The underlying objective of this research is to improve the overall understanding of how spatial and temporal variability in macroporosity and soil hydraulic properties in the shallow subsurface influence the long term mobility of agricultural nutrients, and specifically the movement of liquid swine manure, in macroporous, tile drained soils. The principal motivation for the work was to provide insight into dynamic nutrient mobility in this type of agricultural environment in order to guide both the efficiency and environmental sustainability of nutrient management practices. The results of this work facilitate the advancement of our conceptual understanding and our ability to simulate preferential flow and transport in structured agricultural soils that are subject to seasonal hydrologic patterns similar to those found in the humid continental climate of southwestern Ontario

A major challenge to cold regions hydrology and northern water resources management lies in predicting runoff dynamically in the context of warming-induced changes to the rates and patterns of ground thaw and drainage. Meeting this challenge requires new knowledge of the mechanisms and rates of ground thaw and their implications to water drainage and storage patterns and processes. The study carries out to evaluate the concept of energy-based runoff in the perspective of ground heat flux, soil thaw and liquid moisture content, tortuosity of snow-free area, preferential flow and discharge of the hillslope. Based on field measurements, coupled energy and water flow is simulated in the Area of Interest (AOI) with a half-hour time interval by the distributed hydrological model, GEOtop. In the field, the saturated hydraulic conductivity varies exponentially between the superficial organic layer and the underlying mineral layer. In the simulation, the parameters of the soil physical properties are input by fourteen uneven layers below the ground surface. Starting from the initially frozen state, the process of soil thaw is simulated with dynamic variables such as soil liquid moisture and ice content, hydraulic conductivity, thermal conductivity and heat capacity. The simulated frost table depths are validated by 44-point measurements and the simulation of point soil temperature is also compared to data measured in an excavated soil pit. As a result, the frost table topography is dominated by both the snow-free pattern and the energy fluxes on the ground surface. The rate and magnitude of runoff derived from snow drift and the ice content of frozen soil is greatly influenced by the frost table topography. According to the simulation, the frost table depth is closely regressed with the ground surface temperature by a power function. As soil thawing progresses, ground heat flux reduces gradually and the rate of soil thaw becomes small when the frost table descends. Along with the snow-free area expanding, the average soil moisture of the AOI increases prior to that time when the average frost table is less than 25 cm deep. The snow-free patches expand heterogeneously in the AOI, which causes the spatial and temporal variation of hydraulic conductivity due to the non-uniform frost table depth. According to the simulation, the transit time of the flow through the AOI decreases to the shortest span on May 13 with the average frost table of 10 cm. Before this date, the time lag between snowmelt percolation and slope runoff is about 8-10 hours; while after this date, the time lag is no more than 5 hours. The pattern of the preferential flow in the AOI highly depends on the frost table topography. When the snow-free patches are widely scattered and the average frost table is between 0 and 10 cm, the preferential flow paths are inhibited. With soil thaw progresses, the preferential flow paths are prominent with the largest single contributing area occurring when the average frost table is between 10 cm to 15 cm. When the average frost table reaches 25 cm, the importance of preferential flow is not apparent, and matrix flow prevails.

Univ., Diss.--Konstanz, 1994.

Doctor of Philosophy / Department of Chemistry / Paul E. Smith / Kirkwood Buff (KB) theory is one of the most important theories of solutions. The theory can relate integrals over radial (pair) distribution functions (rdfs) in the grand canonical ensemble to common thermodynamic properties. An inversion of the KB theory has been proposed by Ben-Naim and this has led to the wide spread popularity of KB theory. The idea of the KB inversion procedure is to calculate KB integrals from available thermodynamic properties. The KB theory can be used to validate the force field (ff) parameters used in molecular dynamics simulations. We have tested a series of small molecule ff parameters using KB theory that consists of both atom centered partial atomic charges and extra charge sites. The results indicate that using extra charge sites, derived from QM calculations, does not necessarily provide a more accurate representation of condensed phase properties. A further study aimed at an ongoing project of deriving new biomolecular ff parameters based on KB theory, has developed ff parameters for esters in order to represent the ester conjugation of the phospholipid molecule. The models were further tested against experimental properties. Preferential solvation (PS) is an important concept of solution mixtures that can be described using KB theory. The difference between local composition and bulk composition in solution mixtures leads to the concept of PS. A generalized explanation based on local mole fractions was derived by Ben-Naim using KB theory. However, the original expressions have been modified over years. Here, we propose a new approach based on local volume fractions to explore PS in binary and ternary solution mixtures. Experimental and simulation data were used to examine different approaches to PS. A relationship between the rdf and the triplet distribution function can be obtained using the Kirkwood Superposition Approximation (KSA). A combination of Fluctuation Solution Theory and experimental rdfs are used to examine the KSA at a series of state points for pure water. The accuracy of several other approximate relationships between the pair and triplet correlation functions was also investigated and are in good agreement for regions of the phase diagram where the compressibility is small.

A turbulência gerada em equipamentos de grade oscilante presta-se a uma série grande de comprovações experimentais de proposições teóricas. Isto ocorre tanto para a turbulência propriamente dita, como para os fenômenos de transporte a ela associados. Usualmente não se considera a presença de correntes preferenciais nas constatações experimentais conduzidas nesses equipamentos. Entretanto, para que as previsões teóricas possam ser definitivamente corroboradas, é preciso quantificar as correntes preferenciais e a sua forma, de modo que se possa inferir a sua influência nos fenômenos medidos. No presente estudo apresentam-se resultados da quantificação das correntes preferenciais em escoamentos gerados por grades oscilantes. / Turbulence generated by oscillating grids is used in a series of experimental procedures to support or to test theoretical proposals. This way to conduct the studies is usual for turbulence itself and also for associated transport phenomena. Usually the preferential currents are not taken into account during the experiments conducted in oscillating grids equipments. However, to definitively corroborate theoretical predictions, it is necessary to quantify the preferential currents and to determine the shape of the flow, in a way that permits to infer the effects on the measured phenomena. In the present study, results related to preferential currents generated in a stirred grid equipment are presented.

Unlike municipal water supplies, provincial regulations do not require systematic testing of domestic well water, which may adversely impact local residents should contamination occur. Private wells are typically shallow relative to municipal wells, and thus, are particularly vulnerable to sources of surficial contamination if preferential recharge pathways such as natural fractures or faulty seals are present. In order to determine the relative importance of well seal integrity as a preferential pathway, a practical detection method was developed based on infiltrometry. This method successfully detected faulty well seals in a wide range of geological settings across Canada, including: Hobbema, Alberta; Lindsay, Ontario; and Chelsea, Québec. It was most successful in areas of minimal heterogeneity and where the surficial geology is composed of fine-grained sediments. The community of Chelsea (Québec) was also the primary study site to examine a range of factors affecting water quality including physical characteristics, faulty well seals, other anthropogenic activities and seasonality. Water samples were collected over a period of 14 months and analyzed for bacteria and major-ion chemistry. The results show that the consideration of physical features alone is not enough to predict vulnerability in the study area. Seasonal fluctuations in ionic concentrations (e.g. ionic strength, NO3-N and Cl-) and coliform bacteria are observed and result from disperse and rapid recharge events. Multivariate analysis techniques (e.g. principal components analysis and hierarchical cluster analysis) demonstrate that preferential recharge pathways and anthropogenic activities, such as domestic effluents affect the groundwater quality. The data and findings of this study were used to assist in the design of a probabilistic risk assessment model based on the Poisson distribution. This study demonstrates the complexity and the challenges related to bacterial contamination in drilled wells. In spite of these challenges, this analysis was useful as a baseline to assess the impact of anthropogenic activities, and may be used in future studies to assist municipalities in the evaluation and protection of groundwater supplies.

My theses scope is description of the Spanish relationship to European Union from the first integration tendencies after the WW II till the preferential agreement ratification in 1970. I will try to analyze part of the Spanish economic history within the context of west-European integration. This period precedes the political transformation of autocratic Spain to modern democracy. These democratic cabinets were able to aspire seriosusly to fully-fledged European Union membership. In my opinion it is not possible to view political transformation as a start-up for democratically elected governments to setup new relationships with EU but it is necessary to understand it as an important condition which is part of a long-term process of Spanish convergence to west-European integration. In my theses I primarily concentrate on the economic development but I mean that it is important to mention the political situation as well.

Cette thèse a été effectuée dans le cadre du projet ANCRES. Son rôle est d'assurer la compréhension physique du milieu récepteur, le sol, alors qu'une autre équipe étudie l'impact physico-chimique des eaux usées traitées sur le sol. Pour cela, il faut connaître ses propriétés texturales et structurales contrôlant ses fonctions d'épuration et d'évacuation. La problématique est donc de comprendre le processus de l'infiltration imposée par un dispositif d'ANC dans un sol caillouteux. D'abord, suite au positionnement du site pilote d'ANC au pied d'un versant au cœur du plateau portlandien dans le département de l'Yonne en France, on a identifié là un type de sol hétérogène et complexe, caillouteux, une colluvion qui n'était pas cartographiée sur la carte géologique BRGM de cette région et sur laquelle on focalise la thèse. Ensuite, dans le sol complexe du site pilote, on a d'abord mesuré la conductivité hydraulique du sol par l'appareil Guelph sur 15 m² de la fouille de l'ANC à une profondeur de 120 cm : au total, on a fait 15 essais d'infiltration. De plus, on a récupéré 15 échantillons du sol accompagnant ses essais de Guelph pour la caractérisation physique au laboratoire. On a mesuré la texture, l'humidité résiduelle (HR), la teneur en cailloux (Rw) et la matière organique (MO) des échantillons au laboratoire. Ensuite, pour l'étude du processus d'infiltration, on a instrumenté ce site par un dispositif de surveillance hydrique (tensiométrie, teneur en eau, piézométrie) et de prélèvement d'eau interstitielle du sol. De plus, la masse volumique (densité) apparente d'un sol hétérogène a été déterminée. Parmi les paramètres mesurés, certains sont choisis comme indicateurs pour caractériser un sol comme milieu récepteur potentiel des eaux usées traitées en ANC. Puis, en utilisant la MO et la texture des échantillons, on a estimé la masse volumique apparente de la matrice du sol du site piloteau moyen de fonctions de pédotransfert appelées BD-FPTs et on a testé la relation entre la conductivité hydraulique à saturation Ks et la texture de ce sol complexe. Pour cela, une méthodologie en quatre phases a été développée pour évaluer la capacité prédictive des fonctions Ks-FPTs. Cette méthodologie de sélection n'a pas été trouvée dans la littérature mais est élaborée pour les besoins de la thèse. On a déduit les meilleures Ks-FPTs pour ce type de sol. Enfin, avec les données d'humidité volumique et du potentiel matriciel du sol, acquises par une centrale d'acquisition des données, le régime hydrodynamique du sol sous le massif filtrant de l'ANC a été étudié et on a mis en évidence l'écoulement préférentiel dans un sol caillouteux. Les résultats ont montré que dans la colluvion, bien que la matrice du sol soit fine, la conductivité hydraulique mesurée est plus élevée qu'attendu. Cela démontre que la fraction des cailloux dans le sol joue un rôle essentiel en accélérant l'évacuation des eaux usées traitées et aussi l'eau pluviale vers les couches sous-jacentes, et finalement vers la nappe. Cette propriété serait un point fort pour la fonction de transfert du sol et on peut en déduire une méthode pour améliorer la capacité de transfert de l'eau des sols lourds dans les projets d'aménagement urbain ou périurbain : l'ajout de graviers et graves calcaires par mélange au sol en place. On conclut que cette expérimentation, unique en son genre, a été utile pour évaluer la fonction de rétention / transfert de l'eau dans le sol recevant les eaux usées traitées. On a identifié les paramètres prédicteurs pertinents et les relations empiriques qui permettent de faire l'économie de nombreux essais in situ d'eau / The soil is an essential compartment in hydrologic cycle of water in the nature. Therefore, it is clear that taking into account the properties and organization of the soil is essential to the understanding and management of flows involved in the development of the quality of groundwater and surface water. The on-site sanitation (ANC) is a management method of domestic wastewater, by which the water is sent into the soil after settling and filtration liquefaction / aerobic degradation. The second step was often provided by the top soil in place himself, and this continues to this day on many plots of on-site sanitation.This thesis was carried out under ANCRES project. Its role was to ensure the physical understanding of the receptor medium, soil, while another research team was investigating the physico-chemical impact of treated wastewater on the sol. To ensure it, we have to understand its textural and structural properties controlling its purifying power and hydrodynamic processes. So, the problematic is to understand the process of infiltration imposed by an ANC in a heterogeneous stony soil. At first, due to the positioning of the pilot ANC site, at the foot of a slope in the Yonne department in France, a type of complex and heterogeneous soil, a colluvion, was identified. This soil has not been mapped on the BRGM (Bureau de recherches géologiques et minières) geological map of the area. So, the thesis was focalised on this soil. Then, in this soil complex at a depth of the 120 cm of the excavation of the ANC, the soil hydraulic conductivity was first measured by a Guelph apparatus on 15 m². We totally made 15 infiltration tests. Furthermore, we have collected 15 soil samples with each Guelph test for physics laboratory physical characterization. Then, in order to study the soil functions, this site was instrumented by the water monitoring devices (tensiometers, water content probes, and piezometer) and the interstitial water sampling device from the soil. In addition, the bulk of this heterogeneous soil was determined. Among the measured parameters, a series of indicators chosen to characterize the soil as a potential receptor medium of treated wastewater of the ANC. Then, the bulk density of the soil matrix using pedotransfer functions called BD-FPTs was estimated and the relationship between saturated hydraulic conductivity Ks and the texture of the soil complex (by Ks-FPT function) was tested. For this aim, a four-phase methodology was developed to assess the predictive ability of Ks- FPTs functions. This methodology in four phases is not found in the literature but was prepared for the purposes of the thesis. We concluded the best Ks- FPTS for this type of soil. Finally, with the volumetric water content and soil matrix potential data acquired by a the data loggers, the hydrodynamic regime of the soil under the sand pack of the ANC has been studied and demonstrated the preferential flow in a stony soil was demonstrated. The results showed that in the colluvion, although the soil matrix is fine, the measured hydraulic conductivity is higher than expected. This shows that the stone fraction in the soil plays an important role in accelerating the evacuation of treated wastewater and also rainwater to the underlying layers, and finally to the water table. This property would be a strong point for the transfer function of the soil and we can deduce a method to improve the transfer function of heavy soils in urban or peri-urban development projects. This could be possible by adding the gravel and -limestone to soil matrix and mixing them. It has been concluded that this experiment, unique in its kind, has been useful in evaluating the function of retention / transfer of water in the soil receiving treated wastewater. In addition, the relevant predictor parameters and empirical relationships that make the economy of many water tests were identified

Philosophiae Doctor - PhD / With the advent of democracy, the ANC government was faced with the problem of addressing abject poverty, persistent unemployment and rank economic inequality that beset black South Africans under apartheid. To address these problems in a structured and comprehensive fashion, the Broad-Based Black Economic Empowerment Act 53 of 2003 (BBBEE Act) was promulgated. Several economists believed that growth in the economy is the bedrock upon which black economic empowerment would provide the foundation to correct these economic problems. This study sought to interrogate black economic empowerment as a means to address economic inequality and unemployment. The method of analysis and critique employed in this study is based on theories that Marx formulated in Capital: A Critique of Political Economy. In particular, this study draws on Marx’s theories of fictitious capital, surplus value production and appropriation, and the creation of the industrial reserve army. The thesis uses the theory to examine two BEE cases namely the Sanlam and Sasol equity transactions. It also analyses the relationship between productive capital and fictitious capital through an examination of Lonmin plc and Shanduka Pty Ltd, with a focus on the use of labour power to produce surplus value. Finally, it looks briefly at Sanlam and Sankorp to understand the rise of the black middle class in South Africa. Ultimately, this study charts a Marxist path to explain why black economic empowerment is unable to address economic inequality and unemployment. At the centre of this study is the problematisation of the capitalist mode of production on which black economic empowerment rests. The central argument advanced is that the very capitalist structure upon which this growth strategy was based, in fact laid the foundation for the reproduction of these self-same phenomena.

Emissions keep rising, states keep trading, and Earth will be 1.5°C warmer within five years. These are results of inadequate global governance. As globalisation has brought complexity to the international settings, creating overlapping webs of interactions: no International Organisation has properly responded. In this context, we are now situated in a trade regime complex with overlapping rules and norms, but what agency can be claimed? The thesis investigates the trade-environment nexus by addressing how legitimate climate leadership in a trade regime complex is pursued.   By challenging the conventionality of international leadership theory with a separation from hegemony and applying it outside multilateral negotiations, the thesis found it applicable for this new setting. Through mixed methods, statistics and textual analysis, the United States (US) Preferential Trade Agreements (PTA) were a surprisingly fitted case for this. To understand climate leadership performance and underlying objectives for such, the TREND database was adopted. Within, all US PTAs are shown and to what extent it has adapted 294 environmentally-related norms. Coded into means for leadership, the US legalistic approach of structurally directing others to mitigating measures seems to be a double-edged sword. Done right, it creates non-derogative measures. Done wrong, it creates a hegemon.