>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.

Ph.D. (Geology) / The successions of the Cape- and Karoo Supergroups preserve an integrated history of sedimentation along the paleo-Pacific margin of Gondwana from the Paleozoic to the Early Mesozoic. The Cape- and Karoo Supergroups have been well studied with regard to stratigraphy, sedimentary facies and depositional environment. However, the nature and location of their source regions, especially for the changeover from deposition within an Atlantic-type continental margin basin for the successions of the Cape Supergroup to an Andean-type continental foreland basin for some of the units of the Karoo Supergroup, remains poorly understood. In order to shed light on the nature of these source regions, a comprehensive U-Pb detrital zircon study of the successions of the Cape- and lower Karoo Supergroups was launched. A representative number of samples from the upper and lower successions of the Table Mountain- Bokkeveld- and Witteberg Groups of the Cape Supergroup as well as the Dwyka and Ecca Groups of the Karoo Supergroup were collected throughout the western, southwestern and southern Cape region. A few samples of the Dwyka Group were also collected within the more eastern outcrop regions of the succession located in Kwazulu-Natal. The sedimentary rocks of the Natal Group and Msikaba Formation have long been regarded as coeval with the Cape Supergroup. Similar to the successions of the Cape- and Karoo Supergroups, very little is known about their sedimentary source regions. Also, their relative age of sedimentation remains poorly constrained. The U-Pb detrital zircon study of the successions of the Cape- and lower Karoo Supergroups was thus extended so as to include the successions of the Natal Group and Msikaba Formation. The detrital zircon age populations of the successions of the Natal Group and Msikaba Formation would not only improve the present understanding with regards to the sedimentary source regions to these units but would also facilitate the evaluation of possible correlations between these units and the stratigraphic units of the Cape Supergroup. Samples of both the lower Durban Formation and the upper Mariannhill Formation of the Natal Group and the Msikaba Formation (which is presently regarded as being part of the Cape Supergroup) were therefore collected within their respective outcrop regions in the Kwazulu-Natal area. The similarities in litho- and bio-stratigraphy between the successions of the Cape- and Karoo Supergroups and those of the Ordovician to Early Permian successions of the Ventania System and the Ordovician to Silurian successions of the Tandilia System in Argentina have long been recognized. Although the detrital zircon populations of some of the formations within these Systems have been evaluated in the past, it is yet to be determined whether these successions and those of the Cape- and lower Karoo Supergroups have certain source regions in common. In order to facilitate such a comparison, samples of selected units of the Ventania System were therefore collected near Sierra de la Ventania, while a sample of the Balcarce Formation of the Tandilia System was obtained near Mar del Plata. The detrital zircon age populations of the successions of the Ventania and Tandilia Systems were also further evaluated in the light of establishing or confirming a time-correlation between these formations and those of the Cape- and lower Karoo Supergroups. U-Pb age determination of the detrital zircons population of the samples was conducted by means of Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS). Although LA-ICP-MS is a routine, well-established technique where the U-Pb age determination of detrital zircons is concerned, it was yet to be established at the centralized analytical facility of the University of Johannesburg, SPECTRUM, using the instrumentation currently available (i.e. 213nm Nd:YAG laser coupled to Quadrupole-based ICP-MS). The U-Pb age determination of detrital zircons was therefore preceded by a fair amount of instrument optimization and method development. Well studied shortcomings of U-Pb detrital zircon dating by LA-ICP-MS such as laser induced elemental fractionation, mass discrimination effects and as well as the possible occurrence of minor common-Pb needs were addressed and corrected for. The detrital zircon populations of successions in the Cape Supergroup have a distinct major Neoproterozoic to Early Cambrian age component, which can be attributed to an input of detritus from successions related to the Pan-African Orogeny in South Africa, such as the Gariep- and Saldania Belts located towards the north of the Cape Basin. A substantial amount of Mesoproterozoic detrital zircon grains is also present in all the samples from the successions of the Cape Supergroup. These grains of Mesoproterozoic age were probably derived from the Namaqua-Natal Metamorphic Province, which is also regarded as the source of some minor amounts of Paleoproterozoic detrital zircon grains. The near absence of Archean grains from the detrital zircon populations of the successions of the Cape Supergroup is notable, and is thought to be due to the Namaqua-Natal Metamorphic Province acting as a geomorphological barrier at the time of their deposition. The minor Paleozoic (Ordovician to Carboniferous) detrital zircon populations in the samples from the formations of the Cape Supergroup increase progressively upwards through the succession. ....

M.Sc. / The strontium isotope ratio 87Sr/86Sr in the wine and soil of four wine-producing regions in South Africa has been determined using quadrupole ICP-MS. Isotope ratio measurements with fairly good precision had been obtained and 87Sr/86Sr ratio values in wine and soil samples were statistically evaluated to determine whether the regions investigated could be distinguished. Statistical interpretation of data revealed that the Robertson wine-producing region could be distinguished from Stellenbosch, Swartland and Walker Bay wine regions on the basis of their 87Sr/86Sr ratio. By using a combination of 87Sr/86Sr and multielement data, canonical discriminant functions with very good classification abilities could be obtained to correctly distinguish between wine and soil samples originating from a specific production region. Due to the isobaric overlap of strontium and rubidium at mass 87, a very good strontium-rubidium separation method had to be developed. The chelating properties of EDTA and DCTA in combination with ion exchange chromatography were explored in order to achieve such a separation. Due to the advanced rubidium separation ability of the developed DCTA elution method, it has been employed in all wine and soil sample preparations. Since chromatographic ion exchange procedures are not capable of removing all the rubidium from the sample matrices, 87Sr/86Sr ratio values were mathematically corrected for residual rubidium using an 88Sr correction. Since strontium isotope ratio measurements require very good precision, it is traditionally determined using TIMS. However, due to the ease of operation, shorter analysis time and widespread availability of quadrupole ICP-MS, the technique was evaluated for its merit for determining strontium isotope ratios. The optimization of acquisition parameters for the determination of the 87Sr/86Sr ratio in wine and soil samples with good precision of below 0.1% RSD has been conducted. Furthermore, selected sample matrix components were assessed as possible matrix interferences as well as for their ability to affect the precision of measurements. It was concluded that with adequate optimization of acquisition parameters, proper sample preparation and reliable mathematical correction of data, 87Sr/86Sr ratio measurements with reasonable precision could be obtained using quadrupole ICP-MS.

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

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京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19687号 / 工博第4142号 / 新制||工||1639(附属図書館) / 32723 / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 斧 髙一, 教授 稲室 隆二, 教授 青木 一生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM