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This comparative study attempts to determine the importance of soil fertility in determining how much of an element a plant absorbs.

Understanding fuel use is important in researching ancient communities. This project developed methods to identify archaeological fuel from midden, hearth, and ash samples using comparison to modern analogues. Modern analogue fuels were ashed at 2000C, 4000C, and 9000C then analysed with a suite of methods, the results were then used to inform the development of an approach for the identification of archaeological fuels. These methods were tested using samples from Ness of Brodgar, Knowe of Swandro, and Smerquoy/Muckquoy in Orkney. Magnetic susceptibility, scanning electron microscopy with energy dispersive X-ray spectroscopy, pH and Munsell colour assignment were chosen based upon previous archaeological, biofuel, and soil pollution research. The methodologies were refined with the analysis of ash from fuels including peat, seaweed, driftwood, willow, hazel, heather, grasses, cow dung, sheep dung, and bone. Modern analogue fuels at increasing temperatures showed an intensification in magnetism and alkalinity, and an alteration to mineral components during the chemical reaction of combustion that is indicative of fuel type and temperature. Principal components analysis confirmed matches between archaeological samples and modern ash, indicating a strong relationship between peat fuels and the archaeological samples. A correlation is also demonstrated between some of the archaeological samples and sheep dung, driftwood, willow, and animal bone. It is evident that each archaeological site has unique patterns of both fuel type and temperature. This shows that in the absence of abundant traditional wood fuel resources, the occupants of these sites used a combination of alternative fuels.

In this dissertation, mesoporous silica thin films with tunable features at the nanoscale were fabricated using the triblock copolymer template pathway, with the aim of specifically harvesting the low molecular weight peptides and proteins from human serum, which has been regarded as a potential source of diagnostic biomarkers for the early detection of disease. The superior properties of mesoporous silica have been demonstrated in applications which include chemical sensing, filtration, catalysis, drug-delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the materials, which in turn are determined by the processing parameters in evaporation-induced self-assembly (EISA). Using the different polymer templates and polymer concentration in the precursor solution, various pore size distributions, pore structures and surface hydrophilicities were obtained and applied for nanotexture-selective recovery of low mass proteins. With the assistance of mass spectrometry and statistic analysis, we demonstrated the correlation between the nanophase characteristics of the mesoporous silica thin film and the specificity and efficacy of low mass proteome harvesting. In addition, to overcome the limitations of the pre-functionalization method in polymer selection, plasma ashing was used for the first time for the treatment of the mesoporous silica surface prior to chemical modification. Opposite surface charges due to the different functional groups used, resulted in a distinctive selectivity of the low molecular weight proteins from the serum sample. The mesoporous silica chips operate with extraordinary rapidity, high reproducibility, no sample pre-processing, and substantial independence from sample acquisition and storage temperature.In conclusion our study demonstrates that the ability to tune the physicochemical properties of mesoporous silica surfaces has the potential to promote the use of this material as a tool for the selective separation and concentration of the low molecular weight proteome from complex biological fluids. / text

Low-k dielectrics with porosity are being introduced to reduce the RC delay of Cu/low-k interconnect. However, during the O2 plasma ashing process, the porous low-k dielectrics tend to degrade due to methyl depletion, moisture uptake, and densification, increasing the dielectric constant and leakage current. This dissertation presents a study of the mechanisms of plasma damage and dielectric recovery. The kinetics of plasma interaction with low-k dielectrics was investigated both experimentally and theoretically. By using a gap structure, the roles of ion, photon, and radical in producing damage on low-k dielectrics were differentiated. Oxidative plasma induced damage was proportional to the oxygen radical density, enhanced by VUV photon, and increased with substrate temperature. Ion bombardment induced surface densification, blocking radical diffusion. Two analytical models were derived to quantify the plasma damage. Based on the radical diffusion, reaction, and recombination inside porous low-k dielectrics, a plasma altered layer model was derived to interpret the chemical effect in the low ion energy region. It predicted that oxidative plasma induced damage can be reduced by decreasing pore radius, substrate temperature, and oxygen radical density and increasing carbon concentration and surface recombination rate inside low-k dielectrics. The model validity was verified by experiments and Monte-Carlo simulations. This model was also extended to the patterned low-k structure. Based on the ion collision cascade process, a sputtering yield model was introduced to interpret the physical effect in the high ion energy region. The model validity was verified by checking the ion angular and energy dependences of sputtering yield using O2/He/Ar plasma, low-k dielectrics with different k values, and a Faraday cage. Low-k dielectrics and plasma process were optimized to reduce plasma damage, including increasing carbon concentration in low-k dielectrics, switching plasma generator from ICP to RIE, increasing hard mask thickness, replacing O2 by CO2 plasma, increasing CO addition in CO/O2 plasma, and increasing N2 addition in CO2/N2 plasma. By combining analytical techniques with the Kramers-Kronig dispersion relation and quantum chemistry calculation, the origin of dielectric loss was ascribed to the physisorbed water molecules. Post-ash CH4 plasma treatment, vapor silylation process, and UV radiation were developed to repair plasma damage. / text

Coals, from mines in the Highveld coalfield, as well as gasification ash samples were characterised, in order to understand the mineralogical and chemical properties of the individual components in the gasification feedstocks. X-ray diffraction of low temperature oxygen-plasma ash indicates that the coals contain significant proportions of kaolinite, quartz and a fluxing elements-bearing mineral (dolomite), plus minor concentrations of illite and other fluxing elements-bearing minerals namely calcite, pyrite and siderite. Of the feed coal, the -75+53 mm size fraction has a high pyrite, and to a lesser extent a high calcite and dolomite content. However, the small proportion of iron-bearing phases (from the reaction between kaolinite and pyrite) in samples taken from the gasifier implies that pyrite contributes minimally to sintering or slagging in this case. Calcite is mainly present in the >1.8 g/cm3 density fraction of the feed coal, whereas dolomite is mainly present in the 1.5-1.8 g/cm3 density fraction, as inclusions or fine cleats in the coal matrix. Electron microprobe analyses of coals from the six different South African mines confirmed that some Ca, Mg, Al, Si, Na, K, Ti and Fe are present in the organic matrix in the coal samples tested in this study, but the amounts of these are small compared with the fluxing elements in minerals. XRD and microprobe analyses indicate that the ash clinker samples taken from the gasifiers contain a number of crystalline high temperature phases, including anorthite, mullite, cristobalite, quartz and diopside. FactSage confirmed that anorthite and mullite are equilibrium phases at elevated temperatures in the ash clinkers and heated rock fragments. Limited reaction takes place between the included coal minerals and the extraneous rock fragments. / Thesis (PhD)--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / unrestricted