Slope-channels act as conduits that transport sediments from the shelf staging area to the basin floor. The Pliocene-Pleistocene section of the Columbus Basin in the deep-water slope offshore eastern Trinidad provides an opportunity to study slope-channel morphology and evolution, as well as any association between deep-water deposits, palaeo-seafloor bathymetry, shelf sediment feeder mechanism and changes in sediment supply types and volumes. Approximately 3250 km2 of 3D seismic data allow imaging and interpretation of channels within an interval between two regional surfaces termed P30 and P40. Observations of seismic cross-sections and stratal slices reveal a number of features including channels, mud diapirs, mass transport deposits (MTDs), and faulted anticlinal ridges. Channels appear leveed and unleveed, and alternate with MTDs in a cyclic vertical succession. Nineteen channels were mapped and divided into two groups based on their degree of levee development and stratigraphic position relative to MTDs. Group 1 channels, positioned below MTDs near the base of the interval, are shallowly incised, and show limited levee development. Group 2 channels, situated above MTDs, are relatively deeply incised, and have comparatively larger, well-developed levees throughout their lengths. Morphometric data from these channel groups reveal significant variability in channel width, channel depth, meander belt width, and sinuosity downslope. This variability is associated with influences of temporally equivalent local features and regional sea-floor slope changes. Increased slope gradient causes a marked increase in sinuosity. Diapirs and anticlinal ridges confine channel paths, divert their flow, and cause post-depositional deformation of both levees and channels. Levee height decreases downslope while levee width shows considerable asymmetry, which is related to occurrences of mud diapirism and MTDs. Irregularities on the upper surface of MTDs create accommodation space that confines turbidity flows, enabling ponding of sediments and volumetrically large levee construction. This accounts for dispersion of turbidity flows below the MTD which creates a series of small channels spread over a wide area, and comparatively fewer, confined channels above the MTDs with large levees. / text

Degassing and in situ formation of a mobile gas phase takes place when an aqueous phase equilibrated with a gas at a pressure higher than the subsurface pressure is injected in water-saturated porous media. This process, which has been termed supersaturated water injection (SWI), is a novel and hitherto unexplored means of introducing a gas phase into the subsurface. Herein is a first macroscopic account of the SWI process on the basis of continuum scale simulations and column experiments with CO2 as the dissolved gas. A published empirical mass transfer correlation (Nambi and Powers, Water Resour Res, 2003) is found to adequately describe the non-equilibrium transfer of CO2 between the aqueous and gas phases. Remarkably, the dynamics of gas-water two-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional two-phase flow theory which allows the corresponding gas phase relative permeability to be determined. A key consequence of the finding, that the displacement of the aqueous phase by gas is compact at the macroscopic scale, is consistent with pore scale simulations of repeated mobilization, fragmentation and coalescence of large gas clusters (i.e., large ganglion dynamics) driven entirely by mass transfer. The significance of this finding for the efficient delivery of a gas phase below the water table in relation to the alternative process of in-situ air sparging and the potential advantages of SWI are discussed. SWI has been shown to mobilize a previously immobile oil phase in the subsurface of 3-phase systems (oil, water and gas). A macroscopic account of the SWI process is given on the basis of continuum-scale simulations and column experiments using CO2 as the dissolved gas and kerosene as the trapped oil phase. Experimental observations show that the presence of oil ganglia in the subsurface alters gas phase mobility from 2-phase predictions. A corresponding 3-phase gas relative permeability function is determined, whereas a published 3-phase relative permeability correlation (Stone, Journal of Cana Petro Tech, 1973) is found to be inadequate for describing oil phase flow during SWI. A function to predict oil phase relative permeability is developed for use during SWI at high aqueous phase saturations with a disconnected oil phase and quasi-disconnected gas phase. Remarkably, the dynamics of gas-water-oil 3-phase flow, observed in a series of SWI experiments in homogeneous columns packed with silica sand or glass beads, are accurately predicted by traditional continuum-scale flow theory. The developed relative permeability function is compared to Stone’s Method and shown to approximate it in all regions while accurately describing oil flow during SWI. A published validation of Stone’s Method (Fayers and Matthews, Soc of Petro Eng Journal, 1984) is cited to validate this approximation of Stone’s Method.

The continental margin off Nova Scotia (the Scotian margin) forms the northern edge of the North American Basin. The Cenozoic stratigraphy and geological history of the outer margin is not well known. This study examines aspects of the Upper Cretaceous-Cenozoic geological history of the outer Scotian margin addressing the following objectives: 1) determine the geological history of a large deep-water depocenter, 2) investigate processes that led to deep-water unconformity formation in the study area, 3) determine the role of deep-ocean circulation in margin evolution, 4) examine the effects of morphological heritage on subsequent depositional patterns. High quality 2-D and 3-D seismic reflection data along with lithostratigraphic and biostratigraphic data from hydrocarbon exploration wells provide the basis for this investigation. The seismic stratigraphy of a large deep-water depocenter along the western Scotian margin was broadly divided into four units. Unit 1 (Upper Cretaceous-Upper Eocene) is attributed to repeated, widespread erosion events interspersed with periods of hemipelagic and pelagic, carbonate-rich sedimentation. Unit 2 (Lower Oligocene-Middle Miocene) consists of a variety of seismic facies overprinted by dense, small-offset faults. Unit 3 (Middle Miocene-Upper Pliocene) is dominated by sediment drift deposition. Unit 4 (Upper Pliocene-present) is characterized by channel development and gravity flow deposition. The processes that led to regional seismic stratigraphic horizons were complex. Both large mass-wasting events and along-slope bottom currents contributed to the formation of unconformities in the study area. Most of the succession preserved in the depocenter belongs to seismic units 2 and 3. These deposits are mainly confined to the area seaward of the Abenaki carbonate bank and landward of shallow salt structures below the slope. Locally, however, modification of the slope profile through mass-wasting and bottom current processes greatly influenced subsequent depositional patterns. The Cenozoic geological evolution of the study area was strongly affected by northeast-to-southwest flowing bottom currents. The earliest indication of bottom current activity was in the Eocene. Upper Miocene and Pliocene sediment drifts represent >50% of the preserved stratigraphic section in the thickest part of the depocenter. It is clear that along-slope sedimentary processes were far more important in shaping the margin than previously understood.

The remediation of soil contaminated with polycyclic aromatic hydrocarbons (PAHs) is endorsed by environmental protection agencies worldwide. Recent studies demonstrated the removal of these contaminants from soil utilizing polymer beads, with subsequent PAH release and degradation in solid-liquid two phase partitioning bioreactors (TPPBs). Although such a process was successful, significant mass transport limitations involving PAH release from the polymers hampered productivity. The current work examined the possibility of applying sonication in solid-liquid partitioning systems to enhance delivery and degradation of PAHs. Small scale physical testing revealed delivery rates of PAHs from Desmopan, increased by 5 fold under intermittent sonication relative to non-sonicated conditions. Enhancements were also displayed as shifts to higher release equilibria under sonicated conditions, agreeing with sonochemistry concepts. Improvements were demonstrated across a range of polymers, suggesting that sonication could enhance PAH release with any polymers deemed feasible for environmental applications. A PAH-degrading microbial consortium was enriched, and it was demonstrated that sonication also improved the rate of phenanthrene degradation delivered from Desmopan by four times, confirming transport improvements while minimizing cellular inactivation effects. A mass transport analysis showed that without sonication, delivery of PAHs was restricted by the external resistance at the solid-liquid interface. Ultrasound was shown to enhance both external and internal transport properties, allowing rates not achievable through increased liquid mixing. Diffusivities quantified with and without ultrasound decreased as a function of permeant molecular size. Additionally, partitioning coefficients under sonicated and non-sonicated conditions decreased with PAH molecular size. Finally, an examination of permeant property data demonstrated that polarizability was the best descriptor of thermodynamic and transport behaviour in solid-liquid systems. The possibility of inducing equivalent improvements was investigated in a bench scale TPPB, in which sonic exposure improved degradation rates of phenanthrene by 2.7 fold when delivered from Desmopan. A window of on/off operation for ultrasonic cycling was also demonstrated, providing potential for optimizing sonication via rational selection of exposure times. DNA analysis also revealed that the consortium composition was maintained in the presence of sonication and also demonstrated that the consortium was comprised of bacteria belonging to the Pandoraea, Sphingobium, and Pseudoxanthomonas genera. / Thesis (Master, Chemical Engineering) -- Queen's University, 2009-08-26 13:04:26.229

This thesis presents the recent progress of diffusion measurements in nanoporous host systems by micro-imaging. Interference microscopy is applied as a powerful tool to record transient, intracrystalline concentration profiles of different sorbate species in the porous framework of two different zeolites, viz. ZSM-5 (MFI) and ZSM-58 (DDR). These profiles, yielding high temporal and spatial resolutions of about 10 s and 0.45 μm, follow the change of the refractive index of the host-guest system during uptake and release of certain guest molecules. With the thus accessible changes of concentration and particle fluxes, mass transport parameters, such as intracrystalline diffusivity and surface permeability, can be obtained by the use of the very fundamental equations on diffusion. Additionally, in two examples of never before performed types of experiments, further insights into challenging fields of host-guest interactions are provided: The well known phase transition in MFI type zeolites covering high benzene loadings is investigated in a single crystal study, allowing to follow the change of the sorbate phase in great detail. Furthermore, in DDR zeolites, a new way of data analysis facilitates to study the uptake and release of binary mixtures. Here, from the two-dimension profiles obtained by interference microscopy, the local concentrations of the sorbate species could be retrieved by using the so-called ideal adsorbed solution theory.

Nowadays, the development of novel materials involves diverse branches of science as a consequence of the new requirements imposed by modern society. This includes aspects ranging from the optimization of the manufacturing processes to the durability of the materials themselves. Ideally, some synergism should exist between the durability, the properties of interest in the material. Although metals in their pure state are often desired, the best properties or combination of properties often cannot be satisfactorily achieved with a single metal. In these situations, the desired properties can be attained by the formation of alloys of these metals with others. Ni-Co alloys are no exceptions and so have received considerable attention especially in microsystem technology due to the magnetic properties of cobalt and the corrosion and wear resistance of nickel. Moreover, this interest has been further stimulated by its use in the manufacture of sensors, magnetic devices, microrelays, inductors, actuators, memory devices and hard drives. The fabrication of these alloys (particularly coatings) via electroplating has been shown to be techno-economically feasible in comparison with other processes: capability of high volume production, low cost and the ability to coat thin layers on non-planar substrates. In addition, the materials fabricated by this technology exhibit excellent characteristics such as refined grain structure, smoothness, low residual stress and coercivity, etc., making them advantageous to materials produced by other physical methods of deposition. Nevertheless, one of the biggest problems faced during the formation of Ni-Co alloys is its anomalous behavior whereby cobalt preferentially deposits over nickel under most conditions, even when the Ni(II) concentration is significantly higher than that of Co(II). This problem has complicated the prediction and control of the metal composition in these alloys during their production and as a consequence the ability to obtain the desirable properties associated with high nickel content. Although this problem is not recent, the studies that have been carried out so far to analyze this system have not always been as comprehensive as they could be in terms of the experimental conditions investigated or the reaction mechanisms and mathematical models developed to describe its behavior. Consequently, the origin of this behavior is still not completely understood. Thus, this work presents a contribution in terms of the analysis of the reaction mechanisms for single metal deposition of nickel and cobalt and for the formation of Ni-Co alloys in sulphate media with the intention of gaining a better understanding of the phenomena controlling the anomalous behavior of this system. Analyses of the single metal deposition of nickel and cobalt are first carried out to better understand their reaction mechanisms. Such an approach should allow the contributions of the reduction of each metal ion and interactions between the two systems during alloy co-deposition to be more clearly understood. In order to analyse the aforementioned systems, both steady state and transient techniques are employed. Among these techniques, electrochemical impedance spectroscopy (EIS) is employed since it is a robust and powerful method to quantitatively characterize the various relaxation phenomena occurring during the electrodeposition of metals. The experimental data acquired from this technique are analyzed with comprehensive physicochemical models and the electrochemical processes are quantified by fitting the models to these data to determine the kinetic parameters. During the development of the physicochemical models, several assumptions (e.g. neglect of convection, homogeneous reactions and single electron-transfer steps) made in former models are relaxed in order to investigate their combined impact on the predicted response of the system. Estimates of the kinetic parameters determined by EIS for the deposition of the single metals reveals that the first step of Co(II) reduction is much faaster tha the corresponding step of Ni(II) reduction. Some limitations of the EIS technique (i.e. analysis at high overpotentials) are exposed and compared in the case of the nickel deposition using linear sweep voltammetry (LSV). Likewise, physicochemical models accounting for most of the important phenomena are derived and fitted to experimental data. Ni-Co alloy formation is analyzed using LSV and steady state polarization experiments for different pH, current density and electrolyte composition. Current efficiencies for metal depsoition and alloy composition are also evaluated. To date, no experimental study considering all these variables has been reported in the literature. Then a steady state model is presented to describe the electrode response during alloy formation and used to provide insight into the anomalous behavior of this system. This model is based on information obtained from previous studies reported in the literature and from the current research. After being fitted to the experimental data, the model reveals that the anomalous behavior observed for this alloy is likely caused by the much faster charge-transfer of Co(II) reduction than that of Ni(II) reduction and not by other previously proposed mechanisms such as competition between adsorbed species for surface sites, formation of aqueous hydroxides (MeOH+) or mixed intermediate species (NiCo(III)ads) on the surface of the electrode.

L'électrochimie permet la mise en œuvre de techniques de détections pertinentes et adaptées aux contraintes de miniaturisation imposées par la conception de laboratoires sur puce. L'objectif de la thèse a été d'étudier la détection d'espèces électroactives circulant à l'intérieur d'un canal microfluidique, sous la forme de gradients de concentration localisés, ou d'espèces contenues à l'intérieur de gouttes. Pour cela, deux approches ont été menées au moyen d'électrodes microbandes intégrées dans des microcanaux. La première a été d'étudier la possibilité de générer puis de détecter électrochimiquement de façon contrôlée des gradients de concentration en écoulement monophasique. Les réponses ampérométriques ont été analysées en fonction des caractéristiques des gradients de concentration après les phases de génération et de propagation. Deux comportements limites ont été mis en évidence par simulations numériques puis vérifiés expérimentalement. La seconde approche a été de mettre en œuvre une détection électrochimique du contenu de gouttes en écoulement diphasique. L'enjeu a été à la fois de démontrer la faisabilité des mesures mais aussi d'établir des relations entre les courants mesurés et les concentrations ou quantités d'espèces à l'intérieur des gouttes. Dans ce cadre, un microdispositif innovant a été proposé puis testé expérimentalement, démontrant la possibilité d'effectuer des électrolyses totales de gouttes. / Electrochemistry enables the implementation of relevant and appropriate detection techniques to the miniaturization constraints imposed by the design of labs-on-a-chip. The aim of this thesis was to study the detection of electroactive species flowing within microfluidic channels under the form of concentration gradients or microdroplets. Therefore, two approaches were undertaken by means of microband electrodes integrated within microchannels. The first one was to study the opportunity to control the electrochemical generation and detection of concentration gradients in continuous flow. The amperometric responses were analyzed as a function of the characteristics of concentration gradients after the generation and propagation processes. Two boundary behaviours were evidenced by numerical simulations and validated experimentally. The second approach was to implement the electrochemical detection of droplet content in segmented flow. The challenge was both to demonstrate the feasibility of the experiments and to introduce relationships between currents and concentration or amount of species inside droplets. In this context, an innovative microdevice was designed and tested experimentally allowing the total electrolysis of the droplets.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Este trabalho desenvolveu uma metodologia, com base na aplicaÃÃo da teoria fuzzy, em modelos de transporte de poluentes, para estudar o risco fuzzy de contaminaÃÃo, na concessÃo de outorga de lanÃamentos de efluentes em rios. Para isso, as equaÃÃes diferenciais do modelo de transporte sÃo transformadas em equaÃÃes diferenciais fuzzys, de modo que o campo de concentraÃÃes representado pelo modelo matemÃtico seja transformado em campos de funÃÃes de pertinÃncias de concentraÃÃes. O estudo se utiliza de parÃmetros definidos na lei para estabelecer a classe do rio e, assim, calcular, para cada tipo de lanÃamento, o risco de contaminaÃÃo e a capacidade de assimilaÃÃo do mesmo. Para a soluÃÃo do modelo matemÃtico foi usado o mÃtodo das diferenÃas finitas, com esquema implÃcito para o equacionamento das equaÃÃes das diferenÃas. Para a realizaÃÃo das simulaÃÃes foi desenvolvido um programa computacional, em linguagem FORTRAN que deu suporte na obtenÃÃo dos resultados para os mais diversos cenÃrios propostos. Os resultados mostraram que a teoria fuzzy pode se tornar uma alternativa segura no auxilio do controle de poluiÃÃo dos rios em geral, fornecendo, assim, fundamentos para a gestÃo dos recursos hÃdricos / This research developed a methodology, based on application of fuzzy theory in the pollutant transport models, to study the fuzzy risk of contamination, in awarding grants for discharge of effluents into rivers. In such way, the differential equations of the transport model are transformed into fuzzy differential equations, so that, the field of concentrations, represented by the mathematical model is transformed into fields of concentration membership functions. The study makes use of parameters defined in the law to establish the class of the river, so that, it calculates, for each type of release, the risk and its assimilative capacity of the river to receive effluents. For the solution of the mathematical model the finite difference method was used, with implicit scheme on order to get the difference equation. For the accomplishment of the simulations a computational program, in FORTRAN language, was developed, that gave support in the obtaining of the results for the most several proposed sceneries. The results have shown that the fuzzy theory can become a safe alternative to help control pollution of rivers in general, providing, in such way, subsidies for resources management

Torres de resfriamento são equipamentos muito utilizados na indústria e que muitas vezes operam sob condições adversas, particularmente, temperatura de água acima dos 50°C na entrada da torre. Nesta condição, tem-se alta taxa de evaporação e eventualmente condição de alto transporte de massa, normalmente não considerado no equacionamento de torres de resfriamento. Apresenta-se assim uma análise comparativa de diferentes métodos de cálculo de torres de resfriamento: Merkel, Poppe e o modelo proposto. No modelo proposto neste estudo, consideram-se os balanços diferenciais de massa e energia e os mecanismos de transporte simultâneo de calor e massa, na condição de alto transporte de massa e de supersaturação do ar, caso o vapor de água condense na forma de névoa. Para os casos em que há saturação do ar, os balanços diferenciais de massa e energia passam a contemplar este fenômeno a partir do momento em que ocorre a saturação. O modelo matemático desenvolvido consiste de equações diferenciais ordinárias e equações auxiliares, e foi implementado em uma interface Matlab. Os principais parâmetros investigados foram: as vazões de água e ar, a temperatura de bulbo úmido do ar, a temperatura da água na entrada da coluna e a altura da torre. A partir das simulações matemáticas, foram obtidos resultados de temperaturas do ar, da água e da umidade do ar ao longo da coluna, para os diferentes métodos. / Cooling towers are equipment widely used in industrial plants, where these operate under severe conditions such as cooling water inlet temperatures above 50oC. Under this condition, there are high evaporation of water and high mass transfer, generally not considered in performance analysis of a cooling tower. This work presents and analyzes the differences between the proposed model and the Merkel and Poppe approaches. The proposed model in this work is based on differential equations for energy and mass balances and on the mechanisms of combined heat and mass transfers, at high mass transfer condition and considering the supersaturated air from the height of the tower that the excess of water vapor condenses as a mist. At the point that the air became supersaturated, the differential equations for energy and mass balances start to consider the supersaturation phenomena. The mathematical model developed in this work is composed by ordinary differential equations and auxiliary equations which were solved at Matlab. The parameters investigated were water and air mass flow rates, air wet bulb temperature, water inlet temperature and tower height. The results of air and water temperatures, humidity air across the tower height are presented for each method analyzed.

No description available.