Manito Lake is a large, perennial, Na-SO4 dominated hypersaline lake located in the northern Great Plains of western Canada. Significant water level decrease over the past several decades has lead to reduction in volume and surface area. Today, the lake is 15% of its mid -20th century volume and 46% of its former area. This decrease in water level has exposed large areas of nearshore microbialites. These organosedimentary structures have various external morphologies, vary in mineralogical composition, and show a variety of internal fabrics from finely laminated to massive and clotted. These features range from small, mm-scale, finely laminated encrustations to large, reef-like structures up to 5 m high and over 500 m long. Although there is relatively little consistent lateral variability in terms of morphology, the structures do vary significantly with elevation in the basin. Petrographic evidence confirms a strong biological involvement in the formation of these structures. Nonetheless, inorganic and trapping mechanisms may also play a role. Dolomite, aragonite, and calcite are the most commonly found minerals in these structures, however, monohydrocalcite, magnesian calcite, hydromagnesite, dypingite, and nesquehonite are also present. The calcite is a pseudomorph after ikaite, which forms an open porous dendritic and shrub-like fabric, comprising the interiors of massive shoreline microbialite mounds and pinnacles. These ikaite pseudomorphs are encased in millimeter to centimeter-scale laminated dolomite-aragonite rinds. Radiocarbon dating and stable isotope analysis have indicated microbialite formation began about 2200 yBP in a shallow, productive, saline and cold lake. Over the next 900 years, the microbialites record a transgressing lake in a cool climate, which corresponds to a period not previously documented in this region but is referred to as the Dark Ages Cold Period, which has been documented in other parts of the Northern Hemisphere. This is followed by 500 years of warmer conditions coinciding with the Medieval Climate Anomaly. Starting about 600 years ago the lake experienced a dramatic decrease in level resulting in formation of extensive carbonate pavements, cemented siliciclastics, rinds, and coatings.

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

Carbonate preservation in the oceans occurs at a depth called the carbonate compensation depth (CCD). The CCD is where the input rate of carbonate from the surface of the ocean is balanced by the dissolution rate. Factors controlling the CCD are the CO2 in the atmosphere, weathering, and productivity in the surface water, the depth of the lysocline and deep water currents (and their ocean circulation). Two previous studies have investigated the variation of the CCD through geologic time, one in the equatorial Pacific (Pälike et al., 2012) and the other compiled results from the Pacific, Atlantic and Indian Oceans (Van Andel, 1975). The project consisted of compiling a database of sediment lithologies for many more sites in the Atlantic since the compilation by Van Andel, 1975, and together with a subsidence model of the ocean crust the systematic variations of CCD could be investigated. The results show that the CCD varies both spatially and temporally in accordance with previous studies. The reconstruction of the CCD needs further analysis, and possibly data from the oldest drilling program, the Deep Sea Drilling Project (DSDP). One result that is very important is that this study includes a total of 91 sites in the Atlantic Ocean, far more than in any of the other two studies. Future work can build upon the already started database of sediment lithologies.

Une fois déposé, un sédiment est affecté au cours de son enfouissement par un ensemble de processus, regroupé sous le terme diagenèse, le transformant parfois légèrement ou bien suffisamment pour le rendre méconnaissable. Ces modifications ont des conséquences sur les propriétés pétrophysiques qui peuvent être positives ou négatives, c'est-à-dire les améliorer ou bien les détériorer. Une voie alternative de représentation numérique des processus, affranchie de l'utilisation des réactions physico-chimiques, a été adoptée et développée en mimant le déplacement du ou des fluides diagénétiques. Cette méthode s'appuie sur le principe d'un automate cellulaire et permet de simplifier les phénomènes sans sacrifier le résultat et permet de représenter les phénomènes diagénétiques à une échelle fine. Les paramètres sont essentiellement numériques ou mathématiques et nécessitent d'être mieux compris et renseignés à partir de données réelles issues d'études d'affleurements et du travail analytique effectué. La représentation des phénomènes de dolomitisation de faible profondeur suivie d'une phase de dédolomitisation a été dans un premier temps effectuée. Le secteur concerne une portion de la série carbonatée de l'Urgonien (Barrémien-Aptien), localisée dans le massif du Vercors en France. Ce travail a été réalisé à l'échelle de la section afin de reproduire les géométries complexes associées aux phénomènes diagénétiques et de respecter les proportions mesurées en dolomite. De plus, la dolomitisation a été simulée selon trois modèles d'écoulement. En effet, la dédolomitisation étant omniprésente, plusieurs hypothèses sur le mécanisme de dolomitisation ont été énoncées et testées. Plusieurs phases de dolomitisation per ascensum ont été également simulées sur des séries du Lias appartenant aux formations du groupe des Calcaire Gris, localisées au nord-est de l'Italie. Ces fluides diagénétiques empruntent le réseau de fracturation comme vecteur et affectent préférentiellement les lithologies les plus micritisées. Cette étude a permis de mettre en évidence la propagation des phénomènes à l'échelle de l'affleurement.

Recent work has described how gas exchange can occur through sea ice. First, carbon fluxes over sea ice surfaces have been measured. Second, sea ice brine has an elevated capacity over seawater to absorb CO2(g) due to its cold temperature and chemical equilibrium promoting carbon phase changes. Sea ice pCO2 profiles were collected using a new method of remotely sampling gas in situ via diffusive membranes placed within growing sea ice. Gas analysis was complimented by measurements of local meteorology and ice chemistry. The work was part of the CASES 2004 project. The observed elevation in sea ice pCO2 coupled with the mobility of the brine points to the role that brine plays in Arctic carbon transport. The gas transport links the Arctic atmosphere and ocean and indicates that a thinning and receding ice cover may not result in creating a negative feedback to the increasing atmospheric CO2(g) concentration.

Catalysis is an important field of study in chemical engineering and chemistry due to its application in a vast number of chemical transformations. Traditionally, catalysts have been developed as homogeneous molecular species or as heterogeneous insoluble materials. While homogeneous catalysts are typically very active and selective, they are difficult to recover. Conversely, heterogeneous catalysts are easy to recover and reuse, but they generally are less selective. To address these issues, the immobilization of homogeneous catalyst analogs onto solid supports has been a subject of research for the past few decades. Nonetheless, the effects of immobilization are still not completely predictable, and so continued effort is required to develop new immobilized catalysts as well as to develop a better understanding of how different parameters affect catalytic behavior. This dissertation presents the synthesis, characterization, and evaluation of new immobilized catalysts for different applications. First, a solid base catalyst supported on silica was developed and studied in the synthesis of cyclic carbonates from epoxides and carbon dioxide. Next, polymer and silica supported vanadium Schiff base catalysts were developed and evaluated for use in the oxidative kinetic resolution of alpha-hydroxy esters, an enantioselective reaction. Lastly, salen catalyst analogs with amine reactive functional groups were synthesized and characterized for grafting onto aminosilicas with different degrees of amine group isolation. The grafted catalysts were then tested to determine how catalyst spacing on the surface affects their behavior. Throughout the presentation of these results, comparisons are made amongst the new supported catalysts and relevant existing catalysts to discern general trends which could be applied to a wider range of immobilized catalysts. Finally, research opportunities for further improvements in these areas are suggested.

The understanding of multiphase flow properties is essential for the exploitation of hydrocarbon reserves in a reservoir; these properties in turn are dependent on the geometric properties and connectivity of the pore space. The determination of the pore size distribution in carbonate reservoirs remains challenging; carbonates exhibit complex pore structures comprising length scales from nanometers to several centimeters. A major challenge to the accurate evaluation of these reservoirs is accounting for pore scale heterogeneity on multiple scales. This is the topic of this thesis. Conventionally, this micron scale information is achieved either by building stochastic models using 2D images or by combining log and laboratory data to classify pore types and their behaviour. None of these capture the true 3D connectivity vital for flow characterisation. We present here an approach to build realistic 3D network models across a range of scales to improve property estimation through employment of X-ray micro-Computed Tomography (μCT) and Focussed Ion Beam Tomography (FIBT). The submicron, or microporous, regions are delineated through a differential imaging technique undertaken on x-ray CT providing a qualitative description of microporosity. Various 3-Phase segmentation methods are then applied for quantitative characterisation of those regions utilising the attenuation coefficient values from the 3D tomographic images. X-ray micro-CT is resolution limited and can not resolve the detailed geometrical features of the submicron pores. FIB tomography is used to image the 3D pore structure of submicron pores down to a scale of tens of nanometers. We describe the experimental development and subsequent image processing including issues and difficulties resolved at various stages. The developed methodology is implemented on cores from producing wackstone and grainstone reservoirs. Pore network models are generated to characterise the 3D interconnectivity of pores. We perform the simulations of petrophysical properties (permeability and formation resistivity) directly on the submicron scale image data. Simulated drainage capillary pressure curves are matched with the experimental data. We also present some preliminary results for the integration of multiscale pore information to build dual-scale network models. The integration of multiscale data allows one to select appropriate effective medium theories to incorporate sub-micron structure into property calculations at macro scale giving a more realistic estimation of properties.

Doctor of Philosophy(PhD) / Soil Stiffness is an important parameter for any geotechnical engineering design. In laboratory tests it can be derived from stress-strain curves or from dynamic measurement based on wave propagation theory. The second method is a more accurate and direct method for measuring stiffness at very small strains. Until now dynamic measurements have usually been obtained manually from the triaxial test. Attempts have been made to automate the procedure but have apparently failed due to the high level of variability in dynamic measurements. Moreover, triaxial tests of soil can be very lengthy and manual dynamic measurements can be very tedious and impractical for long stress-path tests. In this research a computer program has been developed to automate the stiffness measurement (using bender elements) based on the cross- correlation technique. In this method the program records all the peaks and corresponding arrival times in the cross-correlation signal during the test. The stiffness is calculated and displayed on the screen continuously. The Bender Element enabled to get the small strain shear modulus. An arbitrary “Chirp” waveform of 4 kHz frequency was used for this purpose. Subsequently Bender Element test results were checked by ‘Sine’ waveforms of frequencies 5kHz to 20kHz, as well as by manual inspection of the arrival time. This thesis discusses the method and some of the difficulties in truly automating the process. Finally some results from a number of stress path tests on uncemented and cemented calcareous sediments are presented. Bender elements have been used by many researchers to determine the shear modulus at small strain. Most previous studies have used visual observation of arrival time, which is time consuming and often requires some judgement from the operator. This thesis will describe the use of cross-correlation as a method for automation of Gmax measurement. Cross-correlation has been claimed to be unreliable in the past. However, it will be shown that provided several peaks in the cross-correlation signal are monitored it is possible to follow the variation of Gmax throughout consolidation and shearing. The measurement can be made at regular intervals within the software controlling a stress-path apparatus. Details of the apparatus used and practical considerations including selection of waveform and frequency are discussed. A series of drained cyclic triaxial tests was carried out on artificially cemented and uncemented calcareous soil of dry unit weights 13, 15, and 17 kN/m3 and sheared with constant effective confining stress 300 kPa. Gypsum cement contents of 10%, 20% and 30% of the dry soil weight were used. In addition a series of stress path tests were performed on Toyuora sand samples. Results will be presented for two uncemented and one cemented sand. In addition to the bender elements, all tests had internal instrumentation to monitor axial and lateral strains. Results will be presented for Toyura sand to show that the measurements are consistent with those obtained by other methods. Results will also be presented for carbonate sand subjected to a wide range of stress paths. Finally, results will be presented for the carbonate sand cemented with gypsum. The degradation of Gmax of the cemented soil subjected to variety of monotonic and cyclic stress-paths is presented. Analysis of the results includes assessment of the factors influencing Gmax for uncemented sand. Preliminary analysis indicates that in order of importance these are the mean effective stress, the stress history, void ratio and stress ratio. For cemented sand, Gmax is initially constant and independent of stress path. After yielding the modulus degrades, becoming increasingly stress level dependent and eventually approaches the value for uncemented sand. Factors influencing the rate of degradation are discussed. For the Toyuora sand samples the effects of end restraint on the stress-strain response at small strains were investigated. The conventional method of mounting triaxial specimen has the effect of introducing friction between sample and end platen during a compression test. This inevitably restricts free lateral movement of the specimen ends. Frictional restraint at the sample ends causes the formation of 'dead zones' adjacent to the platens, resulting in non-uniform distribution of stress and strain (and of pore pressure if undrained). On the other hand the specimen with 'free' ends maintain an approximate cylindrical shape instead of barrelling when subjected to compression, resulting in a more uniform stress distribution.

Thesis (Ph.D.)--McMaster University (Canada), 1988. / Source: Dissertation Abstracts International, Volume: 62-13, Section: A, page: 0000.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 4 uppsatser.