M.Sc. / The South African wine industry is well respected internationally for producing high quality wines. The possible adulteration of these wines can lead to loss of reputation and a loss of sales and could also be dangerous to consumer’s health. Multi-element analysis of wines is one way of implementing quality control and the same multi-element data can also be used to prove the point of origin. The metal content of the fruit (grapes) should represent the metal content of the soil in which the plants (vineyards) were grown. An Inductively Coupled Plasma Mass Spectrometer (ICP-MS) was used with correct internal standard and interference correction to obtain reliable concentrations for 27 elements (Li, B, Al, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Se, Rb, Sr, Zr, Nb, Mo, Cd, Sn, Sb, Ba, Ce, Nd, W, Tl, Pb and U) of 1:1 diluted wines and microwave digested vineyard soil from four South-African wine-producing regions: Stellenbosch, Swartland, Robertson and Walker Bay. This multi-element data was then interpreted using multivariate statistical analysis in order to determine which elements have the ability to discriminate between the four regions. Li, B, Sc, Ni, Mn, Co, Cu, and Rb were the elements that were identified to have discrimination ability. 96% of wines and 100% of vineyard soils were correctly classified. Indirectly it has been proven that the metal content of the soil can be correlated to the metal content of the wine. This methodology can be reliably used in industry for quality control and routine provenance determination

Please read the abstract in the section 00front of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

We investigate the quantum dynamics of the spins on different Heisenberg antiferromagnetic spin lattice systems. Firstly, we applied the coupled-cluster method to the spin-1/2 antiferromagnetic XXZ model on a square lattice by employing an approximation which contains two-body long-range correlations and high-order four-body local correlations. Improvement is found for the ground-state energy, sublattice magnetization, and the critical anisotropy when comparing with the approximation including the two-body correlations alone. We also obtain the full excitation spectrum which is in good agreement with the quantum Monte Carlo results and the high-order spin-wave theory. Secondly, we study the longitudinal excitations of quantum antiferromagnets on a triangular lattice by a recently proposed microscopic many-body approach based on magnon-density waves. We calculate the full longitudinal excitation spectra of the antiferromagnetic Heisenberg model for a general spin quantum number in the isotropic limit. Similar to the square lattice model, we find that, at the center of the first hexagonal Brillouin zone Γ(q=0) and at the magnetic ordering wavevectors ±[Q= (4π/3,0)], the excitation spectra become gapless in the thermodynamic limit, due to the slow, logarithmic divergence of the structure factor. However, these longitudinal modes on two-dimensional models may be considered as quasi-gapped, as any finite-size effect or small anisotropy will induce a large energy gap, when compared with the counterpart of the transverse spin-wave excitations. We have also investigated the excited states of the quasi-one-dimensional quantum antiferromagnets on hexagonal lattices, including the longitudinal modes based on the magnon-density waves. A model Hamiltonian with a uniaxial single-ion anisotropy is first studied by a spin-wave theory based on the one-boson method; the ground state thus obtained is employed for the study of the longitudinal modes. The full energy spectra of both the transverse modes (i.e., magnons) and the longitudinal modes are obtained as functions of the nearest-neighbor coupling and the anisotropy constants. We have found two longitudinal modes due to the non-collinear nature of the triangular antiferromagnetic order, similar to that of the phenomenological field theory approach by Affleck. The excitation energy gaps due to the anisotropy and the energy gaps of the longitudinal modes without anisotropy are then investigated. We then compares our results for the longitudinal energy gaps at the magnetic wavevectors with the experimental results for several antiferromagnetic compounds with both integer and non-integer spin quantum numbers, and we find good agreements after the higher-order contributions are included in our calculations.

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Landfills are considered to be one of the major sources of anthropogenic methane (CH4) emissions in the environment. A landfill biocover system optimizes environmental conditions for biotic CH4 consumption that controls the fugitive and residual emissions from landfills. A compost material has more oxidation potential in comparison to any other material due to its high porosity, organic content, free flux for gases and water holding capacity. Thermal, hydraulic, bio – chemical and mechanical (THMCB) properties are important factors that can significantly affect the performance of biocover material with regards to CH4 oxidation potential as well as structural stability. Technical data on the thermal, hydraulic and mechanical (THM) properties of compost based biocover materials are quite limited. Hence, a detailed experimental program has been carried out at the University of Ottawa to study the THM properties and behaviour of compost biocover material by conducting experimental tests on small compost samples as well as by performing column experiments. The test results indicate that lower water content (dry of optimum for compaction curve) shows more free air space (FAS) in comparison to higher water content. The compost has almost the same shear strength for various initial water contents and dry unit weights; however, it settles and swells more at higher water content than lower water content per mechanical test results. The thermal and hydraulic properties of compost are a function of the compaction degree in addition to various other parameters. It is also found that the THM properties of compost are strongly coupled and the degree of saturation greatly affects the FAS.

The main result of underground mining extraction is creating of large underground voids (mine stopes). These empty openings are typically backfilled with an engineering cementitious material called cemented paste backfill (CPB). The main purpose of CPB application in underground mining is to provide stability and ensure the safety of underground openings, maximize ore recovery, and also provide an environmental-friendly means of underground disposal of potential acid generating tailings. CPB is a mixture of mine tailings, cement binder and water. CPB has a complex geotechnical behaviour when poured into mine voids. This is because of the different thermal (T), hydraulic (H), mechanical (M) and chemical coupled processes and interactions that take place in CPB soon after placement. In addition to these THMC behaviours, various external factors, such as stope geometry, drainage condition and arching effects add more complexity to its behaviour. In order to acquire a full understanding of CPB behaviour, there is a need to consider all of these THMC factors and processes together. So far, there has not been any study that addresses this research need. Indeed, fundamental knowledge of the THMC behaviour of CPB provides a key means for designing safe and cost-effective backfill structures, as well as optimizing mining cycles and productivity of mines. Innovative experimental tools and CPB testing methods have been developed and adopted in this research to fulfill the objectives of this research. In the first phase of the study, experiments with high columns are developed to study the THMC behaviour of CPB from early to advanced ages with respect to height of the column and curing time. The column experiments simulate the mine stope and filling sequence and provide an opportunity to study external factors, such as evaporation, on the THMC behaviour of CPB. However, an important factor is the overburden pressure from the stress due to self-weight that cannot be simulated through column experiments. Therefore, in the second phase of this study, a novel THMC curing under stress apparatus is developed to study the THMC behaviour of CPB under various pressures due to the self-weight of the CPB, drainage conditions, and filling rate and sequence. Comprehensive instrumentation and geotechnical testing are carried out to obtain fundamental knowledge on the THMC behaviour of CPB in different curing conditions from early to advanced ages. The results of these studies show that the THMC properties of CPB are coupled. Important parameters, such as curing stress, self-desiccation due to cement hydration, temperature, pore water chemistry, and mineralogical and chemical properties of the tailings, have significant influence on the shear strength and compressive strength development of CPB. Factors such as evaporation and drying iii shrinkage can also affect the hydro-mechanical properties of CPB. The curing conditions (such as curing stress, drainage and filling rate) also has significant impact on CPB behaviour and performance. The THMC interactions and the degree of influence of each factor should be included in designing backfill structures and planning mining cycles. This innovative curing under stress technique can be replaced the conventional curing of CPB (curing under zero stress and no THMC loadings), in order to optimize CPB mechanical strength assessment, increase mine safety and enhance the productivity.

Glaciation is considered one of the main natural processes that can have a significant impact on the long term performance of DGRs. The northern part of the American continent has been subjected to a series of strong glaciation and deglaciation events over the past million years. Glacial cycles cause loading and unloading, temperature changes and hydraulic head changes at the ground surface. These changes can be classified as transient boundary conditions. It is widely accepted that the periodic pattern of past glacial cycles during the Late Quaternary period are resultant of the Earth’s orbital geometry changes that is expected to continue in the future. Therefore, from the safety perspective of DGRs, such probable events need to be taken into account. The objective of this thesis is to develop a numerical model to investigate the thermo-hydro-mechanical-chemical (THMC) coupled processes that have resulted from long term past and future climate changes and glaciation cycles on a proposed DGR in sedimentary rocks in southern Ontario. The first application is done on a large geological cross section that includes the entire Michigan basin by using a hydro-mechanical (HM) coupled process. The results are compared with field data of anomalous pore water pressures from deep boreholes in sedimentary rocks of southern Ontario. In this work. The modeling results seem to support the hypothesis that at least the underpressures in the Ordovician formation could be partially attributed to past glaciation. The second application is made on site conditions by using the THMC model. The results for the pore water pressure, tracer profiles, permafrost depth and effective stress profile are compared with the available field data, the results show that the solute transport in the natural limestone and shale barrier formations is controlled by diffusion, which provide evidence that the main mechanism of transport at depth is diffusion-dominant. The third application is made on site conditions to determine the effect of underground changes in DGRs due to DGR construction. The results show that future glaciation loads will induce larger increases in effective stresses on the shaft. Furthermore, it is found that hypothetical nuclide transport in a failed shaft can be controlled by diffusion and advection. The simulation results show that the solute transported in a failed shaft can reach the shallow bedrock groundwater zone. These results might imply that a failed shaft will substantially lose its effectiveness as a barrier. The fourth application is proposed to investigate the geochemical evolution of sedimentary host rock in a near field scale. In this part, a new thermo-hydro-mechanical-geochemical simulator (COMSOL-PHREEQC) is developed. It is anticipated that there will be a geochemical reaction within the host rock that results from interaction with the water enriched with the CO2 generated by nuclear waste.

Consider an iterated function system (IFS) that does not necessarily contract uniformly, but instead contracts on average after a finite number of iterations. Under some technical assumptions, previous work by Barnsley, Demko, Elton and Geronimo has shown that such an IFS has a unique invariant probability measure, whilst many (such as Peigné, Hennion and Hervé, Guivarc'h and le Page, Santos and Walkden) have shown that (for different function spaces) the transfer operator associated with the IFS is quasi-compact. A result due to Keller and Liverani allows one to deduce whether the transfer operator remains quasi-compact under suitable, small perturbations. The first part of this thesis proves a large deviations result for IFSs that contract on average using skew product transfer operators, a technique used by Broise to prove a similar result for dynamical systems. The remaining chapters introduce a notion of 'coupled IFSs', an analogue of the traditional coupled map lattices where the base, unperturbed behaviour is determined by an underlying dynamical system. We use transfer operators and Keller and Liverani's theorem to prove that quasi-compactness of the transfer operator is preserved for 'product IFSs' under small perturbations and for coupled IFSs. This allows us to prove a central limit theorem with a rate of convergence for the coupled IFS.

The aim of this work was to investigate the effect on horizontal ground heat exchanger performance of changing soil and load parameters, and pipe horizontal separation distance for ground-coupled heat pumps under Egyptian conditions.Egypt possesses a variety of energy resources; namely fossil and renewable. The amount of renewable energy available is significant and must be utilized perfectly for the sake of achieving sustainable use of energy resources. Soils in Egypt vary widely from being clay with its thermal conductivity of 1.11 (for clay particles) to sand with its thermal conductivity of 5.77 (for sand particles). Two soil samples were chosen from the literature to be used in the investigation held in this work with boundary conditions that match the weather and ground temperature distribution conditions in Egypt.Conduction heat transfer in soils is a very complicated process especially when it is combined with time dependant boundary conditions and temperature dependent thermophysical properties of the medium. A MATLAB code was used to estimate thermophysical properties of the soil samples with three different moisture contents (0, 0.2, and saturation %) and the upper boundary condition bases on two surface dryness conditions (dry and wet). The results of the code were fed to Abqaus/CAE to analysis and predict the temperature distribution in these soils with implementing the time dependant boundary conditions to investigate the ground thermal behaviour of these soils. Also the temperature distribution around two pipes per trench of horizontal ground heat exchanger with applying synthetic load based on estimated cooling and heating degree days for one set of weather conditions. The horizontal separation distance between pipes was investigated by changing it to be 0.2, 0.3, 0.4, and 0.5 metres.Both the MATLAB code and Abaqus environment were validated against measured data published in the literature and their results agreed well with this data.The results of the simulation showed that the ground thermal behaviour depends mainly on the boundary conditions applied on the model. Dry soils are the worst being affected by the variation of the boundaries, because of its low volumetric heat capacities. The moisture content in the soil should be kept around 0.2 or above to get the most benefits from the presence of moisture in the vicinity of ground heat exchangers. The effect of the soil surface dryness is less significant than that of the moisture content of the entire system but it is more controllable than the moisture content. Also it was found that the horizontal separation distance (HSD) between pipes must be selected on the bases of prior knowledge of the site parameters soil type and moisture level. The results showed that the 0.4m HSD is the optimum HSD for the conditions and load profile included in this study.