bay, was attempted to study the geochronology of two combustion sub-products processes (BC and PAHs - polycyclic aromatic hydrocarbons), which may originate both biomass burning and fossil fuels. Was evaluated their possible relationships between themselves and with the content of organic carbon in the sediment. Also was evaluated the possible PAHs sources in the samples, tracing a burning history in the region, characterized by a marked vehicular traffic pollution and chronic individual compounds. The core was sectioned at intervals of 2 cm, which were used from 0 to 72 cm segments, in a total of 30 samples. The BC analytical determination methodology was the CTO-375, based on organic matter (non-BC) removal by combustion in presence of excess oxygen, leaving only a fraction composed by most refractory BC. Although the BC percentage had an average of 0.36 (+-) 0.08% dry weight over the core, was observed that is a significant fraction of total organic carbon (TOC) in this place representing up to 18% d.w. of TOC. The C/N ratio permitted evaluate that much of organic matter on this site comes from sea sources. The method used for determining the concentration of PAHs was the EPA 3540C, based on the analytes extraction from the matrix, and the extracts purification through the interferences removal. Through diagnostic reasons and principal component analysis (PCA), were possible to evaluate a PAHs transition of the main sources in this environment, showing the PAHs predominance in older pirogenics samples to an increase of petrogenic contamination in the most recent samples. It was also possible to relate an affinity of PAHs pyrogens in the BC presence. Analysis of scanning electron microscopy (SEM) contributed to a better understanding about the sediment morphological characteristics, showing to be rich in amorphous material and centric diatoms. This analysis also allowed the visual identification of the BC particles, however, the lack of a pre-treatment in the samples made it difficult to recognize. Nuclear magnetic resonance (CP/MAS (13)C NMR) analysis were performed in order to future possibilities of BC determination by this technique. The NMR analysis showed that the high aromatic carbon content in the environment sample, is mainly related to the presence of lignin interferes with the signal of NMR for the determination of BC, which requires its oxidation. Analysis of CP/MAS-NQS (13)C NMR allowed the separation of fractions of BC, showing a strong level of carbon non-replaced, suggesting a greater contribution of BC from burning during the core. In the most superficial sample, it was observed the large presence of quaternary carbons, indicating an increase in the input of BC come from combustion of fossil fuels.

Thesis (MTech (Mechanical Engineering))--Cape Peninsula University of Technology, 2016. / The high cost of fossil fuels and the fact that the world has arguably reached its peak oil production, has driven the need to seek alternative fuel sources. The main objective of the current study is to determine the performance of a laboratory-mounted diesel engine when fuelled with varying laboratory prepared biofuel and biodiesel and whether the advancement of the injection timing parameters will improve the engine power output and improve the smoke effect of these different fuel blends. The laboratory prepared biofuels used in this project range from 100% bio-fuel (BF100) to 50%, 30% and 10% biodiesel blends (BF50, BF30 and BF10, respectively). It should be noted that these blends are not commercially available, since they were blended in the laboratory specifically for these tests. The overall results of the study show that there is a distinct opportunity for using certain bio-fuel blends in specific applications as the power outputs are no more than one quarter less than that of base diesel. Concomitantly, the smoke opacity in all of the blends is lower than that of base diesel, which is a significant benefit in terms of their overall air emissions.