As pastagens ocupam uma grande extensão territorial no Brasil constituindo a principal fonte de alimento para os ruminantes. Entretanto, seu manejo, ainda é frequentemente realizado de forma extensiva e extrativista, tornando a atividade pouco competitiva. O estudo de estratégias de manejo do pastejo sob lotação contínua contribui para a diversificação e intensificação dos sistemas de produção de ruminantes baseados em pastagens. O objetivo foi descrever e explicar diferenças no potencial produtivo e nas características qualitativas, através de atributos estruturais e químico-bromatológicos da Brachiaria híbrida (Brachiaria ssp.) Convert HD 364 em resposta ao manejo do pastejo sob lotação contínua mimetizada e taxa de lotação variável. O experimento foi conduzido em Piracicaba, no verão de 2013. Foram testadas três intensidades de desfolhação determinadas por alturas de manejo de dossel (10, 25 e 40 cm) em combinação com dois ritmos de crescimento (50 e 250 kg N ha-1 ano-1) num arranjo fatorial (3 x 2) e delineamento em blocos completos casualizados. Variáveis-resposta medidas incluíram massa, acúmulo e taxa de acúmulo de forragem, IAF, composição morfológica e valor nutritivo (Proteína bruta - PB, Fibra insolúvel em detergente neutro- FDN, Digestibilidade in vitro da matéria orgânica - DIVMO) da forragem. Os maiores valores de acúmulo e taxa de acúmulo foram registrados para os dosséis mantidos a 40 cm de altura (12650 kg MS ha-1ano-1 e 110 kg MS ha-1 dia-1, respectivamente) e para dosséis adubados com 250 kg N ha-1(13974 kg MS ha-1ano-1 e 126 kg MS ha-1dia-1, respectivamente). Esse mesmo tratamento apresentou os maiores valores de IAFs (8,1). A massa de forragem não sofreu influência do N, mas respondeu ao aumento da altura e foi maior para os pastos mantidos a 40 cm (14650 kg MS ha-1). Mais N (250 kg ha-1) resultou em maior proporção de folhas (26 %). Maior proporção de colmo (40%) ocorreu no dosséis de 40 cm e adubados com 50 kg N ha-1 e proporções de material morto foram maiores (49%) nos tratamentos de 10 cm de altura e 50 kg de N ha-1. Dosséis de 10 cm adubados com 50 kg N ha-1, embora com menor produtividade, resultaram em maior DIVMO (670 g kg-1) e PB (153 g kg-1 e 165 g kg-1, para 10 cm e 250 kg N ha-1, respectivamente). O teor de FDN foi maior para 40 cm (545g kg-1) e com 50 kg N ha-1(550 g kg-1). A adubação nitrogenada promove ganhos em produtividade e resulta em forragem com melhor valor nutritivo, enquanto que incrementos em altura do dossel promovem maior acúmulo total e taxa média de acúmulo de forragem, até o ponto em que ocorre estabilidade da produção (25 cm), sendo assim o tratamento que apresentou melhor eficiência produtiva aliada a um bom valor nutritivo foi o com 25 cm de altura do dossel e 250 kg ha-1 de N. / Pastures occupy a large area in Brazil and are key to the country\'s livestock industry, which is almost exclusively forage-based. Grazing management, however, is largely empirical in the country, and technical guidelines for managing specific grasses are either scarce or poorly adopted, which hinders the competitiveness of the activity. Establishing sound management guidelines for key grasses can improve animal output and profitability of the livestock enterprise. The objective was to describe and explain differences in the productive potential and the qualitative traits of Convert HD 364 brachiariagrass through the characterization of agronomic and sward structural attributes as well as forage nutritive in response to three grazing intensities and under two growth rates under continuous stocking and variable stocking rate in a mob-grazing experimental protocol. The study was conducted in Piracicaba, in summer of 2013. Experimental paddocks received treatments corresponding to all possible combinations among three sward heights (10, 25, and 45 cm) and two growth rates generated by two N rates (50 and 250 kg N ha-1) split-applied monthly during the experimental period. The experimental design was a randomized complete block with a factorial arrangement. Response variables included forage accumulation and accumulation rate, LAI, plant-part composition of forage on offer, as well as plant-part composition and nutritive value (crude protein - CP, neutral detergent insoluble fiber - NDF digestibility in vitro organic matter - IVDMD) of forage. The highest values of forage accumulation and accumulation rate were recorded for swards kept at 40 cm (12650 kg DM ha-1 yr-1 and 110 kg ha-1 d-1, respectively) and for swards fertilized with 250 kg N ha-1 (13974 kg DM ha-1 yr-1 and 126 kg DM ha-1 day-1, respectively). This same combination resulted the highest LAI (8.1). Forage mass was affected by sward height but not by N rates being higher for 40-cm (14650 kg DM ha-1). Treatments with higher N (250 kg ha-1) resulted in forage with a higher proportion of leaf (26%). Higher percentages of stem (40%) were measured in swards grazed at 40 cm and fertilized with 50 kg N ha-1 while the proportion of dead material was higher (49%) in 10-cm swards receiving 50 kg N ha-1 of N. Swards kept at 10 cm and receiving 50 kg N ha-1, although less productive, resulted in forage with higher IVOMD (670 g kg-1). Forage in 10-cm swards had 153 g kg-1 crude protein and that from swards receiving 250 kg N ha-1 had 165 g kg-1. Neutral detergent fiber concentration was higher in forage from 40-cm swards (545 g kg-1) and from those receiving 50 kg N ha-1 (550 g kg-1), which is also associated with the maturity of the tissues at the time of harvest. Nitrogen fertilization promotes gains in productivity and results in forage with better nutritive value, whereas increases in canopy height promote higher total accumulation and rate of herbage accumulation, up to 25 cm. The treatment that combines high productivity with high nutritive value is 25 cm canopy height and 250 kg ha-1.

The revision of the CEN/TR 15522-2:2012 methodology contains new biomarkers to facilitate forensic fingerprinting of the variety of oil types that can be a part of different crimes and the purpose of this project is to validate the biomarkers of the new methodology. Biomarkers were validated by examining corresponding diagnostic ratios compatibility with the internationally used sampling cloth, discriminating power, correlation and simulated weathering sensibility through GC-SIM-MS analysis followed by statistical evaluation with t-tests, diagnostic power, Pearson correlation matrices and MS-PW plots respectively. Results based on most of the diagnostic ratios showed good compatibility with the internationally used sampling cloth, expected patterns of biodegradation and photo-oxidation except for observed photo-oxidation of hydro PAHs and that normative ratios and informative ratios with high diagnostic powers, but with strong correlations for some of the tested ratios, could be identified in diesel oils. Due to delimitations however such as the limited number of oils with similar origins that were analyzed the results should be regarded as guidelines that can be expanded.

Os efeitos de cianobactérias sobre organismos aquáticos planctônicos foram avaliados, visando caracterizar e quantificar as cianotoxinas e determinar a toxicidade de uma linhagem em cultura monoespecífica e de florações naturais de reservatórios do rio Tietê, SP. Assim, cultivou-se uma linhagem (NPLJ-4) de Microcystis aeruginosa, reconhecidamente tóxica, em meio ASM-1 a 25°C e fotoperíodo de 12h luz/12h escuro em câmara incubadora, avaliando-se sua toxicidade em diferentes estágios do crescimento populacional (meio e final da fase exponencial, fase estacionária e fase senescente), por meio de testes ecotoxicológicos com os organismos-teste Ceriodaphnia dubia e C. silvestrii. Esses testes foram realizados de acordo com normas padronizadas pela ABNT, sendo utilizados também para avaliar a toxicidade das florações naturais e a eficiência de diferentes processos de tratamento de água na remoção de células, microcistinas e subprodutos de cianobactérias. Os resultados indicaram aumento na concentração de microcistinas com o crescimento populacional da cianobactéria. Os extratos na fase estacionária tiveram menor toxicidade, enquanto nas demais fases causaram efeito tóxico agudo, resultando em valores de CE50; 48h de: 1,4 - 4,7 × \'10 POT.6\' cel/mL (meio fase exponencial), 1,6 - 8,7 × \'10 POT.6\' cel/mL (final fase exponencial), 7,5 - 14,1 × \'10 POT.6\' cel/mL (fase estacionária) e 1,9 - 4,6 × \'10 POT.6\' cel/mL (fase senescente) para C. dubia; e 1,9 - 5,4 × \'10 POT.6\' cel/mL (meio fase exponencial), 1,6 - 10,9 × \'10 POT.6\' cel/mL (final fase exponencial), 10,2 - 15,4 × \'10 POT.6\' cel/mL (fase estacionária) e 2,0 - 4,2 × \'10 POT.6\' cel/mL (fase senescente) para C. silvestrii. Células livres de Microcystis (M. aeruginosa, M. panniformis e M. protocystis) e Pseudanabaena mucicola foram as cianobactérias dominantes nas florações dos reservatórios de Barra Bonita e células livres de Microcystis (M. aeruginosa e M. panniformis), no de Promissão. A dominância das cianobactérias em ambos os reservatórios pode estar relacionada a períodos de estabilidade da coluna de água, razões N/P de 8 - 13 (Barra Bonita) e 19 - 20 (Promissão) na superfície, temperatura da água de 19 - 30°C (Barra Bonita) e 26 - 28°C (Promissão) e disponibilidade de nutrientes (0,05 - 0,26 mg/L de fósforo total para Barra Bonita e 0,01 - 0,05 mg/L P-total para Promissão), devido ao grau de trofia dos reservatórios. A água de ambos os reservatórios, coletada durante as florações, apresentou toxicidade aos dafinídeos, sendo que a água de Barra Bonita foi mais tóxica do que a de Promissão. Todos os extratos brutos de material oriundo das florações naturais apresentaram microcistinas (239 - 1647 µg/L para Barra Bonita e 192 - 1295 µg/L para Promissão) e causaram toxicidade aguda aos dafinídeos, com valores de CE50; 48h de: 87 - 282 mg/L (Barra Bonita) e 146 - 428 mg/L (Promissão) para C. dubia, e 98 - 546 mg/L (Barra Bonita) e 110 - 391 mg/L (Promissão) para C. silvestrii. Concentrações dos extratos a partir de 80 mg/L (Barra Bonita) e 100 mg/L (Promissão) afetaram adversamente a sobrevivência e a reprodução dos dafinídeos. Os resultados mostram riscos à biota natural e à saúde humana, bem como comprometimento dos usos múltiplos dos reservatórios, exigindo ações remediadoras e, sobretudo, preventivas para conter o processo de eutrofização. / The effects of cyanobacteria upon aquatic organisms were evaluated, aiming to characterize and quantify the toxins of both, a monospecific cyanobacterial culture and material from natural blooms occurring in the reservoirs of Tietê river, SP. The already known toxic strain NPLJ-4 of Microcystis aeruginosa was cultured in ASM-1 medium at 25 Celsius degrees and 12h light/12h dark in the incubator, in order to evaluate its toxicity at different stages of the culture growth by ecotoxicological tests using the cladocerans Ceriodaphnia dubia and C. silvestrii as test-organisms. These tests were carried out according to the procedures standardized by ABNT, in order to evaluate also the toxicity of natural blooms and the efficiency of different water treatment processes in removing cells, microcystins and by-products of cyanobacteria. The results obtained indicated an increase in the concentration of microcystins along the cyanobacterial culture growth. Extracts from the stationary phase of the culture were less toxic compared with those from the other phases which had acute toxicity and adversely affected cladoceran survival, resulting in EC50; 48h values of 1,4 - 4,7 × \'10 POT.6\' cells/mL (middle exponential phase), 1,6 - 8,7 × \'10 POT.6\' cells/mL (final exponential phase), 7,5 - 14,1 × \'10 POT.6\' cells/mL (stationary phase) and 1,9 - 4,6 × \'10 POT.6\' cells/mL (senescent phase) for C. dubia; and 1,9 - 5,4 × \'10 POT.6\' cells/mL (middle exponential phase), 1,6 - 10,9 × \'10 POT.6\' cells/mL (final exponential phase), 10,2 - 15,4 × \'10 POT.6\' cells/mL (stationary phase) and 2,0 - 4,2 × \'10 POT.6\' cells/mL (senescent phase) for C. silvestrii. Cells of Microcystis (Microcystis aeruginosa, M. panniformis and M. protocystis) and Pseudanabaena mucicola were cyanobacteria species dominant in the Barra Bonita reservoir and cells of Microcystis (M. aeruginosa and M. panniformis), in the Promissão reservoir. The dominance of cyanobacteria in both studied reservoirs was related to the stability of the water column, N/P ratios of 8 to 13 (Barra Bonita) and 19 to 20 (Promissão), high water temperatures (19 - 30°C for Barra Bonita and 26 - 28°C for Promissão) and high nutrient availability (0,05 - 0,26 mg/L total phosphorus for Barra Bonita, and 0,01 - 0,05 mg/L total P for Promissão) as a consequence of the trophic state of the reservoirs. The water from Barra Bonita reservoir during the cyanobacterial blooms was more toxic to daphnids than that from Promissão reservoir. Crude extracts from all cyanobacteria blooms tested presented microcystins (239 - 1647 µg/L for Barra Bonita and 192 - 1295 µg/L for Promissão) and caused acute toxicity to daphnids, resulting in EC50; 48h values of 87 - 282 mg/L (Barra Bonita) and 146 - 428 mg/L (Promissão) for C. dubia, and 98 - 546 mg/L (Barra Bonita) and 110 - 391 mg/L (Promissão) for C. silvestrii. Crude extracts concentrations above 80 mg/L to Barra Bonita and 100 mg/L to Promissão adversely affected the survival and reproduction of daphnids. The results obtained evidenced the risks to the natural biota and possibly to the human health, and can therefore jeopardize the multiple uses of the reservoirs. They reveal the urgent necessity for remedial action, particularly to slow down and to prevent eutrophication.

O presente trabalho de pesquisa teve como objetivo principal avaliar o efeito da carga orgânica volumétrica aplicada (COVA) na produção de hidrogênio usando o reator AnSBBR com recirculação operado em batelada e biomassa imobilizada. Para este efeito, o reator foi operado a 30ºC com dois tempos de ciclo (3 e 4 h), alimentado com três concentrações afluentes (3000, 4000 e 5000 mgDQO.L-1), uma velocidade de recirculação de 30 L.h-1, usando glicerol como única fonte de carbono e a biomassa de uma estação de tratamento de abatedouro de aves. A combinação destes fatores fez com que o reator fosse operado com seis cargas orgânicas volumétricas aplicadas diferentes (7565, 9764, 12911, 10319, 13327 e 16216 mgDQO.L-1.d-1). Os resultados mostraram que não existiu uma tendência clara entre a carga orgânica aplicada e a produção de hidrogênio. Porém, os melhores resultados quanto à produção de hidrogênio foram atingidos quando o reator foi operado com 4 horas de tempo de ciclo e alimentado com uma concentração afluente de 5000 mgDQO.L-1 (COVA de 12911 mgDQO.L-1.d-1), sendo sua produtividade molar média de hidrogênio (PrM) de 67,5 molH2.m-3.d-1. Esta condição também atingiu o melhor rendimento molar de hidrogênio por carga orgânica aplicada RMCAS,m e o melhor rendimento molar de hidrogênio por carga orgânica removida (RMCRS,m), sendo estes de 5,2 e 21,1 molH2.kgDQO-1, respectivamente. Adicionalmente foi estudada a diferença na produção de hidrogênio entre o uso de biomassa pré-tratada e não tratada termicamente, cuja análise de variância (ANOVA) mostrou que a diferença não foi estatisticamente significativa. Finalmente o reator foi operado usando glicerina bruta industrial para comparar os resultados com aqueles obtidos operando com glicerol, observando-se uma clara desvantagem na produção de hidrogênio quando foi usada glicerina bruta. Em geral, o reator AnSBBR operado em batelada sequencial apresentou resultados promissores na produção de hidrogênio usando glicerol como fonte de carbono, porém estudos mais profundos ainda são necessários no intuito de otimizar o sistema para a utilização de glicerina bruta. / This study evaluated the influence of applied volumetric organic load on biohydrogen production in an anaerobic sequencing batch biofilm reactor (AnSBBR) with 3.5 L of liquid medium and treating 1.5 L of glycerin based wastewater per cycle at 30ºC. The reactor was operated with two cycle periods (3 and 4 hours), three influent concentrations (3000, 4000 and 5000 mgCOD.L-1), recirculation rate of 30 L.h-1 and an inoculum from a poultry slaughterhouse. Six applied volumetric organic loads (AVOLCT) were generated from the combination of cycle period and influent concentrations (7565, 9764, 12911, 10319, 13327 e 16216 mgCOD.L-1.d-1). There was not a clear relation between the applied volumetric organic load and hydrogen production. However, the highest hydrogen molar production (MPr: 67.5 molH2.m-3 .d-1) was reached when the reactor was operated with a cycle period of 4 h and an influent concentration of 5000 mgCOD.L-1 (AVOLCT: 12911 mgCOD.L-1. d-1). This condition also reached the highest molar yield per removed load based on organic matter (MYRLC,m: 5.2 molH2.kgCOD-1) and the highest molar yield per applied load based on organic matter (MYALC,m: 21.1 molH2.kgCOD-1). In addition, it was studied whether existed or not a statistical significant difference on molar productivity averages pre-treating and not pre-treating the inoculum. It was observed that this was not statistically significant (p>0.05). Finally, the reactor was operated using crude glycerol as a sole source of carbon to evaluate hydrogen production. The disadvantage on hydrogen production when crude glycerol was used comparing to pure glycerol was clearly observed. The AnSBBR used on hydrogen production experiments operated with pure glycerol as a sole carbon XIV source showed an important potential. Nevertheless, additional studies are required in order to optimize results.

A economia mundial é fortemente dependente da disponibilidade de óleo, no entanto as reservas de óleo leve, mais atrativas ao mercado, tendem nos próximos anos ao esgotamento, trazendo à luz as reservas de óleo pesado para atender as demandas do mercado. No entanto, os processos associados ao transporte e processamento desses óleos viscosos consomem muita energia, impondo um grande desafio para a indústria do petróleo. Nesse contexto, se transportar óleos viscosos com água através de um escoamento bifásico em padrão Core Annular Flow (CAF) é muito promissor. Nessa prática, uma película anular de água envolve o núcleo que contém o óleo, minimizando o contato entre este e a parede do duto e reduzindo as perdas de energia por atrito. Visou o presente estudo mapear os padrões de escoamento de óleo pesado com água em dutos horizontais e verticais, mensurar os fatores de redução de potência e do diferencial de pressão associados à um trecho reto e à uma válvula de gaveta aberta e determinar o holdup para avaliar a eficiência do CAF. Para atingir esses objetivos, uma unidade de bancada foi construída, consistindo de tanques de armazenamento e de separação da mistura. Interligando os tanques, foram dispostos dutos transparentes com 27 mm de diâmetro interno e 8 m de extensão, contendo duas seções horizontais e uma vertical para análise e diversos acessórios hidráulicos. O óleo utilizado possuía viscosidade de 3200 cP a 22 °C e densidade de 945 kg/m3 . Os resultados experimentais demonstraram haver diversas configurações de fluxo segundo o posicionamento do duto, e que a diferença de densidade dos fluidos descentraliza o óleo nos escoamentos horizontais. Além disso, o trecho vertical intercalado entre os trechos horizontais se comportou como um retificador de fluxo, melhorando os índices do CAF. Foi determinado um fator de redução de perda de pressão máximo de 250 vezes para o trecho reto e de 12 vezes para a válvula de gaveta. O fator global máximo de redução de potência foi mensurado em 2,2 vezes. Concluiu-se que, para um trecho reto, o projeto de instalações hidráulicas para o escoamento bifásico deve considerar 15 % a mais de perda de carga em relação ao escoamento de água pura. Já para a válvula de gaveta, esse fator deve ser de 700 %. / The world economy is strongly dependent on the availability of oil, however, light oil reserves, more market-oriented, tend to deplete in coming years, bringing to light the heavy oil reserves to meet the demands of the market. However, the processes associated with the transportation and production of these viscous oils consume a lot of energy and pose a great challenge for the oil industry. In this context, transporting viscous oils through a liquid-liquid two-phase oil-water flow in a core annular pattern (CAF) is very promising. In this method, an annular water film surrounds the oil-containing core, minimizing its contact with the pipe wall and reducing energy losses by friction. The aim of the present work was to map the flow patterns of a biphasic oil-water flow in horizontal and vertical pipes, to evaluate the overall energy savings provided by the CAF technique, to measure the pressure gradient reduction factor along the pipe and in a gate valve and to determine the holdup as a way of assessing the energy efficiency of the biphasic oil-water flow transport. To achieve these goals, an experimental facility was built and it consisted of cargo and separation tanks. Connecting these tanks, approximately 8 m of 27mm-ID clear transparent PVC pipes, two horizontal and one vertical sections and various hydraulic fittings. It was used in the tests lubricating oil with 3200 cP and 945 kg/m3 at 22°C and distilled water. The experimental results showed that there are several flow configurations according to the pipe positioning, and that the oil and the water density difference decentralizes the oil core in horizontal flows. In addition, the vertical section placed between the two horizontal ones behaved like a flow rectifier, improving the core annular flow energy savings basis. An average pressure gradient reduction factor of 250 times in a straight pipe and of 12 times in a gate valve was determined. The maximum overall power reduction factor was measured as being 2.2 times. It was concluded that the design of a hydraulic installation to transport heavy oil with water in a core annular pattern should consider a pressure drop increase by a factor of 15 % in a straight pipe and by a factor of 700 % in a gate valve based on the monophasic water transport at similar flow rates.

La formation d'émulsions eau-dans-huile stables est un problème majeur rencontré par les pétroliers au niveau de la production mais aussi du raffinage. Afin d'essayer de prévoir ce phénomène, Total a développé une méthode de classement des huiles qui permet, à partir de leurs propriétés physico-chimiques, de déterminer a priori leur capacité à former ou non des émulsions stables. Cependant, les mécanismes interfaciaux sous-jacents ainsi que l’influence des molécules tensioactives du brut sur la stabilité des émulsions n’est pas très clair. Notre travail a consisté à étudier la contribution des acides naphténiques et des asphaltènes dans les phénomènes observés. L’étude d’huiles réelles a permis d’établir un lien entre la stabilité des émulsions et la formation à l'interface d'un gel 2D. Les études menées sur les huiles réelles dont les acides naphténiques ont été extraits ont permis de montrer que ces derniers, en compagnie de leurs formes ionisées, les naphténates, ont la capacité de réduire la stabilité des émulsions en diminuant la résistance du gel interfacial, ou même en empêchant sa formation. Les expériences réalisées sur les huiles réelles dépourvues d’asphaltènes ont permis de confirmer le rôle stabilisant des asphaltènes. Les résultats obtenus suggèrent que les asphaltènes s’adsorbent sur le gel 2D déjà formé par des tensioactifs passés de l’huile vers l’eau et le rapprochent ainsi de sa transition vitreuse. La résistance du gel interfacial s'en trouve alors augmentée, ce qui conduit à la formation d'émulsions plus stables. En croisant le classement industriel des bruts opéré par Total et les résultats de l’étude, un mécanisme global, régi par la compétition entre les acides naphténiques, les naphténates et les asphaltènes à l’interface E/H est proposé pour expliquer les différences de stabilité observées avec les différentes huiles. Lorsque les acides et les naphténates sont suffisamment concentrés, ils empêchent la formation du gel interfacial et les émulsions sont peu stables. Lorsqu’ils sont moins concentrés le rôle des asphaltènes peut alors devenir prépondérant en donnant une cohésion plus importante au gel qui se rapproche de sa transition vitreuse, ce qui conduit en général au renforcement de la stabilité des émulsions formées. / Water-in-crude oil emulsions are a major issue for oil companies in both production and refining facilities. Thanks to physical and chemical characterizations, Total set a classification which allows the decision of a crude oil ability to create stable emulsions. However the interfacial mechanisms implied and the influence of the indigenous surfactants of crude oil remain unclear. Our work consists in studying the naphthenic acids and asphaltenes contribution to the w/o emulsion stability. The study of realistic crude oils enabled the discovery of a link between the emulsion stability with the formation of a very particular interfacial behavior: a two-imensional gel. Experiments with desacidified oils have proven the destabilizing ability of naphthenic acids and their ionized form, naphthenates. They actually decrease the interfacial gel strength and can even prevent the gel formation. Asphaltenes-free crude oils have permitted to confirm the stabilizing role of asphaltenes. Rather than adsorbing directly on the interface, asphaltenes seem to adsorb on the interfacial gel already formed. The gel strength is thus increased and lead to higher emulsion stability. Thanks to these results and the industrial classification of crude oil developed by Total, a global mechanism explaining the emulsion stability process has been proposed. This mechanism is governed by the competition between asphaltenes, naphthenates and naphthenic acids at the water/oil interface. If the concentration of naphthenic acids and naphthenates is high enough, the interfacial gel cannot be formed and the emulsions are unstable. If the crude oil is not acidic enough, the asphaltenes influence increases dramatically and implies the strengthening of the gel which becomes closer to his glass transition. This generally leads to the formation of more stable emulsions.

L’analyse du pétrole et de ses dérivés est d'une grande importance pour l'industrie pétrolière et de l'environnement, et que dans sa matrice contient un ensemble de métaux (V, Ni, Fe, etc) et les non-métaux (S, N, Cl, etc) qui ont un grand impact au cours du raffinage et des procédés de combustion. La quantification de ces éléments est devenu sujet commun dans de nombreux laboratoires d'analyse. À l'heure actuelle, il existe des méthodes standard pour la quantification de ces éléments à l'aide des techniques spectroscopiques telles que la plasma à couplage inductif (ICP), la vaporisation électrothermique (ETV), analyse par activation neutronique (NAA), des métaux et des non-métaux, et des techniques potentiométriques les non-métaux tels que les halogènes. Ces méthodes, bien qu'elles soient validées, montrent des formalités fastidieuses, vous pouvez demander stratégies d’étalonnages bons et, dans certains cas, nécessite l'utilisation de normes coûteuses organométalliques. En raison de ces raisons a été soulevée dans le présent document rechercher de nouvelles formes de dosage pour l'analyse élémentaire dans le pétrole et ses dérivés en utilisant des méthodologies sensibles, rapides et faciles. La première idée qui se pose est de l'échantillon enrobé dans une matrice de xérogel de solide brut, ce qui pose le profit pour préparer les normes d'étalonnage à l'aide de solutions aqueuses de concentration connue et en les encapsulant dans la même manière. Cette huile manière encapsulée dans xérogel a été validée à l'aide LA ICP-MS et LIBS et les limites de détection ont été obtenus à partir de 0,7 ng g-1 pour Ni, 0,8 ng g-1 pour V et 1,5 ng g- 1 S, avec une reproductibilité entre 1 à 3%. L'analyse de spéciation ont également soulevé des molécules associées à V, Ni et S par chromatographie sur couche mince et surveillés par MS PCI ainsi trouvé une famille de différenciation molécules associées à ces éléments entre différentes fractions de pétrole brut et la matrice de l'échantillon même que les limites de détection ont été trouvés pour Ni et V de 18 ng g-1 et 23 ng g-1 respectivement. Il a également été observé que l'utilisation de ces méthodes d'analyse peut prendre moins de temps pour atteindre certains protocoles d'analyse systématique et finalement échouer à générer très peu de déchets dans l'environnement. / Analysis of crude oil and its derivatives is of great importance for the crude oil industry and the environment, and that within its matrix contains a set of metals (V, Ni, Fe, etc.) and nonmetals (S, N, Cl, etc) which have great impact during the refining and combustion processes. Quantification of these elements has become common subject matter in many analytical laboratories. Currently, there are standard methods for the quantification of these elements using spectroscopic techniques such as inductively coupled plasma (ICP), electrothermal vaporization (ETV), neutron activation analysis (NAA), for metals and some non-metals, and potentiometric techniques non-metals such as halogens. These methods, although they are validated, show time-consuming procedures, it can not raise a good calibration strategies and in some cases requires the use of expensive organometallic standards. Because of these reasons was raised in this paper find new forms of quantification for elemental analysis in the oil and its derivatives using sensitive methodologies, quick and easy. The first idea that arises is the sample encapsulated within a crude solid xerogel matrix, this poses the advantage to prepare our own calibration standards using aqueous solutions of known concentration and encapsulating them in the same way. This way crude oil encapsulated in xerogel was validated using LA ICP MS and LIBS and detection limits were obtained from 0.7 ng g-1 for Ni, 0.8 ng g-1 for V and 1.5 ng g-1 S, with a reproducibility between 1 to 3%. Also raised speciation analysis of molecules associated with V, Ni and S by thin layer chromatography and monitored by LA ICP MS, thus was found a family of differentiation-associated molecules to these elements between different fractions of crude and the same sample matrix, as detection limits were found for Ni and V of 18 ng g-1 and 23 ng g-1 respectively. It was also observed that the use of these methods of analysis may take less time to reach some systematic analysis protocols and ultimately fail to generate very little waste to the environment.

Les pétroles utilisés en raffinage étant de plus en plus lourds et chargés en métaux et hétéroélements, il est d’une grande importance pour les activités de raffinage de connaître la spéciation de ces espèces au sein des produits pétroliers et leurs comportements durant les procédés de raffinage. Afin d’apporter des réponses à cette problématique des techniques de caractérisation élémentaire et moléculaire ont été utilisées notamment par ICP MS Haute Résolution et FT ICR MS respectivement. Ces techniques analytiques sont appliquées à différents échantillons pétroliers provenant parfois de procédés de raffinage et les informations obtenues au niveau élémentaire et moléculaire sont utilisées de manières complémentaires pour améliorer notre compréhension des mécanismes se produisant au sein de nos échantillons durant les activités de raffinage. / The crude oils available for the refining industry are heavier and heavier and more concentrated in metals and heteroelements. It is thus of great importance to study the speciation of these species within the petroleum products and their behavior during the refining processes. To answer that problematic, elemental and molecular characterization techniques have been used, mainly High Resolution ICP MS and FT ICR MS for the elemental and molecular characterization respectively. The analytical techniques quoted are used for the analysis of several petroleum products sometimes originating from refining processes and the information obtained at the elemental and molecular level are combined to improve our understanding of the mechanisms occurring within our samples during refining activities.

O objetivo do trabalho foi identificar ferramentas e indicadores adequados ao monitoramento e à otimização de processos de biorremediação, incluindo parâmetros físicos, químicos e microbiológicos definidos em estudos de tratabilidade de solos contaminados por óleo cru em escala de laboratório e comparar estratégias de biorremediação, tais como bioestímulo e bioaumento conduzidas em simulações de biopilhas dinâmicas ou estáticas. Quando três métodos de extração de hidrocarbonetos de petróleo de solo arenoso e franco-argiloso para análise cromatográfica (Soxhlet-SOX, microondas-MARS e extração acelerada por solvente-ASE) foram comparados entre si, concluiu-se que a técnica que promove a melhor recuperação depende da fração de interesse (n-alcanos, HRP, MCNR, HPA), das características texturais do solo (teores de areia, silte e argila) e da idade da contaminação. Dentre os indicadores de densidade populacional microbiana (microrganismos heterotróficos totais-PHT, população de fungos-PF e população microbiana degradadora de óleo (PDO) passíveis de utilização para indicar a taxa de degradação de compostos orgânicos presentes no solo tais como os hidrocarbonetos de petróleo, o PDO mostrou-se o mais adequado em conjunto com a produção de CO2 aferida pelo método respirométrico. Quando a estratégia de biorremediação de solo franco-argiloso contaminado com óleo cru a 3% (m m-1) utilizando bioestímulo (ajuste de pH, umidade e taxa C:N:P) foi comparada ao bioaumento (bioestímulo e adição de inóculo de microrganismos extraídos, enriquecidos e aclimatizados ao óleo cru como fonte de carbono), em sistemas de bancada simulando biopilha dinâmica (microcosmo M) e biopilha estática com aeração forçada (reator B), o tratamento que apresentou melhor remoção (32%) de HTP após 121 dias foi o bioaumento em biopilha estática. Para HPA, o tratamento que alcançou a melhor remoção (33%) foi com bioestímulo também em biopilha estática. A avaliação da taxa de mortalidade (%) de Eisenia andrei exposta tanto a solos recém-contaminados por óleo cru e preparados para bioestímulo (BIOS) e bioaumento (BIOA) a serem tratados em biopilhas dinâmicas e estáticas em escala de laboratório mostrou que após 56 dias de exposição da E. andrei, todos os solos produziram letalidade de 100%, quer fossem os solos recém-contaminados e preparados para os diferentes tratamentos (BIOS M, BIOS B, BIOA M, BIOA B) ou após 121 dias de tratamento. Tal resultado confirma que a biorremediação foi incipiente também do ponto de vista de remoção da ecotoxicidade. Em linhas gerais, a biorremediação de solo franco-argiloso contaminado por óleo cru, contendo tanto contaminação antiga quanto recente, reúne os maiores desafios à biorremediação, tanto do ponto de vista da composição textural do solo quanto da natureza do contaminante. Os processos são aparentemente lentos e requerem ferramentas auxiliares para aceleração dos mesmos. Recomenda-se no futuro, condução de experimentos com o uso de diferentes surfactantes, com ênfase em biosurfactantes / The objective of this investigation was to identify tools and indicators suitable for monitoring and optimizing bioremediation processes, including physical, chemical and microbiological variables defined in treatability studies of crude oil contaminated clayey soils in lab-scale and to compare bioremediation strategies, such as biostimulation and bioaugmentation carried out in lab scale dynamics and static biopiles. When three methods for extraction of petroleum hydrocarbon for chromatography analysis (Soxhlet-SOX, microwaves-MARS and accelerated solvent extraction-ASE) were compared, it was concluded that the most appropriate extraction method depends on the hydrocarbon fraction of interest (n-alkanes, RPH, UCM or PAH), the textural soil characteristics (sand, silt and clay content) and the contamination age. Among the microbiological indicators investigated (total heterotrophic microorganisms-PHT, fungi population-PF and; oil-degrading microorganism population-PDO, the last one was the best indicator for degradation of organic carbon compounds such as petroleum hydrocarbon, together with CO2 generation measured through respirometric method. Bioremediation strategies for oil-contaminated clayey soil (3% m m-1) were compared, including biostimulation (adjustment of pH, C:N:P rate and moisture) and bioaugmentation (biostimulation plus a consortium inoculum extracted from the original aged-contaminated soil, enriched and acclimatized with the crude oil as carbon source) in lab scale system simulating dynamic (microcosms) and static (bioreactors with forced aeration). The treatment which presented the highest TPH removal (32%) after 121 days was the bioaugmented static biopile (BIOA B). For PAH, the most efficient treatment method that removed 33% of PAH was the biostimulated static biopile (BIOS B). The mortality rate (%) for Eisenia andrei exposed to newly contaminated soil prepared for biostimulation (BIOS) and bioaugmentation (BIOA) treatments at day 0 as well as the treated soil in static and dynamic biopiles at different treatment times (after 24, 59 and 121 days) revealed that after 56 of E. andreis exposition, all soils produced mortality of 100%, no matter if newly contaminated or treated (BIOS M, BIOS B, BIOA M, BIOA B). The ecotoxicity tests confirmed that bioremediation as such was incipient also from the toxicity removal viewpoint. In general terms, bioremediation of clayey soils with a complex contaminant such as crude oil raise considerable challenges, both from the soil characteristics as well as the nature of the contaminant. The processes are apparently slow and require auxiliary tools to speed up the process. In the future, it is recommended to test the use of different surfactants, particularly bio-surfactants.

Development and description of the nominal exchange rate of the dollar since 1945. Specification of determinants, which affected dollar exchange rate in the period. Consequences for United states economy and stability of the world fiscal system. Relation between dollar exchange rate and price of gold, relation between dollar exchange rate and price of crude oil. Relation betweén dollar exchange rate and significant financial crisis. Deskripce vývoje nominálního kursu dolaru v období od r. 1945 do současnosti. Určení faktorů, které tento vývoj ovlivňovaly. Důsledky pro ekonomiku USA a stabilitu světového finančního systému. Souvislost vývoje kursu dolaru se změnami cen zlata a ropy. Souvislost s významnějšími finančními krizemi.