Worldwide there is considerable concern over the effects of human activities on the quantity and quality of freshwater. Measurement of infiltration behaviour will be important for improving freshwater management. This study identifies that New Zealand has a sporadic history of measuring soil water movement attributes on a limited number of soil types, although the current practical demand should be large for management of irrigation, dairy farm effluent disposal, as well as municipal / domestic waste- and storm-water disposal. Previous research has demonstrated that infiltration behaviour is governed by the interplay between numerous mechanisms including hydrophobicity and preferential flow, the latter being an important mechanism of contaminant leaching for many NZ soils. Future characterisation will need to recognise the dynamic nature of these interactions, and be able to reliably characterise the key infiltration mechanisms. Since macropores are responsible for preferential flow, it is critical that infiltration studies use a representative sample of the macropore network. The aim of this project was to study the mechanisms governing the infiltration behaviour of a layered soil in large (50 x 70 cm) monolith lysimeters, where the connectivity of the macropore network remains undisturbed. Four lysimeters of the Gorge silt loam were collected, a structured soil with four distinct layers. On each lysimeter there were four separate infiltration experiments, with water applied under suctions of 0, 0.5, 1, and 1.5 kPa by a custom-built tension infiltrometer. Each lysimeter was instrumented with 30 tensiometers, located in arrays at the layer boundaries. There was also a field experiment using ponded dye infiltration to visually define preferential flowpaths. Analysis of dye patterns, temporal variability in soil matric potential (Ψm), and solute breakthrough curves all show that preferential flow is an important infiltration mechanism. Preferential flowpaths were activated when Ψm was above -1.5 kPa. During saturated infiltration, at least 97% of drainage was through the ‘mobile’ pore volume of the lysimeter (θm), estimated among the lysimeters at 5.4 – 8.7 % of the lysimeter volume. Early-time infiltration behaviour did not show the classical square-root of time behaviour, indicating sorptivity was not the governing mechanism. This was consistent across the four lysimeters, and during infiltration under different surface imposed suctions. The most likely mechanism restricting sorptivity is weak hydrophobicity, which appears to restrict infiltration for the first 5 – 10 mm of infiltration. Overall, the Gorge soil’s early-time infiltration behaviour is governed by the dynamic interaction between sorptivity, hydrophobicity, the network of air-filled pores, preferential flow and air encapsulation. Long-time infiltration behaviour was intimately linked to the temporal dynamics of Ψm, which was in turn controlled by preferential flow and soil layer interactions. Preferential flowpaths created strong inter-layer connectivity by allowing an irregular wetting front to reach lower layers within 2 – 15 mm of infiltration. Thereafter, layer interactions dominate infiltration for long-time periods, as Ψm in soil layers with different K(Ψm) relationships self-adjusts to try to maintain a constant Darcy velocity. An important finding was that Ψm rarely attained the value set by the tension infiltrometer during unsaturated infiltration. The results show that ‘true’ steady-state infiltration is unlikely to occur in layered soils. A quasi-steady state was identified once the whole column had fully wet and layer interactions had settled to where Ψm changes occurred in unison through each soil layer. Quasi-steady state was difficult to identify from just the cumulative infiltration curve, but more robustly identified as when infiltration matched drainage, and Ψm measurements showed each layer had a stable hydraulic gradient. I conclude that the in-situ hydraulic conductivity, K(Ψm), of individual soil layers can be accurately and meaningfully determined from lysimeter-scale infiltration experiments. My results show that K(Ψm) is different for each soil layer, and that differences are consistent among the four lysimeters. Under saturated flow the subsoil had the lowest conductivity, and was the restricting layer. Most interestingly this pattern reversed during unsaturated flow. As Ψm decreased below -0.5 to -1 kPa, the subsoil was markedly more conductive, and the topsoil layers became the restricting layers. All four soil layers demonstrate a sharp decline in K(Ψm) as Ψm decreases, with a break in slope at ~ -1 kPa indicating the dual-permeability nature of all layers.

No description available.

The introduction of PPPs in infrastructure provision has changed the way in which governments around the world now view infrastructure provision. However, the introduction of PPPs to deliver the needed infrastructure has benefited only a few companies. Most of these companies are the big construction firms that possess technological know-how and those that have the financial ability to execute large infrastructure projects. Although SMEs are important for employment creation, inequality and poverty reduction, the participation of SMEs in these PPP projects is very low. This is because PPP models in developing countries are based on those used in developed economies, and such models ignore the socio-economic problems facing developing countries. Therefore, this study argues that PPP projects in developing countries present an opportunity for growing the SME sectors in developing countries. It challenges the viewpoint of seeing infrastructure backlogs only as providing opportunities to big private sector companies and argues that infrastructure backlogs can be used by governments to reduce the triple challenges of unemployment, poverty and inequality by linking SMEs to PPP projects. The traditional PPP model that is being applied by many developing countries does not fully encourage the participation of SMEs in PPP projects, as most of the projects executed through this model are bundled into big projects that SMEs cannot execute due to a lack of technological know-how and weak balance sheets. The study therefore suggests different ways in which the participation of SMEs in PPP projects could be improved based on the results of the survey conducted for this study. The study then proposes an “innovative conceptual PPP model for sustainable SME development” that takes into account the needs for developing countries to create jobs, reduce poverty and inequality. It also takes into account all challenges for SMEs identified through the review of literature and the study survey. / Economics / D. Litt. et Phil. (Economics)

Les bassins d’infiltration font partie intégrante des techniques alternatives de gestion des eaux pluviales en milieu urbain. Néanmoins, la potentialité de transfert de polluants vers la nappe est accrue en cas d’écoulements préférentiels dans les sols sous-jacents. Une bonne compréhension du couplage entre processus d’écoulements préférentiels en zone vadose et mécanismes géochimiques est requise. Cette thèse s’inscrit dans le cadre du suivi d’un bassin d’infiltration depuis plusieurs dizaines d’années de fonctionnement. Le site d’étude est situé sur le dépôt fluvioglaciaire hétérogène couvrant une grande partie de la région lyonnaise. Des auscultations sur une fosse sous le bassin (section 13.5m*2.5m) ont mis en évidence une régionalisation particulière de la pollution dans le sol. Cette étude s’appuie sur une étude numérique visant à identifier l’origine de la régionalisation des polluants et à la relier aux écoulements préférentiels résultant des hétérogénéités lithologiques. En amont de l’étude numérique, les lithofaciès sont complètement caractérisés aux regards de leurs propriétés hydrodynamiques, hydrodispersives et géochimiques. La modélisation numérique permet de souligner l’établissement de cheminements préférentiels en lien avec le contraste de propriétés hydrodynamiques, notamment lorsque de faibles débits sont appliqués en surface. Le rôle de chaque lithofaciès et de l’architecture du dépôt (stratification et inclusions) est clairement identifié. Les répercussions de tels écoulements sur les transferts non réactifs sont ensuite investiguées en combinant l’influence des écoulements préférentiels et le fractionnement de l’eau en fractions mobile et immobile résultant de l’hétérogénéité intrinsèque au sein de chaque lithofaciès. Enfin, ces processus physiques sont couplés à la réactivité géochimique pour le cas d’un polluant modèle (le cuivre) en prenant en compte la réactivité différentielle des lithofaciès. Ces résultats permettent de générer un modèle conceptuel d’écoulements préférentiels et de transfert de masse en milieu fortement hétérogène. / An infiltration basin is a stormwater best management practice (BMP) designed to infiltrate runoff volumes in urban areas. Nevertheless, preferential flow paths in the underlying soil may cause rapid migration of pollutants, thus contributing to groundwater contamination. Understanding the coupling between preferential flow processes in the vadose zone and geochemical mechanisms is then required. This thesis is a part of the follow-up of an infiltration basin for several decades of exploitation. The study site was settled over a highly heterogeneous glaciofluvial deposit covering much of the Lyon region. The investigation of an excavated section of the basin (13.5m long and 2.5m deep) pointed out a specific regionalization of pollution in the soil. This research is based on a numerical study to identify the origin of such a pollutant pattern and link this with preferential flow resulting from lithological heterogeneities. Different lithofacies were fully characterized regarding their hydraulic, hydrodispersive and geochemical properties. The numerical study proves that the high contrast in hydraulic properties triggers the establishment of preferential flow (capillary barriers and funneled flow). Preferential flow develops mainly for low initial water contents and low fluxes imposed at surface. The role of each lithofacies and architecture of deposit (stratification and inclusions) is clearly identified. The impact of such flows on non-reactive transfers is then investigated by combining the influence of preferential flow and pore water fractionation info into mobile and immobile fractions, resulting from the intrinsic heterogeneity within each lithofacies. Finally, these physical processes are coupled to the geochemical reactivity for a pollutant model (copper), taking into account the differential reactivity of lithofacies. These results generate a conceptual model of preferential flow and mass transfer in strongly heterogeneous media.

Magister Legum - LLM / South Africa

La compréhension des écoulements préférentiels dans la zone non saturée en fond de bassins d’infiltration est une condition préalable à une gestion optimale de ces ouvrages. Le basin d’infiltration étudié repose sur un dépôt fluvioglaciaire hétérogène constitué d’un lithofaciès majoritaire contenant des lentilles de sable et de gravier. Une étude géophysique (radar) a permis de caractériser cette hétérogénéité sédimentologique le long de radar-grammes (sections de quelques mètres de profondeurs et de plusieurs dizaines de mètre de long). Les écoulements ont été modélisés pour toutes ces sections ainsi qu’une section fictive remplie uniquement du lithofaciès majoritaire (témoin) et pour divers évènements pluvieux type incluant une chronique météorologique complète. Les résultats montrent clairement que l'hétérogénéité lithologique a un effet significatif sur l’écoulement avec la mise en place d’écoulements hétérogènes du fait de phénomènes de barrière capillaire au niveau des lentilles de sable et de gravier en non-saturé. Cet effet se répercute sur les chemins de l’eau dans le dépôt et sur les flux en surface (infiltration et ruissellement). Les résultats montrent aussi que cet effet dépend fortement de la section considérée. La variabilité spatiale de l’hétérogénéité lithologique induit donc une variabilité spatiale des écoulements préférentiels. Certains paramètres architecturaux et géométriques relatifs à l’hétérogénéité lithologique ont été proposés pour expliquer l’effet de l’hétérogénéité lithologique sur les écoulements préférentiels, de sorte à proposer une première tentative de modélisation des écoulements à méso-échelle. / Understanding preferential flows in the vadose zone is a prerequisite for a proper management of infiltration basins. The studied infiltration basin lies on a strongly heterogeneous glaciofluvial deposit made of a predominant lithofacies that embeds lenses of sand and gravel. Geophysics (GPR) were used to characterize the lithological heterogeneity along radar-grammes (sections few meters deep and dozens of meters long). Flow was modelled for all these sections and compared to a synthetic section filled only with the predominant lithofacies (control). Numerical results show that, under unsaturated conditions, the lithological heterogeneity has a strong impact on flow with the establishment of preferential flows induced by capillary-barrier effects in the vicinity of lenses of sand and gravel. These effects have also consequences on water fluxes at surface (infiltration and runoff) and depend strongly on the section considered for numerical modelling. It can thus be concluded that the spatial variability of lithological heterogeneity induces a spatial variability of preferential flow. Geometrical and architectural parameters were defined to quantity lithological heterogeneity and link it to preferential flows, with the aim to propose a first step towards modelling flow in the basin at the meso-scale. / O entendimento do fluxo na zona não saturada em formações heterogêneas é um prérequisito para uma gestão adequada de poluentes em bacias de infiltração inseridas nessas formações. Este estudo aborda o efeito da heterogeneidade litológica nos processo de escoamento numa bacia de infiltração com geologia inserida num depósito fluvioglacial. A bacia de infiltração é a Bacia Django Reinhardt, existente em Lyon. Esta bacia foi objeto de vários estudos que demonstraram algumas avaliações do impacto da heterogeneidade do solo. Os objetivos desses trabalhos foram todos baseados apenas no estudo sedimentológico de uma trincheira. Nenhum estudo abordou a potencial variabilidade espacial dos atributos do solo. Neste trabalho, foi modelizado o fluxo na zona vadosa através de três casos: drenagem interna, infiltração de água durante um evento de precipitação pluviométrica constante e solicitação hidrológica a partir de um fluxo variável escoamento superficial. Estes cálculos foram realizados para várias seções, que foram previamente caracterizadas quanto a sua heterogeneidade estrutural usando a técnica não destrutiva do GPR com uma frequência de 200MHz e 100MHz. O comportamento hidráulico dessas seções foi comparado com a de uma seção homogênea. Foi comparada o efeito da resolução da imagem nas estimativas das variáveis de fluxo. Alguns indicadores arquiteturais, geométricos e texturais foram propostos para esclarecer e avaliar a variabilidade espacial do efeito da heterogeneidade do solo sobre o fluxo em condições não saturadas. Os resultados mostram claramente que a heterogeneidade gera impactos nas variáveis de fluxo em condições não saturadas. Os impactos dependem da seção considerada.Os resultados mostram também que: a) a heterogeneidade estrutural do subsolo na meso-escala apresenta um efeito sobre a geração de escoamento preferencial e isso independe do tipo de solicitação aplicada na seção; b) O efeito da heterogeneidade se mostrou independentende das condições de contorno aplicadas na superfície; c) Nos períodos de ocorrência de chuvas intensas quem controla o comportamento das variáveis de fluxo é a intensidade de precipitação. No entanto, nos períodos em que ocorre ausência de precipitação, as variáveis de fluxo são controladas pela heterogeneidade da zona não saturada; d) A utilização de diferentes frequências influencia na estimativa das variáveis de fluxo. Isso é decorrente do impacto na quantificação da heterogeneidade decorrente do efeito da resolução de cada antena; e) Os indicadores não apresentaram relação direta com as variáveis de fluxo estudadas. Isso demonstra que o efeito da heterogeneidade não pode ser explicado por um único fator, mas por um conjunto de fatores.

Cette thèse comporte trois essais en macroéconomie en économie ouverte et commerce international. Je considère tour à tour les questions suivantes: sous quelles conditions est-il optimal pour un pays de former une union économique? (essai 1); l'augmentation de la dispersion transversale des avoirs extérieurs nets des pays est-elle compatible avec une dispersion relativement stable des taux d'investissement? (essai 2); le risque de perte de marché à l'exportation du fait de l'existence des zones de commerce préférentiel joue t-il un rôle dans la décision des pays exclus de négocier des accords commerciaux à leur tour? (essai 3). Le premier essai examine les conditions d'optimalité d'une union économique. Il s'intéresse à une motivation particulière: le partage du risque lié aux fluctuations du revenu. Dans la situation initiale, les pays ont très peu d'opportunités pour partager le risque à cause des frictions: les marchés financiers internationaux sont incomplets et il n'y pas de mécanisme pour faire respecter les contrats de crédit entre pays. Dans ce contexte, une union économique apparait comme un arrangement qui pallie à ces frictions entre les pays membres seulement. Cependant, l'union dans son ensemble continue de faire face à ces frictions lorsqu'elle échange avec le reste du monde. L'arbitrage clé dans le modèle est le suivant. D'un coté, l'intégration économique permet un meilleur partage du risque entre pays membres et la possibilité pour le partenaire pauvre d'utiliser la ligne de crédit du partenaire riche en cas de besoin. De l'autre coté, l'union peut faire face à une limite de crédit plus restrictive parce que résilier la dette extérieure est moins coûteux pour les membres l'union. De plus, le fait que le partenaire pauvre peut utiliser la limite de crédit du partenaire riche génère une externalité négative pour ce dernier qui se retrouve plus fréquemment contraint au niveau des marchés internationaux des capitaux. En conformité avec les faits observés sur l'intégration économique, le modèle prédit que les unions économiques sont relativement peu fréquentes, sont plus susceptibles d'être créées parmi des pays homogènes, et généralement riches. Le deuxième essai porte sur la dispersion des avoirs extérieurs nets et la relation avec la dispersion des taux d'investissement. Au cours des récentes décennies, la dispersion croissante des déséquilibres extérieurs et les niveaux record atteints par certaines grandes économies ont reçu une attention considérable. On pourrait attribuer ce phénomène à une réduction des barrières aux mouvements internationaux des capitaux. Mais dans ce cas, il est légitime de s'attendre à une augmentation de la dispersion au niveau des taux d'investissement; ceci, parce que le financement des besoins en investissements constitue une raison fondamentale pour laquelle les pays échangent les capitaux. Les données indiquent cependant que la dispersion des taux d'investissement est restée relativement stable au cours des récentes décennies. Pour réconcilier ces faits, je construis un modèle d'équilibre général dynamique et stochastique où les pays sont hétérogènes en raison des chocs idiosyncratiques à leurs niveaux de productivité totale des facteurs. Au niveau des marchés internationaux des capitaux, le menu des actifs disponibles est restreint à une obligation sans risque et il n'y a pas de mécanisme pour faire respecter les contrats de crédit entre pays. A tout moment, un pays peut choisir de résilier sa dette extérieure sous peine d'exclusion financière et d'un coût direct. Ce coût direct reflète les canaux autres que l'exclusion financière à travers lesquels les pays en défaut sont pénalisés. Lorsque le modèle est calibré pour reproduire l'évolution de la dispersion transversale des avoirs extérieurs nets, il produit une dispersion relativement stable des taux d'investissement. La raison principale est que les incitations que les pays ont à investir sont liées à la productivité. Avec l'intégration financière, même si les opportunités d'emprunt se sont multipliées, les incitations à investir n'ont pas beaucoup changé. Ce qui permet de générer une dispersion accrue de la position des avoirs extérieurs nets des pays avec une dispersion relativement stable des taux d'investissement. Le troisième essai analyse un aspect de l'interdépendance dans la formation des accords commerciaux préférentiels: j'examine empiriquement si le risque de diversion des exportations en faveur des pays membres des zones de commerce préférentiel est un facteur déterminant dans la décision des pays exclus de ces accords de négocier un accord à leur tour. Je construis un indicateur qui mesure le potentiel de diversion des exportations auquel font face les pays et estime un modèle probit de formation des zones de commerce préférentiel créées entre 1961 et 2005. Les résultats confirment que les pays confrontés à un plus grand potentiel de détournement des échanges sont plus susceptibles de former une zone de commerce préférentiel à leur tour. / This thesis consists of three essays in open economic macroeconomics and international trade. I consider the following questions: Which countries find it individually optimal to form an economic union? (essay 1); is the rising cross-sectional dispersion in net foreign asset positions consistent with a relatively stable dispersion in investment rates? (essay 2); is the risk of trade diversion due to existing preferential trade areas an important factor in excluded countries decision to seek one? (essay 3). The first essay studies the individual optimality of economic integration. It emphasizes the risk-sharing benefits of economic integration. In an initial situation, countries have very limited possibilities to share idiosyncratic endowment risk because of financial frictions: international financial markets are incomplete and contracts not enforceable. A union is an arrangement that solves both the market incompleteness and the lack of enforcement problems among member countries. The union as a whole still faces these frictions when trading in the world economy. The model emphasizes the following key trade-off. There are two benefits from economic integration: better risk-sharing among member countries and the possibility for poor partners to use the rich partners' credit lines. The costs are the following: borrowing limits become tighter because defaulting on international debt becomes less costly for union partners. Since poor partners may benefit from the rich partner's credit limit, this generates a negative externality: rich partners will find themselves more often borrowing-constrained in a union compared to standing alone in the world economy. Consistently with evidence on economic integration, the model predicts that economic unions occur relatively infrequently and are more likely to emerge among homogeneous and rich countries. The rising dispersion of external imbalances over the recent decades and the record-high levels reached by some major economies has received considerable attention during the recent years. The second essay focuses on one of such imbalances: the net foreign asset positions (NFA). One can view this rising dispersion as a consequence of the reduction in barriers to capital flows. But in such case, one would expect the dispersion in investment rates to go up as well because one fundamental reason countries borrow and lend internationally is to finance their investments needs. Instead, the dispersion in investment rates was relatively stable. To explain this puzzling fact, I undertake a quantitative analysis of the global dispersion of net foreign asset positions and investment rates. The framework is an integrated model of world economy where countries differences arise from idiosyncratic shocks to their total factor productivity levels. International capital flows is restricted: the menu of assets traded is exogenously restricted to a risk-free bond, and international lending contracts are not legally enforceable. At any time, a country may choose to repudiate its foreign debt subject to financial exclusion and an output cost. The output cost captures margins other than financial exclusion through which defaulting countries can be punished. When calibrated to match the evolution of the cross-sectional dispersion in net foreign asset positions, the model produces a relatively stable dispersion in investment rates. The reason is because the incentives to invest are related to the productivity, not to the borrowing and lending opportunities. Although the opportunities to borrow and lend internationally have increased, the incentives to invest have not changed much, thereby generating a large cross-sectional dispersion in NFA positions with a relatively stable dispersion in investment rates. The third essay investigates empirically whether the risk of trade diversion faced by countries excluded from preferential trade areas (PTA) is determinant in their decision to seek a preferential trade agreement. Using the trade complementarity index, I derive a measure of the potential of trade diversion and estimate a probit model of the formation of PTAs between 1961 and 2005. The results show that country-pairs facing a larger potential of trade diversion are more likely to form a PTA in the future.

Diese Arbeit ist Teil eines Weges, der die Polarisationsdynamik von Polynukleinsäure-Helices (DNA) zum Ziel hat. Die Dynamik kann im Prinzip von innen beobachtet werden, über Femtosekunden-zeitaufgelöste optische Spektroskopie eines Farbstoff-Moleküls anstelle einer Nukleinbase. Der optische Chromophor soll als solvatochrome Sonde der DNA Umgebung funktionieren. Dafür wurde 2-Amino-7-Nitro-Fluoren (ANF) gewählt, welches ideale solvatochrome Eigenschaften hat. Bevor der Einbau des Sondenmoleküls erfolgt, müssen dessen photophysikalischen Eigenschaften in reinen Lösungsmitteln und in Lösungsmittel-Mischungen weitgehend verstanden sein. Dieses Thema bestimmt den größeren Teil der Arbeit. ANF, aliphatische Derivate, und das entsprechende Nukleosid wurden synthesitsiert. Ihre thermodynamischen Eigenschaften, optischen Spektren, und ps Fluoreszenzlebensdauern werden für eine Reihe von Lösungsmitteln beschrieben. Präferentielle Solvatation in wässrigen Mischungen wird mit optischer Absorptions- und 1H NMR-Spektroskopie untersucht. Inclusionskomplexe mit Cyclodextrinen werden ebenfalls charakterisiert. Auf diese "klassischen" Studien folgt die fs-transiente optische Absorptionsspektroskopie von ANF und Derivaten. Die transienten Spektren werden zeilegt und die Banden für stimulierte Emission als Funktion der Zeit in den meisten Fällen erhalten. Damit erhält man eine Solvatations-Relaxationsfunktionen C(t) für die meisten Lösungsmittel (50 fs Zeitauflösung). Unterschiede zu bekannten Relaxationsfunktionen für die vieluntersuchte Sonde Coumarin 153 werden diskutiert. Wichtig ist, daß derart C(t) für ein ANF Nukleosid in Wasser existiert. Dies kann mit einer simulierten Kurve für ANF in DNA-Helices verglichen werden. Es folgt, dass gestapelte Chromophore im Innern dynamisch von jenen unterschieden werden können, die in die wässrige Umgebung herausgedreht sind. Der Cyaninfarbstoff Thiazol Orange (TO) wird von anderen Gruppen verwendet, um die Hybridisierung von DNA-Strängen zu verfolgen. Die Fluoreszenz von TO wird durch schnelle Isomerisation im S1 Zustand stark gelöscht. In dieser Arbeit wird die entsprechende innermolekulare Verdrillung mit fs-transienter Absorptionsspektroskopie und mit fs-zeitaufgelöster Fluoreszenzspektroskopie (Summenfrequenz-Erzeugung) zum ersten Mal zusammenhängend untersucht. Transiente Spektren in Lösung werden mit stationären Spektren in verschiedenen PNA/DNA Duplex-Konstrukten verglichen. Eine hochfrequente Schwingungsmode ist bei der strukturellen Reorganisation von TO nach S0 to S1 Anregung beteiligt. Zunehmende Aktivität begleitet die Verdrillung. Deshalb sollte die Form der stationären Fluoreszenzbande dazu geeignet sein, das verfügbare freie Volumen in DNA-Konstrukten abzuschätzen. / This work is part of an effort to observe the polarization dynamics of duplex polynucleic acids from the inside, through femtosecond time-resolved optical spectroscopy of a dye molecule which has been stacked into the structure at a well-defined site. The dye chromophore should act as a solvatochromic probe of its DNA environment. For a probe, 2-amino-7-nitro fluorene (ANF) had been selected since it has ideal solvatochromic properties. Before being linked into DNA, its photophysical properties in liquids and liquid mixtures should be understood. The larger part of this thesis deals with this topic. ANF, aliphatic derivatives, and the nucleoside were synthesized. Their thermodynamic properties, optical spectra, and ps fluorescence decay are examined in a wide range of solvents. For preferential solvation in aqueous mixtures, absorption results are compared with 1H NMR spectra. Inclusion properties were also explored. Femtosecond transient absorption spectroscopy of ANF and derivatives follows after these "classical" studies. The transient spectra are analyzed and, in most cases, the stimulated-emission band can be obtained as function of time. Ultrafast solvation relaxation functions (50 fs resolution) for many solvents are constructed from these data and discussed by comparison with a well-studied probe, Coumarin 153. Most importantly, the solvation relaxation of the ANF nucleoside in water is obtained and compared with a simulated relaxation of the chromophore in a DNA duplex. It follows that chromophores stacked inside DNA can be distinguished from chromophores which extend into the aqueous boundary layer. The cyanine dye Thiazole Orange (TO) is used by other groups to monitor the hybridisation of DNA strands. Its fluorescence is strongly quenched by intramolecular twisting in the excited state S1. In this thesis the twisting process is characterized by femtosecond transient absorption and fluorescence upconversion spectroscopy, combined, for the first time. The transient spectra are compared to stationary spectra in a PNA/DNA duplex where the degree of twisting is restricted. A high-frequency mode is shown to play an important role in the structural reorganisation of TO following S0 to S1 excitation. Its vibrational activity is correlated with twisting. Therefore the shape of the emission band may be used to estimate the available volume in DNA constructs.

This work entails a study of some of the schemes that are employed by country residents when companies and trusts are used as vehicles for investing in offshore tax-haven and low tax jurisdictions so as to avoid taxes. The study also entails a critical analysis of the effectiveness of the some of the laws in South Africa that curb such offshore tax avoidance schemes. Similar laws in the United Kingdom and in the United States are analysed in order to come up with some recommendations that could be considered for possible reform of the relevant South African laws where they are found wanting. Since offshore tax avoidance is an international issue, the effectiveness of the recommendations of some international organisations in preventing the depletion of countries' tax bases are also analysed. / JURISPRUDENCE / LLD

Text in English / This is a study of community protest against Barberton Mines (Pty) Ltd. It is a study of conflict and conflict resolutions. Barberton Mines (Pty) Ltd is one of the three gold mining companies in Barberton, and is in dire need of a bankable community/stakeholder relation management strategy, which should at least reduce, if not eliminate, the endless violent community protests against its operations. Methodologically, the study is predicated on a qualitative approach backed by oral interviews and the use of a survey. The study reveals that as much as the community appreciates Barberton Mines for its delivery in socio-economic development initiatives, Barberton Mines’ recruitment and procurement departments are not doing any justice in terms of preferred policy in favour of the locals/Barberton community. This is a key source of conflict. The results also reveal that the Barberton Mines Transformation Trust (BMTT), a vehicle established for socioeconomic development in Barberton, is considered to be ineffective by the community and is one of the causes of the conflict. The resolutions of the conflict include the effective implementation of the mining legislation and unrolling of the Mining Charter. The effectiveness and lack thereof of these conflict resolutions are subjected to analysis in this study. / Development Studies / M.A. (Development Studies)