Conflict in Libya was the most serious of a series of uprising at the beginning of the year 2011 in the Middle East and North Africa. Following the current situation of world production and consumption of oil, the work focuses on the reaction of oil markets to the conflict and estimates the future development of the oil industry. The aim is to analyze how much the Libyan Civil War influences the development of oil prices on world markets. The second main point of this work is to determine to what extent the current situation in the country could damage the Libyan economy. Much of the information comes from documents and statistics of the U. S. Energy Information Administration, the International Energy Agency and the Organization of Petroleum Exporting Countries.

Orientadores: Marcos Nogueira Eberlin, Alexandra Christine Helena Frankland Sawaya / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T16:06:57Z (GMT). No. of bitstreams: 1 Schmidt_EduardoMorgado_D.pdf: 4816547 bytes, checksum: a63a426882376e7714bd6aea39b9f5ba (MD5) Previous issue date: 2015 / Resumo: A espectrometria de massas é uma técnica analítica que atualmente permite desde a análise de um único íon molecular até um perfil da distribuição de íons em amostras complexas. Isso vem sendo possível por meio da análise direta com diferentes fontes de ionização e também ao desenvolvimento de analisadores de massas de altíssima resolução tais como o FT-ICR e Orbitrap. Para amostras complexas como o petróleo a fonte de ionização mais adequada para análise dos compostos polares é o Eletrospray (ESI) devido a sua estabilidade e consequentemente reprodutibilidade. Uma alternativa foi testada com a fonte ionização V-EASI, no entanto, as respostas obtidas não foram satisfatórias. O analisador de massas FT-ICR foi utilizado para análise direta de petróleo bruto e permitiu monitorar e investigar o petróleo e seus derivados adicionando novas informações desde a exploração até o refino e, ainda, em um aspecto forense como em derrame de petróleo bruto e investigação de diferentes óleos de motor. Nesse trabalho avaliou-se pela primeira vez o analisador MegaOrbitrap (ainda em fase experimental) para análise de petróleo bruto, que se mostrou tão eficiente senão melhor que o já consagrado FT-ICR. Deixando a parte amostras complexas e retornando para a análise de um único íon, em uma abordagem forense, essa técnica permite a caracterização da composição de corantes utilizados na impressão de notas de Real genuínas e falsas, e ainda, de corantes utilizados para marcar notas de real furtadas de caixas eletrônicos quando estes são violados. Sendo assim, esta tese mostra resultados obtidos da análise de petróleo bruto por ambos os analisadores de massa citados, fato esse inédito na literatura, e também resultados de análises forenses de petróleo, notas de Real falsificadas e também com indicio de furto por meio de corantes e resíduos de explosivos / Abstract: Mass spectrometry is an analytical technique that currently allows from the analysis of a single molecular ion to a profile of the distribution of ions in complex samples. This has been possible through direct analysis with different sources of ionization and also the development of ultra-high resolution mass analyzers such as the FT-ICR and Orbitrap. For complex samples such as oil, the most appropriate source of ionization is the electrospray (ESI) due to its stability and consequently reproducibility. Even though an alternative has been tested with the EASI-V ionization source, the responses obtained were not satisfactory. The analyzer FT-ICR mass is already being used for direct analysis of crude oil and allows monitoring and investigating of the crude oil and its derivatives. This new data about polar compounds may be useful to add new information starting from the oil crude exploration until refining. Additionally, it may also be useful in forensic analysis such as in crude oil spills and in the investigation of the compliance of different motor oils (mineral, semi-synthetic and synthetic) with their labels. In this study we have evaluated for the first time the MegaOrbitrap analyzer (still experimental) for crude oil analysis, which has proved to be as effective, if not better than, the widely used FT-ICR. Dealing with the analysis of a single ion in a forensic aspect, this technique allows the characterization of the dye composition used in the actual printing of genuine and counterfeit banknotes, and further, the dyes used to mark Real banknotes stolen from ATMs after they have exploded. Thus, this thesis shows results obtained from crude oil analysis performed by both mass analyzers mentioned, a fact unprecedented in the literature, and also forensic analysis results of oil, derivatives, Brazilian fake banknotes and also banknotes with theft indicators applied by explosives / Doutorado / Quimica Inorganica / Doutor em Ciências

Abstract embargoed until 2030-11-11

Genomic modifications occur slowly across generations, whereas short-term epigenetic transgenerational inheritance of adaptive phenotypes may be immediately beneficial to large numbers of individuals, acting as a bridge for survival when adverse environments occur. In this study we used dietary exposure to crude oil as an example of an environmental stressor to assess its effects from the molecular to the organismal levels in piscine and avian animal models. In addition, we assessed the role of the parental exposures on their offspring F1 generation. The research developed in this dissertation has contributed to several areas of investigation including molecular biology, animal physiology, and evolutionary biology. The quantitative information from these studies may be utilized to supplement information regarding the proximate and ultimate effects of environmental stressors on fish and bird populations. Furthermore, this information may be used as additional support for understanding the conservation of the responses from the molecular to the whole organismal levels across the vertebrate taxa, as well as their implications for population survival and maintenance. Additionally, the zebrafish (Danio rerio), the Siamese fighting fish (Betta splendens) and the king quail (Coturnix chinensis) have proven to be excellent models to start building a strong basis for understanding the effects of environmental stressors and transgenerational epigenetic phenomena using a multi-level approach. Furthermore, as more raw data and information is discovered, the concatenation of development, organismal variation, epigenetics inheritance, natural selection, speciation and evolution is being slowly decrypted.

A set of crude oil samples with different composition and characteristics is studied by means of Fast Field Cycling (FFC) 1H relaxometry, which probes the distribution of longitudinal relaxation times T1 as a function of the Larmor frequency. Investigation of T1 profiles at different temperatures is able to provide an insight into the dynamics and structural changes of oil components, with our particular interest being the high temperature behaviour of asphaltene. It is well-known that asphaltenes tend to form porous clusters in crude oils, which can cause severe problems for the process of oil extraction. Therefore, FFC experiments are conducted on Stelar Spinmaster FFC2000 in the temperature range 203K < T <443K, where the upper limit of 443K is aimed at approximating the typical maximal in-situ well temperatures. FFC relaxometry data of crude oils at such a high temperature are obtained for the first time with the use of a specially modified NMR probe. Inverse Laplace transformation is applied to the longitudinal agnetization decays, yielding T1 distributions at different frequencies. A comparative analysis of these distributions for different Larmor frequencies and temperatures showed that there is a systematic variation of the frequency dependence of T1 correlating with the asphaltene content in the samples, at temperatures similar to the well conditions.

<p>This dissertation presents several examples of diverse applications of mass spectrometry. For example, high-resolution mass spectrometry was utilized for qualitative and quantitative chemical characterization of ionized compounds in petrochemical samples, specifically, in condensate-like oil samples. Further, the ability to use tandem mass spectrometry to rapidly detect trace amounts of short-lived reaction intermediates in solution reactions is demonstrated. Finally, selective tandem mass spectrometry methods based on diagnostic gas-phase ion-molecule reactions were developed for the identification of carboxylic acid functionalities in protonated analytes.</p>

This study demonstrated the presence of hyperthermophilic organisms in the upper Jurassic Smackover formation in Womack Hills, AL. Evidence for the presence of these organisms was shown by the cultivation of an aerobic and an anaerobic, oil-degrading hyperthermophilic culture from the cuttings of an oil well in the Jurassic Smackover at 90¢ªC. Viability of microorganisms in the formation was established through electron microscopy, by carbon dioxide production, and by protein production during incubation in medium at 90¢ªC. Not only was the presence of viable microorganisms in the reservoir established, but as a result of this study, new cultivation methods were also developed that may prove useful in future studies of these types of organisms.

This work presents a techno-economic analysis of multiple direct hydrogen production technologies using different blends of Arabian crude oil and natural gas as feedstock: Auto thermal reforming, steam reforming, and combined reforming technologies are thermodynamically and technically evaluated through development of process flowsheets. Comparative analysis indicates that combined reforming using Arabian light crude oil achieves a 22.69 % of hydrogen recovery with carbon capture, which is higher than auto thermal reforming and steam reforming by 0.7 %. At the same time, auto thermal reforming achieves a 26.70 % of hydrogen recovery without carbon capture, which is higher than steam reforming and combined reforming by 4 %. Arabian heavy, medium, light, and extra light are evaluated using auto thermal reforming technology to estimate hydrogen recovery values. A wide range of crude oil and natural gas prices are included in the analysis to calculate hydrogen production cost. With crude oil price at 90 USD/bb, the hydrogen production cost is 2.9 USD/kg, and natural gas prices at 30 USD/MMBtu (Europe), 20 USD/MMBtu (Japan), and 2.5 USD/MMBtu (GCC region), the hydrogen production cost is 4.5, 3.0, and 0.4 USD/kg respectively.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental toxicants found in anthropogenic mixtures such as crude oil, air pollution, vehicle exhaust, and in some natural combustion reactions. Single PAHs such as benzo[a]pyrene (BaP) also impact fish behavior when animals are exposed in early life stages and for short periods of time. Aquatic animals such as fish may encounter BaP through road runoff and oil spills, but few studies have examined the impact of aqueous exposure on adult fish, and fewer have examined the resulting fitness-relevant behavioral consequences of BaP and PAH mixtures and their long-term persistence. This dissertation targets this gap in the literature by examining how aqueous exposure to BaP influences anxiety-like behavior, learning, and memory in adult zebrafish, and how parental exposure to the PAH mixture, crude oil, combined with hypoxia affects social and exploratory behavior in unexposed larval zebrafish. We found that learning and memory were not affected by 24 hour exposure to BaP, that anxiety-like behavior was minimally affected, and that locomotor parameters such as distance moved and times spent in darting and immobile states were significantly altered by exposure to BaP. Additionally, we found that parental exposure to crude oil and hypoxia decreased larval velocity. Additionally, we examined how crude oil, BaP, and the detergent COREXIT influence a monolayer of mouse and fish endothelial cells, as an in vitro blood-brain barrier (BBB) model. We found that exposure to BaP in particular caused significant damage to both fish and mammal in vitro BBB models, and damage to the BBB is one potential mechanism by which neural integrity and behavior may be influenced. Understanding how these toxicants influence fish brains and behavior will give insight into how fish populations explore and interact with their environment and with predators, and how these interactions persist even when toxicants are no longer present.

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