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Exploring unconventional hydrocarbon reservoirs and enhancing the recovery of hydrocarbon from conventional reservoirs are necessary for meeting the society's ever-increasing energy demand and requires a thorough understanding of the multiphase interfacial and transport phenomena in these reservoirs. This dissertation performs pore-scale studies of interfacial thermodynamics and multiphase hydrodynamics in shale reservoirs and conventional oil-brine-rock (OBR) systems. In shale gas reservoirs, the imbibition of water through surface hydration into gas-filled mica pores was found to follow the diffusive scaling law, but with an effective diffusivity much larger than the self-diffusivity of water molecules. The invasion of gas into water-filled pores with width down to 2nm occurs at a critical invasion pressure similar to that predicted by the classical capillary theories if effects of disjoining pressure and diffusiveness of water-gas interfaces are considered. The invasion of oil droplets into water-filled pores can face a free energy barrier if the pressure difference along pore is small. The computed free energy profiles are quantitatively captured by continuum theories if capillary and disjoining pressure effects are considered. Small droplets can invade a pore through thermal activation even if an energy barrier exists for its invasion. In conventional oil reservoirs, low-salinity waterflooding is an enhanced oil recovery method that relies on the modification of thin brine films in OBR systems by salinity change. A systematic study of the structure, disjoining pressure, and dynamic properties of these thin brine films was performed. As brine films are squeezed down to sub-nanometer scale, the structure of water-rock and water-oil interfaces changes marginally, but that of the electrical double layers in the films changes greatly. The disjoining pressure in the film and its response to salinity change follow the trend predicted by the DLVO theory, although the hydration and double layer forces are not simple additive as commonly assumed. A notable slip between the brine film and the oil phase can occur. The role of thin liquid films in multiphase transport in hydrocarbon reservoirs revealed here helps lay foundation for manipulating and leveraging these films to enhance hydrocarbon production and to minimize environmental damage during such extraction. / Doctor of Philosophy / Meeting the ever-increasing energy demand requires efficient extraction of hydrocarbons from unconventional reservoirs and enhanced recovery from conventional reservoirs, which necessitate a thorough understanding of the interfacial and transport phenomena involved in the extraction process. Abundant water is found in both conventional oil reservoirs and emerging hydrocarbon reservoirs such as shales. The interfacial behavior and transport of water and hydrocarbon in these systems can largely affect the oil and gas recovery process, but are not well understood, especially at pore scale. To fill in the knowledge gap on these important problems, this dissertation focuses on the pore-scale multiphase interfacial and transport phenomena in hydrocarbon reservoirs. In shales, water is found to imbibe into strongly hydrophilic nanopores even though the pore is filled with highly pressurized methane. Methane gas can invade into water-filled nanopores if its pressure exceeds a threshold value, and the thin residual water films on the pore walls significantly affect the threshold pressure. Oil droplet can invade pores narrower than their diameter, and the energy cost for their invasion can only be computed accurately if the surface forces in the thin film formed between the droplet and pore surface are considered. In conventional reservoirs, thin brine films between oil droplet and rock greatly affect the wettability of oil droplets on the rock surface and thus the effectiveness of low-salinity waterflooding. In brine films with sub-nanometer thickness, the ion distribution differs from that near isolated rock surfaces but the structure of water-brine/rock interfaces is similar to their unconfined counterparts. The disjoining pressure in thin brine films and its response to the salinity change follow the trend predicted by classical theories, but new features are also found. A notable slip between the brine film and the oil phase can occur, which can facilitate the recovery of oil from reservoirs.

Research was conducted at Virginia Tech on a high-pressure uncooled plasma torch to study torch operational characteristics with hydrocarbon feedstocks and to determine the feasibility of using the torch as an igniter in scramjet applications. Operational characteristics studied included electrical properties, such as arc stability, voltage-current characteristics and start/re-start capabilities, and mechanical properties, such as coking, electrode erosion and transient to steady-state torch body temperature trends. Possible use of the plasma torch as an igniter in high-speed combustion environments was investigated through the use of emission spectroscopy and a NASA chemical kinetics code. All feedstocks tested; argon, methane, ethylene and propylene, were able to start. The voltage data indicated that there were two preferred operating modes, which were well defined for methane. For all gases, a higher current setting, on the order of 40 A, led to more stable torch operation. A low intensity, high frequency current applied to the torch, along with the primary DC current, resulted in virtual elimination of soot deposits on the anodes. Electrode erosion was found to multiply each time the complexity of the hydrocarbon was increased. Audio and high-speed visual analysis led to identification of 180 Hz plasma formation cycle, related to the three-phase power supply. The spectroscopic analysis aided in the identification of combustion enhancing radicals being produced by the torch, and results of the chemical kinetics analysis verified combustion enhancement and radical production through the use of a basic plasma model. Overall, the results of this study indicate that the plasma torch is a promising source for scramjet ignition, and further study is warranted. / Master of Science

Les structures d’échappement de fluides et leurs mécanismes de migration à travers la pile sédimentaire sont un phénomène connu sur les marges continentales. Elles ont été largement étudiées depuis une vingtaine d’années, notamment en raison de l’amélioration de la résolution des données sismiques, et de l’abondance des données dans ces zones, du fait de la prospection pétrolière. Le bassin du Bas Congo, au large de l'Afrique de l’ouest, est une province pétrolière prolifique qui a été largement étudiée et qui est exploitée depuis plus de 30 ans. La zone d’intérêt est située au-dessus d'un champ pétrolier producteur (la zone de Moho), dans laquelle les hydrocarbures sont piégés dans des chenaux turbiditiques. Le travail est principalement basé sur l'analyse de données géophysiques comprenant de la sismique 3D et 2D-THR, de la bathymétrie multifaisceaux et la rétrodiffusion correspondante, ainsi que des données de fond (échantillons prélevés, photos ROV, analyses géochimiques). L'analyse de cet important jeu de données sismiques a révélé de nombreuses évidences de migration de fluides dans la pile sédimentaire mio-pliocène. Ces dernières correspondent principalement à des indices de migration focalisée de fluides, incluant des structures actuelles d’expulsion de fluides sur le fond de l’eau et des structures enfouies, interprétées comme fossiles, et indiquant une activité ancienne du système d’expulsion de fluides. Les indices de migrations de fluides étudiés correspondent principalement à des pockmarks (dépressions) et à des cimentations carbonatées. Ces deux types d’indices peuvent s’empiler sur plusieurs centaines de mètres, mettant en évidence la pérennité des échappements et suggérant le développement de véritables conduits.Un nouveau type de pockmarks a été mis en évidence, les structures en araignée, qui sont localisées au-dessus d'un réservoir turbiditique, et qui résultent d'une migration focalisée des hydrocarbures thermogéniques. Leur fonctionnement est lié aux hydrates de gaz dans le contexte d’un BSR penté (Bottom Simulating Reflector), du fait de la présence du biseau des hydrates. Un modèle dynamique de leur fonctionnement est développé, montrant que ces structures se développent vers l'amont de la pente, du fait de la migration du gaz sous le BSR penté. Une étude du BSR, dans le contexte particulier du biseau des hydrates, permet de proposer un modèle des échappements de gaz liés à la dissociation des hydrates, lors d'une baisse du niveau marin. Ce modèle met en scène une dissociation des hydrates de gaz d'échelle régionale (associée à du gaz biogénique), localisée au niveau du biseau des hydrates du dernier bas niveau marin. Enfin, le réseau de structures d’échappements de fluides de l’intervalle Mio-Pliocène a été investigué dans le but de comprendre son architecture et les mécanismes de migration de fluides dans la zone d’étude. Les hydrocarbures semblent migrer principalement le long de certaines portions de failles et verticalement à travers la pile sédimentaire sous forme de « pipes » ou de cheminées. La base du Pliocène, associée à une baisse du niveau marin, marque la formation des premières paléo-araignées ainsi que d'un niveau contenant de nombreux indices de présence de gaz. Un modèle de ce réseau de migrations de fluides est proposé, intégrant les chemins de migrations des hydrocarbures à travers la pile sédimentaire, et l’événement majeur de la base Pliocène. Cette étude semble indiquer que les phases de baisse du niveau marin constituent des déclencheurs pour la migrations des fluides dans les bassins.Ce travail marque ainsi le point de départ d'une investigation à plus grande échelle qui consiste d'une part à rechercher des structures similaires (araignées et bandes de pockmarks) dans d'autres bassins et d'autres part à comparer les événements d'échappement de fluides à la courbe eustatique. / Evidence of fluid flow features and their mechanisms of migration through the sedimentary pile are a known phenomenon on continental margins. It has been widely studied over the past twenty years, notably due to the improved resolution of seismic data and the abundance of data in these areas due to oil and gas exploration.The Lower Congo basin, offshore West Africa, is a prolific petroleum province that has been extensively studied, and has been in operation for over 30 years. The area of interest is located above a producing oil field (the Moho license), in which hydrocarbons are trapped in turbidite channels. The work is primarily based on the analysis of geophysical data including 3D and 2D-THR seismic, multibeam bathymetry and corresponding backscatter, as well as background data (samples taken from ROV photos, geochemical analyses).The analysis of this important seismic dataset revealed abundant evidence of fluid migration in the Mio-Pliocene sedimentary pile. They mainly correspond to indications of vertically focused migration, including current fluid expulsion structures on the seafloor, and buried structures, interpreted as fossile and indicating former activity of the fluid expulsion system. The studied fluid migration features mainly consist of pockmarks (depressions) and carbonate cementations. These two types of indicators can build vertical stacks, over several hundred meters, highlighting the durability of the fluid escapes and suggesting the development of real pipes.A new type of pockmarks has been discovered, the spider structures, which are located above a turbiditic reservoir, and which result from a focused migration of thermogenic hydrocarbons. They are related to gas hydrates, in the context of a sloping BSR (Bottom Simulating Reflector), due to the presence of the hydrate wedge. A dynamic model of their functioning is proposed, showing that these structures develop upslope, due to the gas migration under the sloping BSR. A study of the BSR, in the particular context of the hydrates wedge, allows to propose a model of gas escapes, linked to the dissociation of the hydrates, during a sea level fall. This model presents a dissociation of gas hydrates of regional scale (associated with biogenic gas), localized at the gas hydrate wedge zone of the last lowstand. Finally, the network of fluid escape structures of the Mio-Pliocene interval was investigated in order to understand its architecture and the mechanisms of fluid migration in the study area. Hydrocarbons appear to migrate mainly along certain portions of faults and vertically crosscutting the sedimentary pile through pipes or chimneys. The base of the Pliocene, associated with a sea level fall, marks the formation of the first paleo-spiders, as well as a level containing numerous evidence of gas. A model of this network of fluid migrations is proposed, integrating the indicators of hydrocarbon migrations through the sedimentary pile, and the major event of the Pliocene base. This study seems to indicate that a the sea level fall constitute a trigger for the fluids migrations, in the basin.This work thus marks the starting point of a larger-scale investigation which consists in, on the one hand, searching for similar structures (spiders and bands of pockmarks) in other basins ; and, on the other hand, by comparing fluid flow events with the eustatic curve.

<p>Chronic exposure to toxicant mixtures is a serious threat to environmental and human health. It is especially important to understand the effects of these exposures for contaminants, such as polycyclic aromatic hydrocarbons (PAHs), which are toxic, ubiquitous, and increasingly prevalent. Furthermore, estuarine systems are of particular concern, as they are highly impacted by a wide variety of pollutants; fish there are often exposed to some of the highest levels of contaminants of any vertebrate populations, along with other stressors such as fluctuations in water level, dissolved oxygen, and temperature. A population of <italic>Fundulus heteroclitus</italic> (the Atlantic killifish or mummichog, hereafter referred to as killifish) inhabits a Superfund site heavily contaminated with a mixture of PAHs from former creosote operations; they have developed resistance to the acute toxicity and teratogenic effects caused by the mixture of PAHs in sediment from the site. The primary goal of this dissertation was to better understand the mechanism(s) by which Elizabeth River killifish resist the developmental toxicity of a complex mixture of PAHs and to investigate the tradeoffs associated with this resistance. Because the aryl hydrocarbon receptor (AHR) pathway plays an important role in mediating the effects of PAHs, one major hypothesis of my work was that suppression of the AHR response plays an important role in the resistance of Elizabeth River killifish. For this reason, investigation of the activation of the AHR pathway, as measured by CYP induction, is a unifying thread throughout the work. Another major hypothesis of this work is that adaptation to PAHs has secondary consequences for Elizabeth River killifish, such as altering their response to other xenobiotics. To investigate these hypotheses, a series of experiments were carried out in PAH-adapted killifish from the Elizabeth River and in reference fish. The morpholino gene knockdown technique was modified for use in killifish; we demonstrated that CYP1A knockdown exacerbates PAH-driven cardiac teratogenesis and AHR2 (but not AHR1) knockdown rescues PAH-driven cardiac teratogenesis. Using acute toxicity tests of larval killifish, we showed that Elizabeth River killifish are less sensitive than reference larvae to chlorpyrifos, permethrin, and carbaryl. These results demonstrated that the adaptation was able to protect from multiple xenobiotics, not just PAHs. Using the in ovo ethoxyresorufin-o-deethylase (EROD) assay and a subjective cardiac deformity screen, we showed that the adaptation was spread throughout the killifish subpopulations of the Elizabeth River estuary. However, the adaptive response varied greatly among the subpopulations, which showed that AHR pathway suppression was not required for some level of protection from PAH toxicity. Finally, using the quantitative real-time PCR, the EROD assay, and cardiac deformity screening, we demonstrated that the adaptation was heritable for two generations of fish reared in clean laboratory conditions. The findings in this dissertation will help to reveal how mixtures of PAHs exert their toxic action in un-adapted organisms. Furthermore, these studies will hopefully demonstrate how chronic exposure to PAH mixtures can affect organisms at the population and even evolutionary level. Perhaps most importantly, they will help us to better predict the consequences and tradeoffs for organisms and populations persisting in PAH-contaminated environments.</p> / Dissertation

Diss. (sammanfattning) Stockholm : Karol. inst., 2002. / Härtill 3 uppsatser.

Diss. (sammanfattning) Stockholm : Karol. inst., 2003. / Härtill 4 uppsatser.

Diss. (sammanfattning) Stockholm : Karol. inst., 2004. / Härtill 6 uppsatser.