Thesis (Ph.D.)--York University, 2006. Graduate Programme in Chemistry. / Typescript. Includes bibliographical references. Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR19763

Thesis (M. Sc.)--University of Pretoria, 2004. / Title from opening screen (viewed 12th March, 2005). Includes summary. Includes bibliographical references.

Thesis (Ph. D.)--Rutgers University, 2007. / "Graduate Program in Chemistry and Chemical Biology." Includes bibliographical references (p. 269-270).

Thesis (M.E.S.), Memorial University of Newfoundland, 1999. / Bibliography: p. 175-183.

Thesis (M. Sc.), Memorial University of Newfoundland, 1999. / Includes bibliographical references.

Thesis (Ph. D.)--University of Hong Kong, 2006.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

>Magister Scientiae - MSc / The main aim of this study is to investigate theelectrochemical determination of two beneficial (selenium and zinc) and two toxic (chromium and vanadium) metals in the potable water within the City of Cape Town's distribution area. The Water Laboratory of the City's Scientific Services Branch analyses for these metals in their elemental state, using the Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). This is a standard method used for the detection of trace metals. The most sensitive voltammetric method for determining these metals is by adsorptive stripping voltammetry, using a thin mercury film electrode with a glassy carbon support. This voltammetric method is used for quantitative determination of specific ionic species. Because of mercury's toxicity it is not really favoured for trace metals anymore. Many other possibilities are under investigation, e.g. bismuth-film, modified glassy carbon and antimony electrodes. The boron-doped diamond (BDD) electrode has distinct advantages when used to determine metal concentrations. Advantages of BDD electrodes include lower detection limit, speciation and wider potential window. In this study cyclic voltammetry (CV) was used to determine the copper, cadmium and lead concentrations in potable water by means of square wave voltammetry (SWV) and a bare glassy carbon electrode (GCE). Furthermore, a boron-doped diamond electrode (BDDE) was used to investigate the possibilities of determining selenium, chromium and vanadium by SWV. Real samples (potable water samples) were analysed electrochemically to qualify and quantify these metals and determine whether they comply with the SANS 241:2006 drinking water guidelines.The copper, cadmium, lead and selenium peaks appear very close to the theoretical values, which indicate that these metals can be detected by SWV method, but further analysis with more samples is advised. Even though responses were observed for vanadium and chromium, it was not reliable and requires further investigation. Further studies into the analyses of zinc are also advised.

M.Sc. / The behaviour i.e. the distribution, bioavailability and toxicity of an element depends on the particular species in which it is present. That being said the prediction of the behaviour of species can therefore not be predicted by determination of the total concentration alone. Speciation analysis is thus an important process, which seeks to identify and quantify the species that occur in a sample. By identifying the species one is better equipped to predict the behaviour of the element if it were released into the ecosystem as well as if it were used in industrial processes. The speciation analysis of the dominant chromium species, Cr(III) and Cr(VI), has received much attention as these contradictory species are involved in many industrial processes such as plating and tanning for example. The species have opposing behaviour as Cr(III) is found to be a necessary micronutrient for mammals where as Cr(VI) is known to be toxic. Of the numerous methods developed for chromium speciation analysis, the on-line process of chromatographic preconcentration followed by simultaneous detection with a sensitive detector produces a synergistic effect for the successful speciation analysis of chromium. It was thus decided to study ion chromatography hyphenated with an ICP-OES as a means of studying chromium species. Anion chromatography coupled with ICP-OES was the basis for the development of the first method. Complexation of Cr(III) with EDTA to form a monovalent anion preceded its separation from Cr(VI) as the chromate anion. A carbonate-bicarbonate eluent was used to elute the species from a Dionex AG 9 guard column coupled with an AS 9 separation column. This method proved to be effective and fast, with each analysis taking less than two minutes. The second method was based on cation chromatography in the form of a Dionex CG12A guard column being coupled with an ICP-OES spectrometer as the detector. This method made use of a gradient elution program in which hexavalent chromium was eluted first with ammonium nitrate followed by trivalent chromium with nitric acid. This method was successfully applied to synthetic samples and was found to be effective.

M.Sc. / The 11B/10B stable isotope ratio in wine- and provenance soil samples of four South African wine regions was determined by means of quadrupole inductively coupled plasma mass spectrometry (ICP-MS). The data obtained was combined with multi-element results for the same samples. Discriminant analysis and ANOVA statistics were utilized to create a footprint of wines compared to their provenance soil. The results showed that the stable boron isotope ratio was a distinguishable characteristic in wine and soil samples for the Stellenbosch, Robertson, Swartland, and Walker Bay wine regions. The potential improvement of precision and accuracy was investigated specifically for ICP-QMS (quadrupole mass spectrometry) analysis of boron isotope ratios. Sample preparation methods for the matrices used in this work were developed and applied. The influence of the matrix components was investigated. Ion exchange separation procedures were developed for the separation of total B from the wine and soil matrices. Results were treated mathematically to minimize mass bias effects. It was found that combined matrix effects and TDS (total dissolved solids) deposition did have a pronounced effect on the 11B/10B isotope ratios of the samples. The possibility of boron isotope fractionation was investigated in vine plants. Hydroponic experiments were set up with test plants of two cultivars. A 10B enriched nutrient solution or growth solution with natural 11B/10B ratio was supplied to the plants during alternating periods of 5 weeks each. New growth leaves were harvested once every week during each of these time periods. All samples were carefully prepared and analyzed to determine the relationship of the 11B/10B ratio in the leaves compared to that of the supplied nutrient solution. It was observed that the 11B/10B isotope ratio of the growth solution had an influence on the 11B/10B stable isotope ratio in new growth leaves of vine plants.