Magister Scientiae - MSc / This research was aimed at employing the broad use of petrophysical analysis and reservoir modelling techniques to explore the petroleum resources in the sandstone units of deep marine play in the Bredasdorp Basin. / South Africa

Magister Scientiae - MSc / The Bredasdorp Basin is one of the largest hydrocarbon producing blocks within Southern Africa. The E-M field is situated approximate 50 km west from the FA platform and was brought into commission due to the potential hydrocarbons it may hold. If this field is brought up to full producing capability it will extend the lifespan of the refining station in Mosselbay, situated on the south coast of South Africa, by approximately 8 to 10 years. An unexpected pressure drop within the E-M field caused the suite not to perform optimally and thus further analysis was imminent to assess and alleviate the predicament. The first step within the project was to determine what might have cause the pressure drop and thus we had to go back to cores drilled by Soekor now known as Petroleum South Africa, in the early 1980’s. Analyses of the cores exposed a high presence of granulation seams. The granulation seams were mainly subjected within sand units within the cores. This was caused by rolling of sand grains over one another rearranging themselves due to pressure exerted through compaction and faulting, creating seal like fractures within the sand. These fractures caused these sand units to compartmentalize and prohibit flow from one on block to the next. With advance inquiry it was discovered that there was a shale unit situated within the reservoir dividing the reservoir into two main compartments. At this point it was determined to use Petrel which is windows based software for 3D visualization with a user interface based on the Windows Microsoft standards. This is easy as well as user friendly software thus the choice to go with it. The software uses shared earth modeling tool bringing about reservoir disciplines trough common data modelling. This is one of the best modelling applications in the available and it was for this reason that it was chosen to apply within the given aspects of the project A lack of data was available to model the granulation seams but with the data acquired during the core analyses it was possible to model the shale unit and factor in the influences of the granulation seams to asses the extent of compartmentalization. The core revealed a thick shale layer dividing the reservoir within two sections which was not previously noted. This shale layer act as a buffer/barrier restricting flow from the bottom to the top halve of the reservoir. This layer is thickest at the crest of the 10km² domal closure and thins toward the confines of the E-M suite. Small incisions, visible within the 3 dimensional models could serve as a guide for possible re-entry points for future drilling. These incisions which were formed through Lowstand and Highstand systems tracts with the rise and fall of the sea level. The Bredasdorp Basin consists mainly of tilting half graben structures that formed through rifting with the break-up of Gondwanaland. The model also revealed that these faults segregate the reservoir further creating bigger compartments. The reservoir is highly compartmentalized which will explain the pressure loss within the E-M suite. The production well was drilled within one of these compartments and when the confining pressure was relieved the pressure dropped and the production decrease. As recommendation, additional wells are required to appraise the E-M structure and determine to what extent the granulation seems has affected fluid flow as well as the degree of sedimentation that could impede fluid flow. There are areas still containing untapped resources thus the recommendation for extra wells. / South Africa

Fossil fuels are currently the primary industrial energy source on Earth. They are principally composed of complex hydrocarbons in either long-chain or cyclic conformation. Industrial use of petroleum, diesel, oil, tar and other coal-derived products inevitably leads to pollution of the environment. The most serious pollution is caused by polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) that are not easily removed from soil after a spill. Long-chain and cyclic conformation makes fossil fuel hydrocarbons difficult to break down. However, certain free-living soil microorganisms have adapted to utilising these PAHs/PCBs as a source of energy. In many cases, their efficacy is greatly enhanced by the presence of plants. By inhabiting the rhizosphere, microbes form a mutualistic relationship with the plant, receiving nutrients from it and in return providing a less polluted environment in which the plant can grow. The purpose of this study was to elucidate some of the microbial population diversity in PAH/PCB-polluted soils in South Africa through the use of denaturing gradient gel electrophoresis (DGGE). In an initial study, DGGE was employed to separate soil communities in polluted and unpolluted soils into a genetic fingerprint, the main bands of which were sequenced and subjected to a BLAST analysis through a database for possible identification of species present. Phylogenetic and distance studies indicated that unpolluted soils have a far greater species diversity. It thus was evident that PAH/PCB pollution of soil leads to a decrease in microbial diversity by selecting for microorganisms with the ability to activate metabolic pathways allowing them to utilise the pollutants as an alternative source of carbon. Population diversity of pro- and eukaryotes found within polluted and non-polluted soils was compared. DGGE was employed to determine the genetic fingerprint of each population. Following this, dendogram analyses based on Shannon indices were done to determine PAH breakdown potential of prokaryotic vs. eukaryotic communities. A higher diversity and better adaptation potential were evident within prokaryotic than eukaryotic communities in pollution-stressed environments, indicating that the prokaryotic component of these samples had the greatest PAH-metabolism potential. To determine the capacity for PAH/PCB metabolism by the organisms within the soil samples being studied, the presence of xylE and ndoB genes, responsible for toluene/xylene and naphthalene biodegradation, respectively, was determined. DGGE was performed to analyse genetic diversity between these two genes, based on community fingerprints. Polluted soil communities tended to have comparable community diversity within their functional genes, depending on their physical situation, plant species proximity and soil conditions. In general, soil contained indigenous microbes with a high natural potential for biodegradation of PAHs/PCBs. A portion of the 16S gene of eight bacterial isolates representing the most dominant culturable taxa in the polluted soils was sequenced and analysed for identification purposes. These identifications were conducted in conjunction with the use of the catabolic gene probes xylE and ndoB to establish the hydrocarbon degrading capacity of the isolates. Pseudomonas, from the rhizosphere of Cyperus esculentus, was the most common PAH-degrading genus found in this study. Considering the well-established rhizosphere competence and PAH-degrading capacity of Pseudomonas, this genus seems to be the best suited for bioaugmentation purposes in South Africa. The presence of the nifH gene, the general marker gene of nitrogen-fixing bacteria in communities from unpolluted and polluted soils, was determined. It was hypothesised that bioremediation could be enhanced by nitrogen addition to polluted environments. Nested-PCR of the nifH gene was conducted on a diagnostic basis and was followed by DGGE of the product to determine the functional gene diversity within pollution-dwelling, nitrogen-fixing bacterial communities. Nitrogen-fixing microorganisms were present in all the soils sampled but, in only 80% of the pure cultures isolated from polluted and unpolluted soils and rhizospheres. Although different rhizospheres and pollutants were examined, it was found that of the polluted soils studied, most nifH gene diversity of polluted soils existed within machinery oil polluted, wood chip mulched, non-rhizosphere soil. Thus, it would appear that the more polluted the soil the higher the free microbe nitrogen fixation diversity possibly due to environmental stress. / Thesis (PhD (Microbiology))--University of Pretoria, 2007. / Microbiology and Plant Pathology / unrestricted

Aquatic organisms in response to toxic insults from environmental pollutants activate defence systems including the aryl hydrocarbon receptor (AhR) in an attempt to metabolize and excrete these toxicants and their metabolites. These detoxification mechanisms however may come with certain energetic costs. I hypothesize that the activation of the AhR by β-Naphthoflavone (β-NF), a model AhR agonist, results in increased energetic costs requiring metabolic reorganization in rainbow trout hepatocytes. While the results obtained suggest that there are no significant energetic costs of AhR activation, analysis of enzyme activities suggests possible metabolic reorganization. This study also showed significant changes in cellular processes in hepatocytes over the incubation periods which previously were not reported. Furthermore, for the first time in fish hepatocytes, metabolic flux analysis (MFA) was used to examine intra-cellular metabolism, the applicability of which is discussed.

Polycyclic aromatic hydrocarbons (PAHs) are produced via the incomplete combustion of organic matter. They are ubiquitously present in the environment, and human exposures typically involve complex PAH mixtures in complex matrices (e.g., soil, urban air). Many PAHs are genotoxic carcinogens; exposures can augment cancer risk and reliable risk assessment of PAH mixtures is a regulatory concern. There is a paucity of in vivo genotoxicity information for most PAHs and PAH mixtures. Risk assessment of PAH mixtures assumes dose addition (i.e., additive, incremental contributions from each PAH); however, there is a lack of evidence to support this assumption. This thesis assessed the in vivo genotoxicity of 9 PAHs and 6 PAH mixtures following sub-chronic oral exposure of transgenic Muta™Mouse (i.e., adduct and lacZ mutant frequency across 5 tissues). The results revealed that PAHs and PAH mixtures induce significant levels of genetic damage; the mixtures induced very high levels of damage and mutations. Differences in the nature and magnitude of the effects in individual tissues appear to be related to the processes that govern PAH metabolism and the processing of genetic damage (e.g., repair and translesion synthesis). Scrutiny of the dose addition assumption revealed more-than-additive effects in tissues proximal to the exposure route (i.e., intestine, liver), but less-than-additive effects in distal tissues (i.e., bone marrow); however, discrepancies between the experimentally-observed and predicted responses were typically small (i.e., within 5-fold). Comparisons of cross-tissue patterns in adduct and mutant frequencies revealed that the frequency of the former is generally inversely related to that of the latter. This appears to be related to the experimental design, and the influence of repair and replication on adduct and mutant frequency. The BMD approach was employed to estimate genotoxic (i.e., adduct) potency and mutagenic (i.e., lacZ mutant) potency for all agent-tissue combinations. The results demonstrate that the mutagenic potency of PAHs and PAH mixtures is empirically related to genotoxic potency; moreover, that there is cross-tissue and cross-compound congruence in the processing of PAH-induced damage. The results obtained significantly advance existing knowledge regarding the genotoxic hazards of PAHs and PAH mixtures; moreover, the empirical relationships between genetic toxicity endpoints.

The combustion of petroleum-based fuels leads to the formation of several pollutants. Among them, soot particles are particularly harmful due to their severe consequences on human health. Over the past decades, strict regulations have been placed on automotive and aircraft engines to limit these particulate matter emissions. This work is primarily focused on understanding the fundamental behaviour of soot particles and their formation. Though the focus of this work is on soot formation and growth pathways, the study of the gas-phase combustion process was also an integral part to validate the mechanism. A reduced mechanism is developed with retaining the larger PAH species till coronene from KAUST-ARAMCO mechanism. Counterflow diffusion flames had emphasized the simulation of canonical configuration where the reduced mechanism is validated and the soot growth pathways are evaluated. The importance of the significant contribution of larger PAH species on the soot growth pathways in both SF and SFO flames is evident in this analysis. The sensitivity of these flames with respect to strain rates, dilution, and at higher pressures are analysed. Direct Numerical Simulation (DNS) of two-dimensional counterflow diffusion flames is conducted to understand the impact of vortex interactions on soot characteristics. The results indicate that the larger PAH species contributes to the soot formation in the air-side perturbation regimes, whereas the soot formation is dominated by the soot transport in fuel-side perturbation. The study is extended to simulate and compare coflow laminar flame using different statistical moment methods MOMIC, HMOM and CQMOM.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第22085号 / エネ博第393号 / 新制||エネ||76(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 河本 晴雄, 教授 石原 慶一, 教授 川那辺 洋 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

In the early 21st century, oil and gas production in the U.S. was conjectured to be in terminal-irreversible decline. But, thanks to the advancement of hydraulic fracturing technologies over the last decade, operators are now able to produce two-thirds of U.S. oil and gas output from almost impermeable shale formations. Despite the enormous success of the ‘shale revolution’, there are still debates about how long shale production will last and if there will be enough to subsidize a meaningful transition to ‘greener’ power sources. Most official pronouncements of shale oil and gas reserves are based on purely empirical curve-fitting approaches or geological volumetric calculations that tend to largely overestimate the actual reserves. As an alternative to these industry-standard forecasting methods, we propose a more reliable, ‘transparent’, physics-guided and data-driven approach to estimating future production rates of oil and gas in shales. Our physics-based scaling method captures all essential physics of hydrocarbon production and hydrofracture geometry, yet it is as simple as the industry-favored Decline Curve Analysis (DCA), so that most engineers can adopt it. We also demonstrate that our method is as accurate as other analytical methods and has the same predictive power as commercial reservoir simulators but with less data required and significantly faster computational time. To capture the uncertainties of play-wide production, we combine physical scaling with the Generalized Extreme Value (GEV) statistics. So far, we have implemented this method to nearly half a million wells from all major U.S. shale plays. Since the results of our analyses are not subject to bias, policy-makers ought not to assume that the shale production boom will last for centuries.

Accurate phase behavior modeling of hydrocarbon and aqueous mixtures plays a critical role in simulation of compositional flow in subsurface reservoirs, such as miscible gas flooding and CO2 sequestration. As Michelsen proposed his groundbreaking works in stability test and phase split calculation, PT flash calculation has been well developed in the past four decades and become the most popular flash technique. However, as research interests move to more complicated reservoir fluids, some inherent drawbacks of PT flash formulations show up and recent researches focus on a promising alternative called VT flash calculation. In this thesis, VT flash calculation is used in place of PT flash to model phase behaviors of hydrocarbon and aqueous mixtures. A dynamical model, together with a thermodynamically stable numerical algorithm, is developed to calculate equilibrium phase amounts and compositions with/without capillary effect to simulate phase behaviors of unconventional/conventional hydrocarbon mixtures. In order to model water-containing mixtures, the cubic equation of state is replaced by the Cubic-PlusAssociation equation of state, and a salt-based Cubic-Plus-Association model is developed to calculate phase behaviors of CO2-brine systems. The combination of VT flash calculation and the salt-based Cubic-Plus-Association model accurately estimate CO2 solubility in both single- and mixed-salt solutions, and it exhibits close prediction accuracy with a more sophisticated electrolyte Cubic-Plus-Association model. At the end, the ultimate goal is to develop an efficient two-phase VT-flash compositional flow algorithm. The multilayer nonlinear elimination method is used to remove locally high nonlinearities based on the feedback of intermediate Newton solutions. To further improve the computational efficiency, a modified shadow region method is used to bypass unnecessary stability tests. Although nonlinear elimination fails to fully resolve the convergence issue, which roots in the nondifferentiable equilibrium pressure at the points of phase boundary, the number of time refinements is significantly reduced and the improved VT-flash compositional flow algorithm with multilayer nonlinear elimination method successfully simulates a number of numerical examples with and without gravity.

Ethylene is the most important organic molecule with regard to production volume. Therefore, the energy spent in its separation processes, based on old-fashioned distillation, takes approx. 33% of total operating costs. Membranes do not require significant thermal energy input; therefore, membrane processes may separate hydrocarbons cheaply and just as reliably as distillation columns. Olefin/paraffin separations are the future targets of commercial membrane applications, provided high-performing materials become available at reasonable prices. This thesis addresses the development of advanced carbon molecular sieve (CMS) membranes derived from intrinsically microporous polymers (PIMs). Chronologically, Chapter 4 of this work reports the evaluation of PIMs as potential ethylene/ethane selective materials, while Chapters 5 to 7 propose PIMs as carbonization precursors. The gravimetric sorption studies conducted in this work regarding both the polymers and their heated-derivatives revealed that this separation is entirely controlled by diffusion differences. The pristine polymers examined in this study presented BET surface areas from 80 to 720 m2g-1. Furthermore, the effect of using bromine-substituted PIM-polyimides elucidated a boost in ethylene permeability, but with a significant drop in selectivity. The hydroxyl functionalization of PIM-polyimides was confirmed as a valuable strategy to increase selectivity. Functionalized PMDA-HSBF is the most selective polyimide of intrinsic microporosity known to date (= 5.1) due to its hydrogen-bonded matrix. In spite of their novelty, pristine PIMs based on the spirobisindane moiety were not tight enough to distinguish between the 0.2 Å difference in diameter of the ethylene/ethane molecules. Therefore, they did not surpass the upper bound limit performance of known polymeric membranes. Nevertheless, the carbons derived from these polymers were excellent ethylene/ethane sieves by virtue of their narrow and tight pore distribution around the 3.6- 4.4 Å range. PIM-based carbons were typically 10 times more permeable than their corresponding low free-volume analogues treated after the weight-loss of the sample reached a plateau. Furthermore, carbons derived from PIM-6FDA-OH and PIM-6FDA at 800 ºC were as ethylene separating efficient as their lower free-volume counterparts. The pore sintering mechanism that takes place above 600 ºC during the carbonization procedure of these films reduced the entropic freedom of the molecules, as was observed from separation factors of up to 25 under pure-gas conditions and 2 bar of pressure— The best performing CMS membranes reported to date for ethylene/ethane separation. The mixed-gas separation of 1:1 binary ethylene/ethane mixtures revealed a significant decrease of the pure-gas measurements due to a carbon matrix dilation effect. This localized ultramicroporous dilation caused the ethane permeation rate to increase monotonically as the pressure rose to realistic operating values. Nevertheless, the CMS obtained from PIM-6FDA and PIM-6FDA-OH surpassed any diffusion-controlled polymer or carbon that has been reported to date.