Thesis (M. Sc.)--University of Alberta, 2009. / Title from pdf file main screen (viewed on July 27, 2009). "A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Master of Science in Petroleum Engineering, Department of Civil and Environmental Engineering, University of Alberta." Includes bibliographical references.

Thesis (M.Sc.)--University of Alberta, 2010. / Title from PDF file main screen (viewed on Apr. 1, 2010). A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Master of Science in Petroleum Engineering, Department of Civil and Environmental Engineering, University of Alberta. Includes bibliographical references.

Obesity, metabolic syndrome, and diabetes represent a major source of morbidity and mortality in the United States and worldwide. Chronic misalignment of an organism’s internal circadian clock with diurnal, cyclic changes in the external environment, prevalent in professions that require shift work, contributes significantly to Type 2 Diabetes development. Experimentally, only short-term models of circadian disruption have been explored. Therefore, the goal of this study was to establish an animal model of chronic circadian disruption, which would more closely mimic the harmful misalignment associated with metabolic syndrome in clinical studies. Moreover, since high fat diet consumption alters circadian behavior and rhythmic gene expression, contributing to the diet-induced phenotype, I hypothesized that chronic circadian disruption interacts with a high fat diet to worsen metabolic syndrome. To investigate circadian misalignment and diet-induced metabolic syndrome, I examined the contribution of the Aryl Hydrocarbon Receptor (AhR). AhR has similar PAS domain containing motifs as circadian clock proteins allowing for protein/protein interactions and crosstalk between AhR signaling and circadian rhythms. Furthermore, AhR activation is implicated in Type 2 Diabetes risk. To examine chronic circadian disruption, male wild-type (WT; C57Bl/6J) and AhR +/- mice were entrained to 12/12-hour light/dark cycles where lights were on from 10pm-10am and off from 10am-10pm. Misalignment was initiated by delaying the time of lights on by 8 hours on Monday. Mice were exposed to the misalignment schedule Monday-Friday then returned to the entrainment schedule Saturday and Sunday to mimic readjustment to society during the weekend. Circadian misaligned mice were exposed to the altered light schedule for 15 weeks and control animals remained on the12/12-hour light/dark cycle. Mice were fed a normal chow diet (10% fat) or a high fat diet (60% fat). Animals were sacrificed and samples were collected at 4-hour intervals on day 2 of the weekend. Exposure to chronic circadian misalignment by light disruption or high fat diet altered circadian rhythms of behavior, metabolic outputs, and expression of circadian clock, clock-controlled nuclear receptor, and lipid metabolism genes. A combination of light misalignment and high fat diet exacerbated the effects of either treatment alone further disrupting behavior, enhancing % body fat and fasting glucose, and dampening circadian clock gene expression. AhR +/- mice also were protected from the metabolic consequences of chronic misalignment and a high fat diet by resistance to altered behavioral and molecular circadian rhythms and disruption of metabolic outputs. With metabolic syndrome and Type 2 Diabetes occurrence on the rise, it is important to understand all contributing factors, including circadian disruption. Differences between chronic circadian misalignment and high fat diet-induced obesity in WT and AhR +/- mice furthers our understanding of the complex mechanisms that underlie Type 2 Diabetes development and advocates the discovery of potential therapeutic targets for the development of novel treatment options.

Magíster en Estrategia Internacional y Política Comercial / This report explores the question: Why do foreign oil companies continue operate in exploration and production activities in Bolivia’s hydrocarbon industry after its 2006 nationalization? The history of Bolivia’s hydrocarbon industry is filled with cycles of nationalization and privatization. Each cycle has produced dramatic changes in Bolivia’s petroleum fiscal regime. Bolivia’s 2006 nationalization of its hydrocarbon industry has given Bolivia an international reputation as a high risk country to investment in. However, foreign direct investment is still occurring since the 2006 nationalization. The most interesting aspect of this continued foreign direct investment is that, the majority of it is from existing foreign companies that were there before the 2006 nationalization. This report exposes the underlying reasons as to why foreign companies continue to operate in Bolivia’s hydrocarbon sector despite its most recent nationalization in 2006. A historical analysis will be conducted on Bolivia’s hydrocarbon industry; more specifically, the time period between 1990 until 2009 will be the main focus of this report. The legal changes in Bolivia’s hydrocarbon industry since the 1990s will be evaluated in order to understand Bolivia’s strategy of nationalization in 2006. Throughout the history of Bolivia’s petroleum fiscal regime, there has been a fluctuation of contractual agreements in use with foreign oil companies. After 2006, Bolivia’s contractual agreements finally began to benefit the state by allowing it to receive its fair share of wealth from its hydrocarbon resources. Additionally, Bolivia’s “nationalization” did not involve expropriation; instead it consisted of the enforcement of renegotiations of contractual agreements between the Bolivian State and foreign oil companies. The renegotiations are instrumental in explaining why foreign companies continue to operate in Bolivia’s hydrocarbon industry after its nationalization in 2006. This report will focus on examining Bolivia’s contractual agreements from 1990 until 2009 in order understand why foreign oil companies continue to operate in Bolivia’s hydrocarbon industry in spite of its 2006 nationalization. Bolivia’s main source of revenue comes from foreign companies’ exploitation and exploration of its hydrocarbon resources, yet Bolivia has always lost its fair share of wealth from its natural resources due to unfavorable contractual agreements with foreign oil companies. 3 Universidad de Chile Before the 2006 Nationalization, Bolivia had continuously given foreign investors the majority of revenue from its hydrocarbon resources in an effort to attract and keep foreign investors in its hydrocarbon industry. In the 1990s, Bolivia wanted to increase its levels of foreign direct investment in order to import new technologies as well as to improve the expertise in exploration, extraction, transport and production activities within its hydrocarbon industry. Bolivia’s main goal behind seeking FDI was to develop its hydrocarbon sector in order to increase its national wealth from its natural resources. In addition, Bolivia’s hydrocarbon sector was extremely undeveloped. The Bolivian State was ill equipped and had inefficient state assets to develop its hydrocarbon industry. Bolivia’s petroleum fiscal regime in the 1990s was designed to favor foreign investors in order to attract and maintain foreign investment within its hydrocarbon industry. However, this caused Bolivia to lose significant control over its hydrocarbon industry as well as the wealth from its hydrocarbon resources. As a result, it became necessary for Bolivia in 2006 to renegotiate their contracts with foreign energy companies in order for Bolivia to obtain its fair share of revenue from its hydrocarbon resources. Since 2005, the government has sought to increase its share of total hydrocarbon revenues. In May 2005, the former president, Carlos Mesa introduced a new Hydrocarbon Law No. 3058 which created a direct tax, the IDH (Direct Tax on Hydrocarbons), which required companies to pay 32% of production value to the state, in addition to an 18% royalty rate that was already required. However, this law was not yet implemented until Evo Morales became the president of Bolivia in 2006. Shortly after Evo Morales became president of Bolivia, he implemented the 2006 Nationalization Decree which mandated the Hydrocarbon Law No. 3058. This law required renegotiation of contractual agreements with all foreign oil companies operating in Bolivia. The Law No. 3058 made the Bolivian State owner of all hydrocarbon resources and private companies were permitted to only keep 18 percent of production value. This law also nationalized refineries and hydrocarbon distribution companies in order to ensure the presence of Bolivia’s national oil company YPFB (Yacimientos Petrolíferos Fiscales Bolivianos) in every stage of the value chain. These actions, together with the rising international hydrocarbon prices have increased the Bolivian state’s hydrocarbon revenues. 4 Universidad de Chile The information obtained from the research in this report, will explain why foreign companies continue to operate in exploration and production activities in Bolivia’s hydrocarbon industry since its 2006 nationalization. Bolivia’s strategy behind its nationalization and its current use of contractual agreements will provide the main arguments as to why foreign companies continue to operate in Bolivia in spite of its hydrocarbon nationalization in 2006.

An integrated NOx adsorption-reduction process has been proposed in this study for the treatment of flue gases under lean-burn conditions by decoupling the adsorption and reduction into two different zones. The hypothesis has then been validated in a novel internal circulating fluidized bed. The adsorption and reaction performance of Fe/ZSM-5 for the selective catalytic reduction (SCR) of NOx with propylene was investigated in a fixed bed reactor. The fine Fe/ZSM-5(Albemarle) catalyst showed reasonable NOx adsorption capacity, and the adsorption performance of the catalyst was closely related to the particle size and other catalyst properties. Fe/ZSM-5 catalyst was sensitive to the reaction temperature and space velocity, and exhibited acceptable activity when O₂ concentration was controlled at a low level. Water in the flue gas was found to slightly enhance the reactivity of Fe/ZSM-5(Albemarle), while the presence of CO₂ showed little effect. SO₂ severely inhibited the reactivity of Fe/ZSM-5(Albemarle), and the deactivated catalyst could be only partially regenerated. Configurations of the reactor influenced the hydrodynamic performance significantly in a cold model internal circulating fluidized bed (ICFB) reactor. For all configurations investigated, the high gas bypass ratio from the annulus to draft tube (RAD) and low draft tube to annulus gas bypass ratio (RDA) were observed, with the highest RDA associated with the conical distributor which showed the flexible and stable operation over a wide range of gas velocities. Solids circulation rates increased with the increase of gas velocities both in the annulus and the draft tube. Gas bypass was also studied in a hot model ICFB reactor. The results showed that the orientation of perforated holes on the conical distributor could be adjusted to reduce RAD and/or enhance RDA. Coarse Fe/ZSM-5(PUC) and fine Fe/ZSM-5(Albemarle) catalysts were used in an ICFB and a conventional bubbling fluidized bed to test the NOx reduction performance. Coarse Fe/ZSM-5(PUC) catalyst showed poor catalytic activity, while fine Fe/ZSM-5(Albemarle) catalyst exhibited promising NOx reduction performance and strong inhibiting ability to the negative impact of excessive O₂ in the ICFB reactor, proving that the adsorption-reduction two-zone reactor is effective for the NOx removal from oxygen-rich combustion flue gases. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

No description available.

Higher temperature (~ 200°C) operation for proton exchange membrane (PEM) fuel cells would have several advantages including enhanced electrochemical kinetics, useful heat recovery, and improved catalyst tolerance for contaminants. Conventional perfluorosulfonic acid membranes (PFSA), such as Nafion show a dramatic decrease in proton conductivity at temperatures above 80°C. For this reason, there has been an increasing effort toward the development of stable, higher temperature membranes with acceptable proton conductivity. This work is directed toward the development of Nafion free membranes for direct hydrocarbon PEM fuel cells containing zirconium phosphate as the proton conductor component. Hence, composite membranes composed of zirconium-phosphate (ZrP), a solid proton conductor, which was precipitated within the voids of a porous polytetraflouroethylene (PTFE) support were synthesized. Amorphous-like zirconium phosphate (ZrP) powder was synthesized in this work. ZrP was prepared by precipitation at room temperature via reaction of ZrOCl2 with H3PO4 aqueous solutions. The proton conduction properties of ZrP powder were studied under the processing conditions found in direct hydrocarbon fuel cell. Our experimental results showed that the ZrP powder processed at 200°C possess a proton conductivity that is greater by one order of magnitude than the oven-dried samples at 70°C. Thereby, it was possible to avoid the normal decrease in conductivity with increasing temperature by having sufficient water in the vapor phase. This thesis reports the first synthesis of composite ZrP/PTFE/Glycerol (GLY) membranes. Glycerol (GLY) was introduced into the pores of PTFE with the ZrP proton conductive material using the successive wetting/drying technique. These membranes had reasonable values of proton conductivities (0.045 S cm-1), approaching that of Nafion (0.1 S cm-1) at room temperature. Samples of these composite membranes were processed at the inlet conditions of a propane fuel cell, at 200°C. Experimental results showed that the proton conductivity remained almost unchanged. This thesis also describes and reports the first synthesis of sulphur “S” or silicon, Si–modified zirconium phosphate (ZrP), porous polytetrafluoethylene (PTFE) and, glycerol (GLY) composite membranes. It was aimed at the substitution of a minor amount of phosphorus “P” in the ZrP by (S or Si) in the ZrP to modify the proton conduction properties. The modification was performed by adding a certain amount of silicic acid or sulphuric acid into phosphoric acid then proceeding with the precipitation in situ. A high proton conductivity, of 0.073 S cm-1,i.e. 73% of that of Nafion, was observed for the Si–ZrP/PTFE/GLY composite membrane.

This study investigates the rate of reaction of various types of hydrocarbons with chlorosulphonic acid at the temperature 10 degrees Celsius.

The Thrace Basin, NW Turkey, is one of the most important basins in Turkey in terms of hydrocarbon potential. Previous studies, starting in the 1930s, focused on tectonics, basin evolution, sedimentation and stratigraphy, depositional systems, and hydrocarbon potential. Eocene turbiditic sandstones and reefal limestones, and Oligocene deltaic sandstones are the major reservoir targets in the basin today. The focus of this research is the Upper Oligocene deltaic sandstones, namely the Danismen and Osmancik formations, which contain potential hydrocarbon reservoirs. The aims of research were to develop a better understanding of the geometric configuration of the Oligocene strata and to identify potential reservoirs within the study area. Accordingly, the geometric configurations of the strata were delineated using 3D seismic reflection data whereas petro-physical properties of the target formations were determined using wireline logs from three wells. A right-lateral strike slip or reverse fault system and associated NW-SE trending asymmetric fold extend across the study area. Both the fault system and the fold are truncated beneath the Miocene unconformity and are thus dated as late Oligocene to early Miocene in age. The Miocene unconformity forms a stratigraphic trap whereas the fault system and associated fold construct a NW-SE trending structural trap. Hydrocarbon-bearing, five main clean sandstone (shale volume less than %10) intervals were identified using wireline logs and evaluated as potential targets. Hydrocarbon concentrations increase through the fold structure. Thus, the fault system and the associated asymmetric fold were the main factors that affected the zonal distribution of hydrocarbons in the study area. / Master of Science

The oxidative degradation of organic materials typically operates through a radical-mediated chain mechanism known as autoxidation; a process that has severe consequences in both biological settings (i.e. accumulation of lipid peroxides) and non-living substrates (i.e. breakdown of petroleum-derived materials, such as lubricants/oils, plastics, polymers, rubbers, etc.). However, autoxidation can be retarded by radical-trapping antioxidants (RTAs); chemical species that capture chain-carrying radicals to break the chain of oxidation. A particular class of RTA, diarylamines, have proven especially effective at elevated temperatures due to a purported catalytic mechanism of inhibiting autoxidation, and thus, have found significant use as protective agents in engine lubricant oils. However, the current diarylamine technology struggles to manage the increased oxidative stress placed on it by modern internal combustion engines (ICEs), which burn fuel at higher temperatures in order to meet emission standards. Designing superior diarylamines is not straightforward, however, as the mechanisms by which they are forced from their catalytic cycle are not well understood. Herein, we report our investigations into the fate of an industrially-representative, isotopically-enriched diarylamine during hydrocarbon autoxidation at elevated temperatures using a novel 2D 1H – 15N heteronuclear multiple bond correlation (HMBC) spectroscopic technique. Synthesis of a small scope of oxidation products allowed for the identification of a previously unreported product of diarylamine autoxidation. Additionally, a consistent pattern of diarylamine speciation under varying conditions was observed spectroscopically. Use of the HMBC technique also confirmed previous reports of the regenerative ability of the diarylamine and the intermediates of its purported catalytic cycle. Quantification studies using ultra performance liquid chromatography (UPLC) during the early stages of autoxidation provided insight into the formation of initial diarylaminic intermediates. Additionally, we examined the fate of the diarylamine during autoxidations in the presence of nitrogen oxides (NOx), which are found in the blow-by gas of ICEs and have been shown to exacerbate hydrocarbon autoxidation. The performance of diarylamine was drastically reduced under such conditions, and HMBC spectroscopy illustrated its rapid conversion to a number of intermediates. The most prominent two intermediates were identified as mono- and di-nitrated analogues of the original diarylamine, and were demonstrated to possess no RTA activity; regardless of temperature or substrate. HMBC spectroscopy also illustrated the differences in product distribution under each set of conditions.