This dissertation thesis consists of six papers on macroeconomics, international economics, and energy economics. All the papers are tied together by the use of meta-regression analysis, which is essential for the derivation of robust policy-relevant conclusions from often conflicting results presented in the empirical literature. I use meta-analysis to quantitatively synthesize the reported research results on a given topic, correct the literature for publication selection bias, and filter out the effect of various misspecifications present in some primary studies. My results can be summarized as follows: 1) The elasticity of intertemporal substitution in consumption, a key input to all dynamic models in finance and macroeconomics, varies significantly across countries. The differences can be explained by the level of stock market participation, when countries with higher participation exhibit larger values of the elasticity; the mean reported elasticity is 0.5. 2) The effect of borders on international trade, which most authors find to be surprisingly large, can be explained away by innovations in methodology introduced in the last decade. When these innovations are taken into account jointly, the border effect disappears for developed countries, and is relatively small for developing countries. 3) When...

Made available in DSpace on 2016-06-02T19:29:26Z (GMT). No. of bitstreams: 1 3129.pdf: 1211425 bytes, checksum: fe662cd2f2192794e3ea63b146284d10 (MD5) Previous issue date: 2010-05-19 / Universidade Federal de Sao Carlos / The aim of this work was to evaluate the effects of the water-soluble fraction of gasolina (WSFG) to the Neotropical fish Prochilodus lineatus. The WSFG was prepared by adding gasoline to water (1:4) this mixture was then exposed to intense sunlight for 6h, simulating a gasoline spill in tropical conditions. After that the upper insoluble phase was discharged and the WSFG was collected. Fish were exposed for 6, 24 and 96h to the WSFG diluted to 5% (EXP group) or only to water (control group or CTR). The following parameters were analyzed: biochemical (antioxidants and EROD) of gills and liver, hematologic, osmo-ionic, metabolic, endocrine (cortisol) besides the density and distribution of chloride cells (CC) and the activity of gills Na+/K+-ATPase (NKA). The increased in ethoxyresorufin-O-deethylase (EROD) and glutathione-S-transferase (GST) activity indicated phase I and II biotransformation of the compounds present in the WSFG in both organs. The activation of CYP1A in the gills pointed out the importance of this organ in the biotransformation of xenobiotics. The liver showed an increase in reduced glutathione (GSH) content at 24 and 96 h exposure to WSFG and the increase in the activity of catalase (CAT) and glutathione peroxidase (GPx) after 96 h exposure. The gills showed an activation of the antioxidant defenses with an increased CAT activity soon after 6h exposure and an increase in GSH content after 24h exposure. However, for both organs the antioxidants defense was not enough to prevent oxidative damage, as shown by the occurrence of lipid peroxidation in liver and gills after 6 and 96h of exposure, respectively. The WSFG also promoted hemolysis, as indicated by the changes in the hematological parameters analyzed and an increase in plasma K+. Fish showed a secondary stress response, noted by the occurrence of hyperglycemia in all the periods of exposure, despite no significant increase in plasma cortisol. The WSFG also lead to an increase in the density of CC, in the activity of NKA, in plasma concentrations of Na+ and in the osmolarity in fish exposed to WSFG for 24h. Taken together these results showed that the compounds present in the WSFG interfere on the functioning of vital organs such as liver and gills of Prochilodus lineatus. / O objetivo deste trabalho foi avaliar os possíveis efeitos da fração solúvel da gasolina (FSG) em alguns parâmetros bioquímicos e fisiológicos do peixe neotropical Prochilodus lineatus. A FSG foi preparada misturando-se gasolina em água (1:4), essa mistura foi exposta à radiação solar intensa durante 6 h, simulando um derrame de gasolina em condições tropicais. Após, a FSG foi coletada e a fração insolúvel foi descartada. Os animais foram expostos por 6, 24 e 96 h à FSG diluída 5 % (grupo EXP) ou apenas à água (grupo controle ou CTR). Foram analisados parâmetros bioquímicos (antioxidantes e indução da CYP1A) em brânquia e fígado, hematológicos, osmo-iônicos, metabólicos, endócrino (cortisol) além da densidade e distribuição de células-cloreto (CC) e a atividade da enzima Na+/K+-ATPase (NKA) nas brânquias. O aumento na atividade da etoxiresorufina-O-desetilase (EROD) e da glutationa-S-transferase (GST) indicou a estimulação das vias de biotransformação de fase I e II dos compostos da FSG em ambos os órgãos. A ativação das enzimas de detoxificação nas brânquias ressaltou a importância deste órgão na biotransformação de xenobióticos. O fígado apresentou aumento na concentração de glutationa reduzida (GSH) após 24 h e 96 h de exposição à FSG e aumento na atividade catalase (CAT) e glutationa peroxidase (GPx) após 96 h de exposição. As brânquias mostraram uma ativação das vias antioxidantes com o aumento da CAT logo após 6 h de exposição, e da concentração de GSH após 24 h de exposição. No entanto, para ambos os órgãos estudados, a ativação das defesas antioxidantes não foi suficiente para impedir os danos oxidativo, como indicado pela ocorrência de peroxidação lipídica (LPO) no fígado e nas brânquias após 6 e 96 h de exposição, respectivamente. A FSG também provocou hemólise comprovada pela diminuição dos parâmetros hematológicos analisados, seguido pelo aumento do K+ plasmático. Os peixes mostraram uma resposta secundária de estresse visualizado pela ocorrência da hiperglicemia em todos os períodos de exposição, apesar da ausência de diferenças significativas na concentração plasmática do cortisol. A FSG também provocou aumento na densidade das CC, na atividade da NKA, nas concentrações plasmáticas do Na+ e osmolaridade nos animais expostos durante 24 h. Esses resultados em conjunto indicam que os compostos presentes na FSG afetaram de maneira significativa órgãos vitais como o fígado e as brânquias do Prochilodus lineatus.

Made available in DSpace on 2014-12-17T14:57:49Z (GMT). No. of bitstreams: 1 CelitonS.pdf: 1872654 bytes, checksum: 0e3a2fa3a25b2b0d3f6314fb9f1b6ab9 (MD5) Previous issue date: 2009-07-13 / The vehicles are the main mobile sources of carbon monoxide (CO) and unburned hydrocarbons (HC) released into the atmosphere. In the last years the increment of the fleet of vehicles in the municipal district of Natal-RN it is contributing to the increase of the emissions of those pollutants. The study consisted of a statistical analysis of the emissions of CO and HC of a composed sample for 384 vehicles with mechanization Gasoline/CNG or Alcohol/Gasoline/CNG of the municipal district of Natal-RN. The tests were accomplished in vehicles submitted to Vehicular Safety's Inspection, in the facilities of INSPETRANS, Organism of Vehicular Inspection. An partial gases analyzer allowed to measure, for each vehicle, the levels of CO and HC in two conditions of rotation of the motor (900 and 2500 rpm). The statistical analysis accomplished through the STATISTICA software revealed a sensitive reduction in the efficiency of the converters catalytic after 6 years of use with emission average it is of 0,78% of CO and 156 (ppm) of HC, Which represents approximately 4 (four) times the amount of CO and the double of HC in comparison with the newest vehicles. The result of a Student s t-test, suggests strongly that the average of the emissions of HC (152 ppm), at 900 rpm, is 40% larger than at 2500 rpm, for the motor without load. This result reveals that the efficiency of the catalytic conversion is limited kinetically in low engine speeds. The Study also ends that when comparing the emissions of CO and HC considering the influence of the fuels, it was verified that although the emissions of CO starting from CNG are 62% smaller than arising from the gasoline, there are not significant differences among the emissions of HC originating from of CNG and of the gasoline. In synthesis, the results place the current criteria of vehicular inspection, for exhaust gases, in doubt, leading the creation of emission limits of pollutant more rigorous, because the efficiency of the converters catalytic is sensibly reduced starting from 6 years of use. It is also raised the possibility of modifications in the test conditions adopted by the current norms, specifically in the speed engine, have seen that in the condition without load the largest emission indexes were registered in slow march. That fact that allows to suggest the dismissal of the tests in high speed engine, reducing the time of inspection in half and generating economy of fuel / Os ve?culos automotores s?o as principais fontes m?veis de Mon?xido de Carbono (CO) e Hidrocarbonetos n?o queimados (HC) lan?ados na atmosfera. Nos ?ltimos anos o acr?scimo da frota de ve?culos no munic?pio de Natal-RN vem contribuindo para o aumento das emiss?es desses gases poluentes. O estudo consistiu de uma an?lise estat?stica das emiss?es de CO e HC de uma amostra composta por 384 ve?culos com motoriza??o a Gasolina/GNV ou ?lcool/Gasolina/GNV do munic?pio de Natal-RN. Os testes foram realizados em ve?culos submetidos ? Inspe??o de Seguran?a Veicular, nas instala??es do INSPETRANS, Organismo de Inspe??o Veicular. Um analisador de gases parcial permitiu medir, para cada ve?culo, os n?veis de CO e HC em duas condi??es de rota??o do motor (900 e 2500 rpm). A an?lise estat?stica realizada por meio do software STATISTICA revelou uma sens?vel redu??o na efici?ncia dos conversores catal?ticos ap?s 6 anos de uso com a emiss?o m?dia de 0,78 % de CO e 156 (ppm) de HC, o que representa aproximadamente 4 (quatro) vezes a quantidade de CO e o dobro de HC em compara??o com os ve?culos mais novos. O resultado de um Teste-T de Student sugere fortemente que a m?dia das emiss?es de HC (152 ppm), a 900 rpm, ? 40% maior que a 2500 rpm, para o motor sem carga. Esse resultado revela que a efici?ncia da convers?o catal?tica ? limitada cineticamente em baixas rota??es. O Estudo conclui tamb?m que ao comparar as emiss?es de CO e HC, considerando a influ?ncia dos combust?veis, verificou-se que embora as emiss?es de CO a partir do GNV sejam 62% menores do que a partir da gasolina, n?o h? diferen?as significativa entre as emiss?es de HC oriundas do GNV e da gasolina. Em s?ntese, os resultados colocam os atuais crit?rios de inspe??o veicular, para gases da exaust?o, em d?vida, conduzindo a cria??o de limites de emiss?o de poluentes mais rigorosos, visto que a efici?ncia dos conversores catal?ticos ? sensivelmente reduzida a partir de 6 anos de uso. Suscita-se tamb?m a possibilidade de modifica??es nas condi??es de teste adotadas pelas normas atuais, especificamente na rota??o do motor, haja vista que na condi??o sem carga os maiores ?ndices de emiss?o foram registrados em marcha lenta. De ante disso, sugere-se a dispensa dos testes em altas rota??es, reduzindo ? metade o tempo de inspe??o e gerando economia de combust?vel

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

Este trabalho teve como objetivo principal propor procedimentos de avaliação de metodologia de coleta e análise de solventes no ar em ambiente de trabalho. Utilizou-se o metanol em mistura MEG (Metanol 33%, Etanol 60% e Gasolina 7%) como exemplo. Na época, a mistura MEG estava sendo indicada para substituir o etanol combustível, devido a sua falta no mercado. Foi montada uma atmosfera controlada dinâmica por injeção, para gerar concentrações conhecidas de vapor metanol em mistura MEG. Essa atmosfera permaneceu estável ao redor de 7,5 horas. O limite de detecção método analítico do CG-DIC, utilizado para o acompanhamento das concentrações geradas, foi de 18mg/m3 para um volume amostrado de 2mL coletado por uma válvula de coleta. Estando a atmosfera controlada apta para os testes de validação, foram realizados estudos de volume de \"breakthrough\" para coleta de metanol em tubos de sílica gel, com a finalidade de se conhecer o volume a ser amostrado em campo. Esses estudos foram realizados levando em conta as possíveis interferências de etanol, gasolina e elevada umidade relativatotal . O tempo de coleta de amostra para a mistura com umidade relativa recomendado para uma vazão de 200mL/min foi de 15 minutos. O método analítico utilizado, para a determinação de metanol coletado em tubos de sílica gel e analisado por CG-DIC. foi uma adaptação de métodos encontrados na literatura do NIOSH, para as condições da mistura. Após encontrar a melhor seletividade para o menor tempo de retenção do metanol em mistura MEG, foi determinado o limite de detecção de 9,7x 10-3µg. A precisão do método analítico encontrada foi de 2,1% e a exatidão esteve entre 89% e 97%. Estabelecida a metodologia analítica, as melhores condições de atmosfera controlada e o volume de coleta de amostra, foram realizados estudos que integram a coleta e análise ou seja, precisão e exatidão de coleta e análise e estabilidade de armazenamento. Para estudos de precisão e exatidão de coleta e análise, foram geradas concentrações de metanol em mistura MEG, com umidade ao redor de 0,5, 1 e 2 vezes o limite de tolerância brasileiro(156ppm); dessorção em água e análise por CGDIC. O coeficiente de variação total calculado para o método de coleta e análise de metanol em mistura MEG foi de 7,3% (precisão) e wazzu exatidão esteve entre 90% e 101%. As concentrações de metanol foram estáveis, em tubos adsorventes armazenados em geladeira, durante o período de estudo de 14 dias. Porém, foi constatada uma migração de metanol através da camada analítica para a camada controle de forma gradativa com o passar do tempo. As soluções, a partir da dessorção dos tubos armazenadas em geladeira, foram estáveis durante o período de estudo de 45 dias. Além desses experimentos foram também realizados estudos de capacidade de adsorção da sílica gel para metanol levando em conta os interferentes, e verificado se eram capazes de dessorver totalmente o metanol, após um certo período de coleta. Constatou-se que após 30 minutos de coleta, os interferentes (etanol, umidade e gasolina) entravam em equilíbrio com o adsorvente e o metanol. / The main objective of this work is to propose procedures for the evaluation of the methodology of the sampling and analysis of solvents in the air in the workplace. Methanol in a MEG mixture (Methanol 33%, Ethanol 60%, and Gasoline 7%) was used as an example. At that time the MEG mixture was being proposed to substitute ethanol fuel due to its shortages on the Brazilian market. An atmosphere, dynamically controlled by injection, was produced to generate the known concentrations of methanol vapour in MEG mixtures. This atmosphere remained stable for about 450 minutes. The detection Iimit, using the GC-FID analytical method to monitor the concentrations produced, was 18mg/m3 for a sample volume of 2mL sampled from a sampling valve. The controlled atmosphere being suitable for the validation tests, studies of the breakthrough volume for the sampling of methanol in silica gel tubes were carried out, with the aim of discovering the total volume to be sampled in the field. These studies were carried out taking into account the possible interference of ethanol, gasoline and the high relative humidity. The sampling time for the mixture with the recommended relative humidity with a flow rate of 200mL/min was fifteen minutes. The analytical method used for the determination of methanol sampled in silica gel tubes and analyzed by GC-FID, was based on the methods found in the NIOSH and OSHA literature, adapted to the mixture conditions. After finding the best selectivity for the lowest retention time for the methanol in the MEG mixture, the detection Iimit of 9.7 x 10-3µg was determined. The precision of the analytical method was 2.1% and the accuracy was between 89% and 97%. Having established the analytical methodology. the best conditions for the controlled atmosphere and the sampling volume, studies were carried out which integrated the sampling and the analysis, that is, the precision and the accuracy of the sampling and the analysis and the storage stability. To study the precision and the accuracy of the sampling and analysis, concentrations 1 or 2 times that of the Brazilian tolerance Iimit of methanol (156 ppm) in MEG mixture, with humidity around 0.5, were generated, using dessorption in water and analysis by GC-FID. The total coefficient of variation calculated for the method of sampling and analysis of methanol in MEG mixture was 7.3% (precision) and the accuracy was between 90% and 101% . The concentrations of methanol were stable, in adsorption tubes stored in the refrigerator, throughout the study period of fifteen days. However, a gradual migration of methanol through the analytical layer to the control layer with the passage of time was noted. The solutions from the dessorption of the tubes, stored in the refrigerator, were stable throughout the study period of 45 days. Besides these experiments, studies of the adsorption capacity of silica gel for methanol, taking into account the interferents, were also carried out, and it was verified whether these were capable of the total dessorption of the methanol, after a certain sampling period. It was noted that after thirty minutes of sampling, the interferents came into equilibrium with the adsorbent and the methanol.

Submitted by Kleber Alencar (kleber.alencar@accenture.com) on 2012-07-24T16:12:07Z No. of bitstreams: 1 Dissertacao MPagro Kleber Alencar final 23072012.pdf: 3485057 bytes, checksum: 5731a15f9a45ea290166bcd294785d22 (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia (suzinei.garcia@fgv.br) on 2012-07-24T19:49:41Z (GMT) No. of bitstreams: 1 Dissertacao MPagro Kleber Alencar final 23072012.pdf: 3485057 bytes, checksum: 5731a15f9a45ea290166bcd294785d22 (MD5) / Made available in DSpace on 2012-07-24T20:26:03Z (GMT). No. of bitstreams: 1 Dissertacao MPagro Kleber Alencar final 23072012.pdf: 3485057 bytes, checksum: 5731a15f9a45ea290166bcd294785d22 (MD5) Previous issue date: 2012-06-29 / Esse trabalho teve por objetivo contribuir para o entendimento da evolução da demanda por etanol e gasolina no Brasil e como este crescimento deverá ser traduzido em disponibilidade de cana de açúcar. Nesse estudo foram usados dados históricos que refletem o comportamento de variáveis no passado para projetar o futuro, considerando que o comportamento permaneça similar. Com as pressões internacionais por sustentabilidade e uma busca por uma matriz energética mais limpa, o etanol passou a ser uma opção real de complemento às demais fontes, sobretudo pelo seu aspecto ambiental. Com essa visão o Brasil já na década de 70 iniciou investimentos e incentivos para a produção de etanol para veículos, impulsionando a produção de carros flex na década de 90. Apesar de altos e baixos, hoje o aumento da demanda por etanol se deve principalmente ao crescimento da produção de veículos flex fuel. Esse crescimento vertiginoso da demanda fez com que houvesse necessidade de cada vez mais etanol e infelizmente a capacidade de produção do Brasil não foi capaz de acompanhar esse movimento, gerando falta de produto e provocando a migração do etanol para a gasolina. Essa migração tipicamente ocorre quando o etanol ultrapassa a paridade de 70% do preço da gasolina. Nesse contexto, o consumo de gasolina aumenta, impactando no volume de importação que a Petrobrás realiza para suprir o mercado interno. Através da análise das curvas de paridade e comportamento do consumidor, foi possível perceber que nos próximos anos a demanda por etanol vai continuar subindo e que a oferta de cana de açúcar não cresce na mesma proporção. Isso quer dizer que o que tínhamos de folga de produção de etanol, vai representar um déficit importante a ser suprido pela gasolina, custando ainda mais para a Petrobrás manter o nível de preço com baixo impacto inflacionário. Caso não sejam feitos investimentos relevantes para aumentar a oferta de etanol, através de novas usinas ou de maior produtividade, ou de gasolina através de mais refino, certamente teremos um cenário de desbalanceamento entre oferta e demanda de etanol e gasolina no Brasil / The objective of this study is to contribute to the understanding of the evolution of demand for ethanol and gasoline in Brazil and how this growth should be translated into the availability of sugar cane. This study was made using historical data that reflects the behavior of the variables in a certain period of time to forecast the future, considering that this behavior remains similar. Due to international pressure for sustainability and clean energy, ethanol has become a real option to complement other sources, especially for its environmental aspect. Looking to the future Brazil has started in the seventies investments and incentives for the production of ethanol for vehicles, boosting the production of hybrid flex fuels cars in the nineties. Despite ups and downs of the ethanol program, the production of flex fuel vehicles is being the main driver to increase demand for ethanol. This tremendous growth in demand has meant that there was need for more ethanol and unfortunately the production capacity in Brazil was not able to follow this movement, leading to a lack of product and causing the migration of ethanol to gasoline. This migration typically occurs when ethanol exceeds 70% of parity price of gasoline. In this context the consumption of gasoline increases, impacting the volume of imports that Petrobras makes to supply the domestic market. By analyzing the curves of price parity and consumer behavior, we can see that in the coming years the demand for ethanol will continue to rise and that the supply of sugar cane does not grow proportionately. That means that the typical excess in supply is not going to happen again in the short term. This will represent a significant deficit to be supplied by gasoline, costing even more to Petrobras to import and to keep the price level with low inflationary impact. If no investments are made to increase the supply of ethanol through the new mills or by increasing productivity, or through more refining gasoline, we will certainly have a scenario of imbalance between supply and demand of ethanol and gasoline in Brazil.

[pt] O transporte eletrocinético de gasolina e óleo através de um solo residual gnáissico é focado na utilização da eletrocinese como uma técnica de remediação para solos finos. Baseia-se na aplicação de uma diferença de potencial através de uma massa de solo, com a conseqüente produção de um fluxo eletrocinético, o qual envolve mecanismos como eletroosmose -fluxo de água- e migração de íons.Na primeira etapa, amostras de solo foram contaminadas com gasolina e com óleo cru. Os ensaios mostraram que a presença desses compostos não variou o comportamento dos parâmetros eletroosmóticos, assim como o pH e a condutividade elétrica dos eletrólitos e do próprio solo. Em dois dos ensaios realizados com óleo, observou-se um notório transporte em direção ao anodo devido à eletroosmose. Já com a gasolina os resultados das determinações analíticas sugeriram o transporte da mesma, embora que em uma escala reduzida. Na segunda etapa analisou-se a remediação dos metais e do óleo presentes em uma borra de petróleo da Bacia de Campos, para a utilização desta como material geotécnico. Nenhum teor significativo de metal foi encontrado na borra antes do ensaio, em contrapartida, observou-se contaminação de zinco pela corrosão dos eletrodos de latão utilizados. E quanto ao óleo, notou-se um transporte considerável devido à eletroosmose. / [en] This study assesses the use of electrokinetics as an innovative technique for remediation of fine-grained soils. It relies on the application of an electrical potential through a soil mass, producing a series of coupled flows, including fluid flow -electroosmosis- and migration of ions. The first stage of the experimental program encompassed a series of tests with samples of residual soil contaminated with gasoline and crude oil. The results showed that the presence of these compounds did not affect the electroosmotic behavior, and there was observed no changes on the pH and electric conductivity of neither the electrolytes solution nor the soil itself.When oil contaminated samples are of concern, it was noticed a clear electroosmotic flow towards the anode. This pattern was also observed, but at a reduced level, on the tests on the gasoline contaminated samples.The second stage of the experimental program consisted on a series of tests with oil ground from Campos Basin aiming on dewatering and de-oiling. The results were satisfying, in all sample there was a noticeable reduction on the water and oil contents. Tests results also showed a zinc contamination on the sample caused by electrolysis on the brass electrodes.

Soot is a carbonaceous materials produced as a result of incomplete combustion of fuels (gasoline, diesel, etc). At the present level of automobile technology, emission of soot from combustion in diesel engine appears to be an inevitability. The disadvantage in the diesel combustion is that it is not homogeneous throughout the cylinder. So the fuel-air ratio cannot be maintained constant throughout the flame zone and hence rich combustion zone leads to the formation of soot. Diesel engine combustion processes produce a large amount of soot, which is one of the major pollutant emissions of the exhaust systems. The fraction of combustion particulate, which is soot, is often estimated by finding the insoluble portion of the particulate. Hydrocarbons or other available molecules may also condense on or beads orbed by soot depending on the surrounding conditions. Other particulate matter constituents include partially burned fuel/lubricant oil bound water, wear metal and fuel derived sulfate. In diesel engine lubrication, soot has long been recognized as the major contaminant that is detrimental to engine lubrication, particularly in friction and wear. Different techniques for soot abatement have been investigated by researchers from the field of combustion and fuel. In spite of the large numbers of investigations of soot formation conducted till date, there is relatively little quantitative information is available about the mechanisms and governing rate processes. Some of the studies focused on the combustion chemistry of soot formation while some emphasized on engine design. On the other hand comparatively a few research works are coming out from the tribological point of view. Considering that internal combustion engines play such an important role in industry, investigative research of the parametric influences of particle size, agglomeration, oil viscosity, additives and surfactant as well as chemistry and electrical properties of particles on wear as well as into the wear mechanisms have not perhaps been as extensive as it is detrimental. Existence of a large numbers of variables in tribological contacts makes the situation very complex and difficult to analyze it quantitatively. In this complex scenario, where many opposed effects are playing their roles in soot tribology, the influence of the physical, structural and mechanical properties of soot on engine tribology has limited attention. We focus our study on one of the end effects of engine soot; friction and wear of the engine components. Since a diesel engine is not particularly suitable for use in a laboratory study of the fundamental processes and parameters of combustion due to its inherent difficulties on control and safety as well as data analysis uncertainty, so the most useful studies of soot fundamentals have emerged from studies of processes which have used simplified environments such as diffusion flames. We focus on soot tribology in steel-on-steel interaction in the presence of soot material suspended in relatively simple paraffinic hydrocarbons, hexadecane; with and without an additive. The physical, structural, chemical and mechanical properties of the particle and their changes as a function of tribological parameters are monitored throughout this study. Three type of soot are used in this work. Firstly, commercial grade carbon blacks has been used as soot simulant. Secondly, to enable controlled variations of the physical, mechanical, chemical and geometrical parameters of the particles, soot is generated in-situ by burning ethylene gas and the particles are extracted thermophoretically from different thermal zones of the flame. Thirdly, to establish the validity of the study, two types of diesel soots are extracted from an engine and studied. The objective is to use such an understanding to elucidate the basic mechanisms of friction and wear in the presence of soot which may limit the performance of a diesel engine. From our study we find that these soots have widely different morphologies, crystallographic orders and reactivity. At tribological contact the soot agglomerates fragment to primary level particles. The physical and chemical properties of such particles determine the friction between and wear of mating components. If the soot is strongly graphitic, the friction and wear are moderate. If the soot is made of chemically active organic groups, the friction and wear are high. The hardness, friction and resistance to material removal of the soot collected near the flame tip and diesel soot are found to be high compared to the other types of soot. Besides, the high hardness, irregular primary particle shape, large inter-particle adhesion leading to agglomeration and more abrasive nature of diesel soot influence the metal wear adversely. This trend of soot tribology is profound when these soots are suitably dispersed in the oil by the addition of dispersants, in our case it is polyisobutylene succinimide. Different functional groups present on the soot surface play important role in defining the interaction between surrounding medium and contacts which, in turn define the contact conditions, particle/agglomerate behavior and soot tribology. Finally, agglomeration is simulated using the features of a dissipative particle dynamics package as the simulation technique. Simulations are performed on a sizeable number of particles to observe agglomeration behavior, on simple environment, in future which can be further extended.

L’objectif de ce travail était de démontrer la possibilité de coupler sur un même catalyseur, la fonction de stockage et réduction des NOx (sur le baryum) avec un effet électrochimique reposant sur un système micropile. Ce système micropile est composé de nanoparticules catalytiques (Pt et Rh) déposés sur conducteur ionique par les ions O2- (YSZ) en contact avec un support conducteur électronique (SiC dopé) de façon à pouvoir générer, sous mélanges réactionnels, une force électromotrice capable de réduire électrochimiquement une partie des NOx sur le Pt et d’oxyder le CO, les hydrocarbures imbrûlés et H2 sur le Rh. L’effet micropile a été observé sur un catalyseur Pt/Ba (matériau de stockage)/YSZ/Rh enduit dans les canaux d’un filtre à particule en carbure de silicium dopé, en condition essence pauvre à 400°C et en condition Diesel à plus basse température (300°C). Une augmentation de la conversion des NOx d’environ 10% a été observé sur les catalyseurs micropile. L’effet électrochimique a été détecté par une surproduction de CO2, en milieu riche (très peu ou pas de O2) provenant de la réaction d’oxydation électrochimique du CO (produit par vaporeformage) en réagissant avec les ions O2- provenant de YSZ. De plus, des tests catalytiques ont montré que YSZ peut être utilisée comme matériau de stockage des NOx. En effet, un traitement réducteur préalable augmente fortement sa capacité de stockage des NOx / The main objective of this study was to demonstrate the coupling between NOx storage/reduction process on barium, with an electrochemical reduction of NOx (micro fuel cell effect) on the same catalyst. The micro fuel cell effect is ensured by a an electromotive force (potential) which is created between catalytic nanoparticules (Pt and Rh) in contact with an ionic conductor (YSZ) and an electronic conductor (doped SiC). The micro fuel cell effect was observed, during the regeneration phase of the catalysts (rich period), on a Pt/Ba/doped α-SiC-YSZ/Rh monolithic system under lean-burn gasoline conditions at 400°C with an enhancement of about 10 % of the NOx conversion over a complete cycle lean/rich. This electrochemical effect was characterized by the electrochemical oxidation of CO (produced by steam reforming) into CO2 by using O2- ions coming from YSZ. Under Diesel conditions, the micro fuel cell system was found to work at low temperature especially at 300°C. In the second part of the work, a new generation of NOx Storage and reduction catalyst was developed consisting only of noble metals (Pt and/or Rh) deposited on YSZ support (Ba free catalyst). The catalytic measurements revealed that YSZ can be used as a NOx storage material in lean burn conditions (Gasoline and Diesel) especially when it was previously reduced under hydrogen. The storage mechanism would take place on the oxygen vacancies created by the removal of O-2 ions from the YSZ structure

In recent years gasoline engines have become increasingly complex, for example through the introduction of electronic control and monitoring systems for ignition, fuel injection and exhaust aftertreatment. Parallel to this the requirements placed upon engines have also increased hence the need to develop new engine technologies. This demand for new technologies is, in part, due to the self obligation of the automobile industry to reduce the CO2 emissions about 25% by 2005, and also to the increasingly stringent future exhaust limits. Some promising solutions are currently in development, e.g. the direct injection gasoline engine and variable valve trains. All these new technologies are characterised by increasing complexity and significantly higher degrees of freedom. The associated application expenditure rises drastically with the number of free parameters and also with improved quality standards. Possible solutions to meet the future requirements of the development process are based on model-based parameter optimisation and the use of test methods, such as "Design of Experiments" (DoE). The idea behind this approach is to produce models to describe the dependence of the responses of interest (i.e. fuel consumption) on the adjusted engine parameters. With these models offline optimisation of the engine can be carry out, independently of testbench resources. The measured data for the models are produced with the help of statistically designed experiments. Thus, the testing and analysis processes are structured and the expenditure limited. In the following the DoE methodology will be employed of a gasoline engine with electromechanical valve train. / Der Ottomotor im Kraftfahrzeug hat in den letzten Jahren mit dem Einzug elektronischer Steuer- und Regelsysteme für Zündung, Einspritzung und Abgasnachbehandlung einen sehr hohen technischen Stand erreicht. Die wachsenden Ansprüche an die Motorenentwicklung im Hinblick auf Verbrauchsreduzierung bei gleichzeitiger Erfüllung der zukünftigen Abgasgrenzwerte, verschärfen den Druck zur Entwicklung weiterführender Technologien. Hierbei gibt es bereits einige vielversprechende Lösungsansätze, wie z.B. die Direkteinspritzung oder variable Ventilsteuerungen. All diese neuen Technologien zeichnen sich durch eine wachsende Komplexität durch die signifikant höhere Anzahl von Freiheitsgraden aus. Der damit verbundene Applikationsaufwand steigt drastisch durch die wachsende Anzahl freier Parameter, aber auch durch die steigenden Anforderungen an die Qualität der Applikationsergebnisse. Einen möglichen Lösungsansatz zur Realisierung der zukünftigen Anforderungen an den Entwicklungsprozess stellen die modellgestützte Parameteroptimierung sowie der Einsatz der "Statistischen Versuchsplanung" (SVP) - "Design of Experiments" (DoE) - dar. Der Grundgedanke basiert auf der Erstellung von Modellen zur Beschreibung der Abhängigkeiten variierter Verstellparameter. Mit diesen Modellen können Offline-Optimierungen unabhängig von Prüfstandsressourcen durchgeführt werden. Die für die Modellbildung benötigten Messdaten werden mit Hilfe der statistischen Versuchsplanung erzeugt. Dadurch wird der Prozess strukturiert und der Aufwand wird begrenzt. In der Arbeit wird der Einsatz der DoE-Methodik am Beispiel eines Ottomotors mit elektromechanischer Ventilsteuerung (EMVS) aufgezeigt.