Metalorganic vapour phase epitaxial growth and characterisation of Sb-based semiconductors
- Authors: Vankova, Viera
- Date: 2005
- Subjects: Compound semiconductors , Epitaxy , Organometallic compounds , Metal organic chemical vapor deposition
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10548 , http://hdl.handle.net/10948/d1019678
- Description: This study focuses on the growth and characterization of epitaxial InAs and InAs1-xSbx. Layers are grown on InAs, GaAs and GaSb substrates by metalorganic vapour phase epitaxy, using trimethylindium, trimethylantimony and arsine as precursors. The growth parameters (V/III ratio, Sb vapour phase compositions) are varied in the temperature range from 500 ºC to 700 ºC, in order to study the influence of these parameters on the structural, optical and electrical properties of the materials. The layers were assessed by X-ray diffraction, electron and optical microscopy, photoluminescence and Hall measurements. Furthermore, the influence of hydrogenation and annealing on the electrical and optical properties of GaSb was investigated. It is shown that the growth temperature and the V/III ratio play a vital role in the resulting surface morphology of homoepitaxial and heteroepitaxial InAs layers. Growth at low temperatures is found to promote three-dimensional growth in both cases, with improvements in the surface morphologies observed for higher growth temperatures. All the investigated epilayers are n-type. It is shown that the electrical properties of heteroepitaxial InAs epilayers are complicated by a competition between bulk conduction and conduction due to a surface accumulation and an interface layer. The low temperature photoluminescence spectra of homoepitaxial InAs are dominated by two transitions. These are identified as band-to-band/excitonic and donor-acceptor recombination. The incorporation efficiency of antimony (Sb) into InAs1-xSbx is dependent on the growth temperature and the V/III ratio. Under the growth conditions used in this study, the incorporation efficiency of Sb is controlled by the thermal stability of the two constituent binaries (i.e. InAs and InSb). Changes in the low temperature photoluminescence spectra are detected with increasing x. From temperature and laser power dependent measurements, the highest energy line is attributed to band-to-band/excitonic recombination, while the peak appearing approximately 15 meV below this line is assigned to donor-acceptor recombination. The origin of an additional “moving” peak observed for higher Sb mole fraction x is tentatively attributed to quasi-donor-acceptor-recombination, arising from increased impurity/defect concentrations and a higher compensation ratio in the material. However, the unusual behaviour of this peak may also be ascribed to the presence of some degree of ordering in InAsSb. The exposure of a semiconductor to a hydrogen plasma usually leads to the passivation of shallow and deep centres, thereby removing their electrical and optical activity. In this study, the passivation and thermal stability of the native acceptor in p-type GaSb is also investigated. It is shown that this acceptor can be passivated, where after improvements in the electrical and optical properties of GaSb are observed. Upon annealing the passivated samples above 300 °C, the acceptor is reactivated.
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- Date Issued: 2005
On the growth and characterisation of AIGaN alloys for optoelectronic applications
- Authors: James, Grant Robert
- Date: 2005
- Subjects: Gallium nitride -- Electric properties , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8824 , vital:26433
- Description: In this study the growth and characterisation of undoped and Si-doped AlxGa1-xN has been performed. The layers were grown using low-pressure metalorganic vapour phase deposition (MOCVD) on sapphire substrates. The optical and electrical properties of the AlxGa1-xN layers were studied using variable temperature Hall effect and photoluminescence measurements. AlxGa1-xN layers were grown over the entire composition range. Room temperature ultraviolet (UV) transmission measurements showed that the material quality was very good for layers with an Al content, x, of 0 _ x _ 0.5. However, the quality of layers of higher composition was seen to rapidly decrease with increasing x. The electrical and optical properties of AlxGa1-xN with x < 0.5 were also good, comparable to those reported on in literature. The study of the Si-doping of AlxGa1-xN was performed in two parts; firstly a series of Al0.23Ga0.77N samples was grown in which the doping level was increased from zero to n _ 3 × 1018 cm-3. A similar, albeit a less rigorous, study was performed for Al0.41Ga0.59N and Al0.5Ga0.5N. A second series of samples was then grown in which the doping level was kept constant, while the Al content was incrementally increased. Room temperature Hall effect measurements performed on Si-doped Al0.23Ga0.77N showed that the electron concentration did not scale linearly with the silane flow, as was the case in GaN. It was also seen that the electron mobility of the layers increased with slight Si-doping, possibly due to an improvement in the crystalline quality and/or a change in the conduction mechanism. It was also found that at higher compositions (x = 0.41 and 0.50) an increase in the doping level resulted in an increase in the mobility. Variable temperature Hall effect and photoluminescence measurements, performed on the Al0.23Ga0.77N samples, revealed a good correlation between the first PL activation energy E1 and the donor activation energy ED, prompting the conclusion that the first PL recombination channel in AlxGa1-xN is due to the delocalisation of excitons bound at neutral Si donors. Furthermore, E1 and ED were seen to decrease with n1/3, as is the case for GaN and other semiconductor materials. It was also observed that strong exciton localisation occurs in slightly Si-doped material, with the amount of localization becoming less at higher doping levels. Possible mechanisms responsible for the second PL recombination channel of activation energy E2 were also proposed. The electrical and optical properties of the second set of AlxGa1-xN samples was then studied. The PL properties of undoped AlxGa1-xN were typical of a homogeneous alloy system, with the increase in the PL FWHM and exciton localisation energies with x following the trend predicted by alloy disorder theory. The variation of the band gap energy with the Al content could not, however, be fitted over the entire composition range using a single bowing parameter. It was proposed that this was due either to an effect of the 9 7 valence band crossover, or due to exciton localisation at alloy disorder and/or impurities. As was the case for GaN and Al0.23Ga0.77N, all undoped material was highly resistive. As was mentioned earlier, the exciton localisation energies increased according to alloy disorder theory in undoped AlxGa1-xN. In the doped samples, however, a large increase in the donor localisation energy was measured for x > 0.3. The possibility that Si could become a DX-centre in AlxGa1-xN was then investigated. However, Hall effect measurements showed that the Si activation energy increased in good agreement with the model of a shallow effective mass state donor, with no sudden increase in ED being observed up to x = 0.4. It was then suggested that the increase in the E1 and E2 activation energies, as well as the exciton localisation energies, could be due to the 9 7 valence band crossover, which occurs at roughly the same composition. However, due to the scarcity of reports on the valence band structure in AlxGa1-xN no conclusions could be made at this stage as to the effect of the 9 7 valence band crossover on the PL properties of AlxGa1-xN.
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- Date Issued: 2005
An investigation of the binding capacities of recombinant domain mutants of the human Polymeric Immunoglobulin Receptor (pIgR)
- Authors: Prinsloo, Earl Adin Gerard
- Date: 2006
- Subjects: Immunoglobulins
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10307 , http://hdl.handle.net/10948/403 , Immunoglobulins
- Description: The membrane bound glycoprotein, polymeric immunoglobulin receptor (pIgR) is the primary transport molecule of the polymeric immunoglobulins, dimeric IgA and pentameric IgM, across epithelial cells. This process, known as transcytosis, is essential in order to establish immunity at mucosal surfaces. Typically, pIgR binds to the polymeric immunoglobulin at the basolateral surface of the epithelial cell, via five homologous immunoglobulin-like domains of the ectodomain. Binding is covalent to IgA and non-covalent to IgM; the IgM binding varying among species. The pIgR-bound complex is released at the apical surface of the cell after cleavage of pIgR at Arg585, thereafter referred to as secretory component (SC). SC confers protective and immunologic functions to the polymeric immunoglobulin. Free SC, i.e. not complexed with polymeric immunoglobulins, is also known to be released into mucosal secretions; and binds to pathogenic bacteria and bacterial products. It is known that domain I of the ectodomain is the primary domain in the interaction with polymeric immunoglobulins, while domain V is involved in a covalent linkage with IgA. However, little is known of domains II-IV and their role in immunoglobulin binding, particularly to IgM. This study aimed to characterize the binding of recombinant human pIgR domain mutants to polymeric IgM using immunological, biophysical and cell based techniques; thereby allowing greater insight into the contribution of each of the five domains. The unique domain structure allowed for selective amplification of single and multiple domain mutants from cloned human PIGR ectodomain cDNA. Mutants were cloned and expressed in Esherichia coli BL21 (DE3) as inclusion bodies. Recombinant mutant proteins were refolded in vitro by equilibrium gradient dialysis and purified to homogeneity. Equilibrium binding data show significant contributions to specific binding as a factor of domain presence. Binding kinetics determined by biophysical surface plasmon resonance measurements show the interplay between association and dissociation rates as defined by individual domains. In vitro competitive binding studies using the human intestinal carcinoma, HT29, known to constitutively express pIgR, show that the constructed recombinant domain mutants outcompete native pIgR. The level of competition is shown to be dependant on the domains downstream of domain I. The data also confirm the biological activity of the first in vitro refolded recombinant human SC.
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- Date Issued: 2006
Epitaxial growth and characterisation of CuGaS2
- Authors: Branch, Matthew Stewart
- Date: 2006
- Subjects: Epitaxy , Chalcopyrite , Semiconductors
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10541 , http://hdl.handle.net/10948/438 , http://hdl.handle.net/10948/d1012893 , Epitaxy , Chalcopyrite , Semiconductors
- Description: In this work, the growth and characterisation of the chalcopyrite semiconductor CuGaS2 is presented. The purpose of this study is to gain a better understanding of the defect chemistry of this class of materials through a systematic study relating the structural and optical properties to the composition of thin films grown by metalorganic vapour phase epitaxy. Details associated with the optimisation of the growth process are presented in a format relating the changes in the composition and morphology to variations in the growth process. The structural properties of thin films grown on GaAs(001) substrates are described. A dominance of polycrystalline growth is found to occur for Cu-rich material, whereas near-stoichiometric to Ga-rich material is typified by epitaxial growth. Secondary phases are identified by X-ray diffractometry and Raman spectroscopy for severely non-stoichiometric material. In some cases, the formation of the cubic zincblende and CuPt polytype of CuGaS2 are identified by transmission electron microscopy. It will be shown that changes in the Cu/Ga ratio of the solid strongly influence the photoluminescence response of the layers. Weak excitonic luminescence is observed for both slightly Ga-rich and Cu-rich material. Near stoichiometric layers exhibit luminescence centered at ~2.4 eV. Cu-rich layers are dominated by a line occurring at ~2.1 eV, whereas a different line at ~2.25 eV dominates for Ga-rich layers. A clear picture emerges of the radiative mechanisms dominating for Cu-rich and Ga-rich layers.
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- Date Issued: 2006
Metabolic effects brought about by tricyclic antidepressants and the contribution of a medicinal plant in alleviating high fat diet induced insulin resistance in male wistar rats
- Authors: Chadwick, Wayne
- Date: 2006
- Subjects: Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10329 , http://hdl.handle.net/10948/461 , Rats -- Metabolism , Diabetes -- Research , Medicinal plants -- South Africa
- Description: Type II diabetes is becoming a growing problem in developed countries worldwide. The median age for diagnosis was around sixty, but recent surveys have shown that the entire age distribution curve shifting left. The incidence of type II diabetes is thought to be parallel with the growing rate of obesity associated with an unhealthy western diet. Type II diabetes is an expensive disease to manage, it is for this reason that cheaper medication needs to be investigated in the form of traditional plants, such as Sutherlandia frutescens. Prescription medication, such as tricyclic antidepressants, may also increase body weight thereby playing a role in obesity. The cause of weight gain in such cases may go unrecognized or lead to cessation of the medication with or without the practitioner’s knowledge or approval. It is therefore necessary to investigate the causative agents responsible for the excessive weight gain. Drinking water containing extracts of S. frutescens or metformin was administered to two groups of eleven insulin resistant male Wistar rats. The insulin resistant control group received water without any medication. Rats were sacrificed after 8 weeks allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. The effect of the medication and the diet on muscle post receptor insulin signaling proteins was determined through Western blots. Liver proteomics was also performed using 2-D electrophoresis. In a separate experiment 26 male Wistar rats were exposed to strepotozotocin toxin, 7 of these rats received intravenous insulin treatment, 7 rats received S. frutescens extract and 7 rats received a combination of both medications, the remaining 5 received no treatment and served as the control. Rats were sacrificed after 6 days allowing for fasting blood glucose, insulin and tissue glycogen content determination. Two groups of 14 male Wistar rats received amitriptyline or trimipramine (common tricyclic antidepressants) in their drinking water, the control group (30 rats) received water without any medication. The rats’ weight and food consumption was monitored throughout the trial and their oxygen consumption was also determined. Rats were sacrificed after 6 weeks or 14 weeks of medicinal compliance allowing for fasting blood glucose, insulin and tissue glycogen content determination. Glucose uptake was also determined using [3H] deoxyglucose. S. frutescens treatment normalized circulating serum insulin levels and significantly increased the rate of glucose clearance. Certain post receptor insulin signaling proteins were also significantly increased relative to the insulin resistant control group. 2-D electrophoresis identified the normalization of protein levels associated with the urea cycle. S. frutescens was also able to, independently; maintain normoglycaemic levels in the strepotozotocin treated group. The tricyclic antidepressants significantly increased blood glucose levels while significantly reducing tissue glycogen levels for both sacrifice periods. Serum insulin remained unchanged while a significant increase in insulin degradation and insulin degrading enzyme levels were found for both antidepressants. S. frutescens shows promise as a low cost antidiabetic medication for future use. Although the antidepressants did not promote weight gain, the increase in blood glucose levels may be cause for concern in patients with a pre-disposition toward developing diabetes.
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- Date Issued: 2006
Characterization of WC-VC-Co and WC-VC-TiC-Co hardmetals
- Authors: Hashe, Nobom Gretta
- Date: 2007
- Subjects: Carbides , Hard materials
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10533 , http://hdl.handle.net/10948/522 , http://hdl.handle.net/10948/d1011723 , Carbides , Hard materials
- Description: This thesis contains the results of a study focused on cubic carbide and carbonitride grain growth retardation in hardmetals. Large additions of VC, or VC and TiC, or (W,V)C were made to the WC-Co hardmetal, which was then sintered in vacuum or nitrogen. The effectiveness of Ti as the grain growth inhibitor, and the influence of nitrogen sintering on grain coarsening were investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffractrometry (XRD) and atom probe field ion microscope (APFIM). Analysis of vacuum-sintered WC-VC-Co revealed that the cubic carbide grains have a core-rim structure. Ti was found to be a core-rim inhibitor in vacuum-sintered WCVC- TiC-Co. The average cubic carbide grain size distribution for the vacuumsintered materials was narrowed in the Ti-containing hardmetal. The nitrogen-sintered WC-VC-TiC-Co consisted of two phases of cubic carbonitride, one with high Ti-content and the other with high (W,V)-content. The surface region of the nitrogen-sintered WC-VC-TiC-Co was covered with a cubic carbonitride phase. Similar phenomena was observed in nitrogen-sintered WC-VC-Co where two types of carbonitrides were found, those with high V-content and the others with low Vcontent. A gradient zone, consisting of fine WC grains in a Co-rich binder and free from cubic carbonitride grains, was created in the surface region. The nitrogensintered materials consisted of a narrow grain size distribution. The use of (W,V)C as a starting powder affected the mechanical properties of the material with the WC-(W,V)C-Co material being the hardest of those produced in this study. Addition of (W,V)C powder to WC-Co was shown to be the most effective way to limit the cubic carbide grain size during sintering and produce a hard material. The cubic carbide grain size in the material produced this way was the smallest of all studied.
- Full Text:
- Date Issued: 2007
Clients' views on construction and design team competencies
- Authors: Crafford, Gerrit Jacobus
- Date: 2007
- Subjects: Construction industry -- Employees , Core competencies
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:9679 , http://hdl.handle.net/10948/490 , Construction industry -- Employees , Core competencies
- Description: The effectiveness of the design and construction team in meeting clients’ requirements entirely depends on the competency proficiency of the design and construction teams. This research presents a model of the important competencies required by the design and construction teams in order to provide a competent service as seen by the client. A review of related literature followed by interviews by selected practitioners yielded 29 architectural competencies, 31 civil engineering competencies, 32 construction management competencies, 31 project management competencies, and 33 quantity surveying competencies that were presented in a structured questionnaire. The questionnaire was completed by 52 developers from a census of developers and municipality managers in South Africa. Respondents were asked to rank or rate: the level of importance of each competency for a career in that specific discipline; how evident that competency is in the specific discipline in South Africa; the level of importance of the performance parameters to clients, and the extent to which the various disciplines realise client satisfaction relative to the various performance parameters. The techniques of re-scaling, principal component analysis, content analysis, ranking and quadrant analysis were applied to the data. Results showed a high degree of consistency among respondents in all disciplines, regardless of the demographic differences in the importance of the competencies. A factor solution was obtained for every discipline using principal component analysis on the important competencies of each discipline. The various factor solutions were in turn used to formulate a simplified model. The model shows that the factors are interdependent and interacting. The model indicates that primary competencies for each profession are supported by mostly secondary competencies. These factors v are in turn influenced by the inter-relationships between the practitioners, continued professional development/ research and universities, which are then in turn, influenced the governing bodies. The local and global environment then ultimately influences the governing bodies. An Importance-Evidence quadrant analysis was undertaken in order to integrate the rankings of the current importance levels and current proficiency levels for each discipline’s competencies, which helped to identify areas in which education and training is immediately needed. Respondents ranked all nine performance parameters above average which indicates that there are more than the traditional performance parameters of cost, quality, and time involved in satisfying clients. The research concluded that vital feedback from clients regarding the competencies required by the respective professionals in the design and construction team was obtained.
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- Date Issued: 2007
Collaborative research with traditional African health practitioners of the Nelson Mandela Metropole : antimicrobial, anticancer and anti-diabetic activities of five medicinal plants
- Authors: Van Huyssteen, Mea
- Date: 2007
- Subjects: Medicinal plants -- South Africa -- Port Elizabeth , Healers -- South Africa -- Port Elizabeth , Anti-infective agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10148 , http://hdl.handle.net/10948/663 , Medicinal plants -- South Africa -- Port Elizabeth , Healers -- South Africa -- Port Elizabeth , Anti-infective agents
- Description: The promotion and development of indigenous knowledge pertaining to the traditional African healing system is one of the prime objectives set out by the South African government. Despite excellent research opportunities and funding, the biggest problem with ethnopharmacological research is a lack of interaction with indigenous communities, which tends to dilute the benefits this research has to offer these communities. The primary aim of this study was thus to promote the traditional African healing system through collaborative medicinal plant research with local traditional health practitioners. The research collaboration aimed to validate some biological activities of traditional remedies used by collaborating traditional health practitioners and ensured interactive sessions where scientific literature, research practices, findings and relevant legislation were discussed and debated. The joint development of a medicinal garden was a valuable tool in realising these goals. Aqueous and ethanol extracts of Bulbine frutescens, Ornithogalum longibracteatum, Ruta graveolens, Tarchonanthus camphoratus and Tulbaghia violacea were selected for antimicrobial, anticancer and anti-diabetic screening, because of their sustainable utilisation potential. The ethanol extract of T. violacea produced the best antimicrobial activity on Bacillus subtilis (100% growth inhibition) and Candida albicans (89% growth inhibition) at 250 μg/ml. The EC50 for the ethanol extract of T. violacea against HT29 colon cancer cells was 101 μg/ml. The aqueous extracts of B. frutescens and T. camphoratus (0.5 and 50 μg/ml) produced the highest overall glucose uptake activity in Chang liver and C2C12 muscle cells. T. camphoratus was unanimously chosen by participating practitioners as the plant to be investigated further. The aqueous extract of T. camphoratus increased glucose uptake in C2C12 muscle cells through increased translocation of GLUT4 to the plasma membrane and activation of the PI3-kinase and AMP-kinase pathways. It produced some alpha-glucosidase inhibitory activity at concentrations of ≥ 200 μg/ml. Apart from interactive feedback seminars at which the findings were presented to participating practitioners, all scientific literature regarding the plants was summarised, translated, compiled and given to participating practitioners in written format. An indigenous knowledge agreement has been negotiated and will formalise the collaboration in future. It is recommended that future research focuses on plants with economic development potential that can be cultivated in the medicinal garden.
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- Date Issued: 2007
Contributions to the use of microalgae in estuarine freshwater reserve determinations
- Authors: Snow, Gavin Charles
- Date: 2007
- Subjects: Microalgae -- South Africa , Estuarine ecology -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10620 , http://hdl.handle.net/10948/709 , Microalgae -- South Africa , Estuarine ecology -- South Africa
- Description: The ecologist Garrett Hardin (1968) introduced a useful concept called the tragedy of the commons, which describes how ecological resources become threatened or lost. The term “commons” is based on the commons of old English villages and is symbolic of a resource that is shared by a group of people. If every person were to use each resource in a sustainable fashion it would be available in perpetuity. However, if people use more than their share they would only increase their personal wealth to the detriment of others. In addition, an increase in the population would mean that the size of each share would have to decrease to accommodate the larger number of people. As a result, resources are threatened by personal greed and uncontrolled population growth. Freshwater is an example of a common resource that is under threat in South Africa where the average annual rainfall is less than 60 percent of the global average (Mukheibir & Sparks 2006). The increasing demands for freshwater as well as its eutrophication are major concerns with regards to estuarine health, environmental resource management and human health. The correct management of water is necessary to ensure that it is utilised in a sustainable manner. The National Water Act (No. 36 of 1998) has provided the rights to water for basic human needs and for sustainable ecological function; the Basic Human Needs Reserve and Ecological Reserve are both provided as a right in law. The amount of water necessary for an estuary to retain an acceptable ecological status, known as the Estuarine Ecological Reserve, is determined through the implementation of procedures (rapid, intermediate or comprehensive) compiled by the Department of Water Affairs and Forestry (1999) in its Resource Directed Measures (RDM) for the Protection of Water Resources. The impact of restricted flow on estuaries can be reduced by manipulating the water released from impoundments, the regulation of water abstractions within the river catchment or both (Hirji et al. 2002). The reserve assessment method is designed to evaluate ecosystem requirements by employing groups of specialists from different disciplines. In South Africa, this includes hydrologists, sedimentologists, water chemists and biologists (including microalgae specialists). The use of microalgae in ecological assessments has largely been based on research that was initiated at the Nelson Mandela Metropolitan University (formerly University of Port Elizabeth) and subsequently at Rhodes University (Grahamstown) and the University of KwaZulu Natal (Durban). The microalgal research can be divided into two main focus areas; phytoplankton and benthic microalgae
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- Date Issued: 2007
On the characterization of photovoltaic devices for concentrator purposes
- Authors: Vorster, Frederick Jacobus
- Date: 2007
- Subjects: Photovoltaic cells , Image processing , Solar cells
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10530 , http://hdl.handle.net/10948/639 , Photovoltaic cells , Image processing , Solar cells
- Description: This study originated from an evaluation of the performance of a commercially available high concentration point focus concentrator PV system. The effect of module design flaws was studied by using current-voltage (I-V) curves obtained from each module in the array. The position of reverse bias steps revealed the severity of mismatch in a string of series-connected cells. By understanding the effects of the various types of mismatch, power losses and damage to the solar cells resulting from hot spot formation can be minimized and several recommendations for improving the basic performance of similar systems were made. Concern over the extent and type of defect failure of the concentrator photovoltaic (CPV) cells prompted an investigation into the use of a light beam induced current (LBIC) technique to investigate the spatial distribution of defects. An overview of current and developing LBIC techniques revealed that the original standard LBIC techniques have found widespread application, and that far-reaching and important developments of the technique have taken place over the years. These developments are driven by natural progression as well as the availability of newly developed advanced measurement equipment. Several techniques such as Lock-in hermography and the use of infrared cameras have developed as complementary techniques to advanced LBIC techniques. As an accurate contactless evaluation tool that is able to image spatially distributed defects in cell material, the basis of this method seemed promising for the evaluation of concentrator cells.
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- Date Issued: 2007
On the microstructure and physical properties of hot pressed (Hf, Ti) C
- Authors: Heiligers, Christiané
- Date: 2007
- Subjects: Transition metal carbides
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10532 , http://hdl.handle.net/10948/523 , http://hdl.handle.net/10948/d1011722 , Transition metal carbides
- Description: The microstructure and physical properties of hot pressed (Hf, Ti) C have been investigated with the aim of producing a cutting tool material with similar hardness to that of WC-Co and TiC-based cermets. Sintered samples were hot pressed from HfC0.7 and TiC0.9 powders using powder metallurgical techniques and the processing cycle was optimized for this system. Ni was used as a binder in selected samples and C black was added to compensate for sub-stoichiometry and to aid in the reduction of oxides formed during milling. Microstructural analyses were performed by scanning and transmission electron microscopy (SEM and TEM) and the composition was determined from X-ray diffraction (XRD) and energy dispersive X-ray spectrometry (EDS). The physical properties measured are density and Vickers hardness, and the indentation fracture toughness was determined using the Shetty formula. The fundamental interactions between HfC, TiC and Ni during hot pressing were investigated and the results obtained used to explain the microstructure that develops in samples made from powder mixtures. The interactions studied are the inter-diffusion of HfC and TiC through the solid state, and the dissolution and re-precipitation rate of the carbides in a liquid Ni binder. EDS analysis revealed that the rate at which Ti diffuses into HfC is higher than the rate at which Hf diffuses into TiC. Upper limits to the diffusion coefficients for these processes are determined and show that solid solution carbides will form from HfC + TiC powder mixtures at 2000 ºC in 1 hour if the average powder particle size is less than 5 μm. The diffusion rates decrease with a decrease in hot pressing temperature but mass transport between the phases can be enhanced by addition of a metallic binder. TEM and EDS analysis shows that Ni wets TiC more efficiently than HfC and that the solubility of TiC in Ni is also higher than that of HfC. The grain size of the carbide phases increases with an increase in the rate at which they dissolve into and re-precipitate from the liquid binder. The crystal structure of the binder phase depends on the concentration of Ti and Hf that remain in the binder after cooling and the carbide phase in which the binder is embedded. Analysis of TEM electron diffraction patterns show that the binder phase consists of cubic solid solutions as well as intermetallic and cubic phases in which atomic ordering is observed.
- Full Text:
- Date Issued: 2007
Prime near-ring modules and their links with the generalised group near-ring
- Authors: Juglal, Shaanraj
- Date: 2007
- Subjects: Near-rings
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10507 , http://hdl.handle.net/10948/714 , Near-rings
- Description: In view of the facts that the definition of a ring led to the definition of a near- ring, the definition of a ring module led to the definition of a near-ring module, prime rings resulted in investigations with respect to primeness in near-rings, one is naturally inclined to attempt to define the notion of a group near-ring seeing that the group ring had already been defined and investigated into by, interalia, Groenewald in [7] . However, in trying to define the group near-ring along the same lines as the group ring was defined, it was found that the resulting multiplication was, in general, not associative in the near-ring case due to the lack of one distributive property. In 1976, Meldrum [19] achieved success in defining the group near-ring. How- ever, in his definition, only distributively generated near-rings were considered and the distributive generators played a vital role in the construction. In 1989, Le Riche, Meldrum and van der Walt [17], adopted a similar approach to that which led to a successful and fruitful definition of matrix near-rings, and defined the group near-ring in a more general sense. In particular, they defined R[G], the group near-ring of a group G over a near-ring R, as a subnear-ring of M(RG), the near-ring of all mappings of the group RG into itself. More recently, Groenewald and Lee [14], further generalised the definition of R[G] to R[S : M], the generalised semigroup near-ring of a semigroup S over any faithful R-module M. Again, the natural thing to do would be to extend the results obtained for R[G] to R[S : M], and this they achieved with much success.
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- Date Issued: 2007
Synthesis, properties and reactions of Novel Quinone Methides
- Authors: Taljaard, Jana Heloïse
- Date: 2007
- Subjects: Quinone , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10408 , http://hdl.handle.net/10948/616 , Quinone , Chemistry, Organic
- Description: Novel p-quinone methides have been synthesized by the dealkylation of 5-(p-alkyloxyaryl)- 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ols and related compounds. Aspects of the dealkylation reaction were investigated using computational methods in order to identify possible intermediates and postulate reasons for the observed reactivity patterns. This included studying the effect of varying the size of the central B-ring, changing the alkyloxy group, and altering the substitution pattern on the parent alcohols. We have assessed the relative energies of reaction intermediates and have also evaluated the influence of factors such as charge delocalisation, LUMO properties of the carbocations and thermodynamic factors on the dealkylation reaction. The use of different dealkylating reagents was also briefly investigated. Demethylation of 1,3- dimethyl-11-(4-methoxyphenyl)-6,11-dihydrodibenzo[b,e]oxepin-11-ol with pyridine hydrochloride led to acid-catalyzed ring-contraction of the parent alcohol to form a novel substituted anthraquinone, 9-(4-hydroxyphenyl)-1,3-dimethyl-anthracen-10-(9H)-one, in good yield. The general reactivity of the p-quinone methides of interest to us was explored by subjecting these compounds to reaction with a range of nucleophiles (bases, Grignard reagents and alcohols). A range of aryl Grignard reagents were reacted with the p-quinone methides, with the main product isolated in almost all cases being the aryl-coupled 1,2-addition product. The nucleophilic addition reactions of alcohols were supported by a computational study and a probable reaction mechanism has been postulated. A base-catalyzed rearrangement is proposed to account for the formation of products in which dehydrogenation of the ethane bridge was observed. These studies showed that in these p-quinone methides, chemical reactivity is strongly influenced by steric crowding, resulting in reversal of the normal 1,2- vs. 1,6- selectivities expected for nucleophilic addition. The ketalization process was explored further using diols and thiols. Products analogous to those obtained with the monohydric alcohols resulted from the diols, along with a series of novel bis-ethers. A range of miscellaneous reactions of 4-(dibenzo[a,d]cycloheptan-5-ylidene)cyclohexa-2,5,- dienone and related systems were investigated. Functionalization by epoxidation, dichlorocarbenation and Diels-Alder reactions, photochemical and [2+2] cycloaddition were attempted and reduction and oxidation reactions were also explored. Photochemical demethylation of an ortho-methoxyl substituent on the p-quinone methide system was observed to occur in good yield. The p-quinone methides underwent reductive coupling in the presence of Zn/AlCl3. The electronic spectra of highly conjugated carbocations were obtained and their potential as novel dyes evaluated. A low-temperature Grignard exchange reaction followed by spontaneous cyclization upon workup, was successful in synthesizing the lactone, spiro[10,11- dihydro-5H-dibenzo[a,d]cyclohepten-(3’,4’H)-phenyl-5,2’(5’H)-furan-5’-one], in one step from the starting ketone. A novel seven-membered Malachite Green dye analogue, 11-(4- dimethylamino-phenyl)-3-morpholin-4-yl-6,11-dihydro-dibenzo[b,e]oxepin-11-ol, was also synthesized and its electronic spectra compared to that of the unannulated Malachite Green dye series. All novel compounds synthesized were characterized using NMR, IR and HRMS-analysis.
- Full Text:
- Date Issued: 2007
The kinetics and associated equilibria of high oxidation state osmium complexes
- Authors: McFadzean, Belinda Julie
- Date: 2007
- Subjects: Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10371 , http://hdl.handle.net/10948/732 , Chemical equilibrium , Osmium , Chemical kinetics , Chemistry
- Description: The reduction of osmium tetroxide by a series of alcohols was studied spectrophotometrically. The reaction was observed to occur in two steps, unlike previously reported studies on this reaction. The identities of both reactants and products were established via a range of techniques. Equilibrium and kinetic data were gathered and reaction models were evaluated using equilibrium and kinetic modelling software. The following complexation reaction model emerged that simulates both the equilibrium and kinetic data. Os(VIII) + RCH2OHOs(VI) + RCHO2 Os(VIII) + Os(VI)k+2k1Complexk-2 Conditional rate constants and equilibrium constants were generated. Rate constants for the alcohol reactions were correlated with the Taft σ* constant. The ρ* value obtained (-1.4) is consistent with a hydride transfer mechanism coupled with synchronous removal of the hydroxyl proton. The identity of the osmium(VIII)-osmium(VI) complex has been suggested. Thermodynamic parameters were also reported. The rate constants for benzyl alcohol and 2-chloroethanol deviated from those predicted by the Taft plot. An explanation of enhanced resonance effects is offered for benzyl alcohol and an alternative reaction mechanism, involving proton abstraction, is offered for 2-chloroethanol. The reaction of the oxidation products of alcohols, namely ketones, with osmium tetroxide produced rate constants that were, perhaps surprisingly, far larger than those of the alcohols. A reaction mechanism for the oxidation of the ketones is suggested, which involves the enolate ion as the reactive starting reagent.
- Full Text:
- Date Issued: 2007
Towards knowing through doing : improving the societal relevance of systematic conservation assessments
- Authors: Knight, Andrew Thomas
- Date: 2007
- Subjects: Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10598 , http://hdl.handle.net/10948/711 , Conservation of natural resources -- Planning , Nature conservation -- South Africa
- Description: Systematic conservation assessments are spatially-explicit techniques for prioritising areas for the implementation of conservation action. There has been considerable reference in the peer-reviewed literature as to the usefulness of these tools, which appear to be primarily used by academics for theoretical research. A literature review and author survey reveals the peer-reviewed literature is largely theoretical, although conservation action results more frequently than reported. The effectiveness of these interventions is generally described as only ‘fairly effective’. This general trend, coupled with previous personal failures in translating systematic conservation assessments into effective conservation action triggered an explicit process of social learning implemented as action research. It examined the workings of the Subtropical Thicket Ecosystem Planning (STEP) project, which included development of a systematic conservation assessment. Systematic conservations assessments simply provide information on where action should be implemented, and so are only useful if situated within broader operational models for conservation planning. Most operational models presented in the peer-reviewed literature are primarily focused upon the testing ecological data, not upon the delivery of conservation action. A new operational model for conservation planning is presented which more accurately reflects the ‘real-world’ process of conservation planning. An implementation strategy is an essential complement to a systematic conservation assessment. It describes how specific, explicitly-stated goals will be achieved, who is accountable for undertaking these activities, and the resources required. As the Implementation Specialist for the STEP Project, I co-lead the collaborative development of an implementation strategy with stakeholders that aimed to mobilise resources towards achieving common goals. Whilst the development and initial uptake of the strategy was good, subsequent implementation has flounder. The reasons for this are explored. The ultimate pragmatic goal of a conservation planning process is the establishment of effective social learning institutions. These develop common visions, mobilise collective action, and adaptively learn and refine their conservation activities. Thicket Forum is one xi such institution established through the STEP Project. My involvement with Thicket Forum since 2004 in implementing an adaptive learning approach facilitates collaboration between land managers, government and research organisations. Systematic conservation assessments evolved in response to the ad hoc way in which protected areas were implemented, leaving unrepresentative, biased protected area networks. Most research is theoretical and without an intimate understanding of the social-ecological system of a planning region, notably opportunities and constraints for implementing conservation action. Highlighting the importance of an approach which is flexible, not only in space, but in time, which can capitalise upon implementation opportunities, is important for stemming the myth that opportunism is the nemesis of systematic conservation assessments. To this end, conservation planners have been slow to include factors influencing effective implementation in systematic conservation assessments. Many studies which identify candidate protected area networks, first, fail to identify the specific instrument(s) to be applied, and second, assume all intact land is available. Having mapped the willingness of land managers in the Albany District, South Africa, to sell their land, it is demonstrated the majority of targets fail to be achieved because land managers will not sell. Knowing this, the current focus of gathering ever-more ecological data is misplaced. Human, social and economic factors influence target achievement, efficiency and spatial configuration of priority areas. Selecting important areas for conservation, particularly at the local-scale, requires the mapping of factors which define opportunities for conservation. Land manager willingness to collaborate and participate, entrepreneurial orientation, conservation knowledge, social capital, and local champions were applied using a method of hierarchical clustering to identify land managers who represent conservation opportunities for private land conservation initiatives.
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- Date Issued: 2007
Identification and characterization of novel oncology related platinum complexes using chromatographic and mass spectrometric techniques
- Authors: Wentzel, Mauritz
- Date: 2008
- Subjects: Chromatographic analysis , Spectrum analysis
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10310 , http://hdl.handle.net/10948/715 , Chromatographic analysis , Spectrum analysis
- Description: In this thesis mass spectral and chromatographic techniques were developed and applied to identify and characterise numerous novel platinum(II) and (IV) compounds designed as anticancer agents. In a novel method for the synthesis of cis-oxalato(trans- -1,2- cyclohexanediamine)platinum(II) or oxaliplatin these techniques could be applied to differentiate between the molecular complex and the autoionised analogue (viz. Ptdach2 2+Ptox2 2-). In another novel synthetic method for the same compound the ligand exchange reactions at various temperatures could be investigated and kinetic curves obtained served to illuminate the chemistry involved, indicating the role of small amounts of water in the essentially non-aqueous solvent systems dmf and isoamyl alcohol respectively. These allowed ligand exchange without resulting in hydrolyses even up to 85°C. The ionisation rate of divalent platinum halide complexes was determined for various amine ligands as well as N-S chelate ligands. A comparison of these could suggest why N-S complexes have poor anticancer action. Ionisation was not only studied for neutral molecular species but also for monocationic ones. Relationships could be found with stereochemical aspects of the chelates used. By investigating results of EV-CAD studies thermodynamic data could be obtained which indicated that bond strength decreases from chloro to iodo analogues although extent of ionisation in aqueous solution, i.e kinetic stability, is the reverse. Products formed by the reaction of NO2 gas with Platinum(II) compounds could be identified and separated which greatly contributed to the understanding of the chemistry involved in the formation of mononitro platinum(IV) complexes. Some of these proved to have exceptional anticancer properties. Studies of the interaction of thiol containing biomolecules were performed as a function of time. The results contributed to the understanding of the action of the anticancer agents.
- Full Text:
- Date Issued: 2008
Novel aspects of platinum-amine coordination compounds: their chemistry and anticancer application
- Authors: Bouwer, Yolanda
- Date: 2008
- Subjects: Coordination compounds , Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10444 , http://hdl.handle.net/10948/d1021052
- Description: The aim in this thesis, was to synthesize novel platinum coordination compounds, in order to develop compounds with improved anticancer action which could lead to an improved understanding of the mechanism by which they operate and at the same time, improve synthetic methods for their products. The initial work included the development of a novel synthetic method for 1R,2R-diaminocyclohexaneoxalato-platinum(II) (oxaliplatin), by using an essentially non-aqueous solvent medium and direct ligand exchange at elevated temperatures. This was done by a study of the kinetics of the reaction in a variety of conditions; such as relative reagent concentrations and ratios as well as solvent mixtures. An effective method was developed which could be applied industrially. An international patent was taken out on this method. Various amine complexes of platinum(II) were synthesized using chloro, bromo and oxalato groups as leaving groups. The non-leaving groups were selected having certain specific characteristics in mind. Novel mononitroplatinum(IV) complexes were synthesized, mostly with oxalato leaving groups. One of these in particular, had excellent anticancer behaviour. Another trichloromononitro complex was also synthesized with very good anticancer properties. Two international patents were filed for the latter two compounds. As far as possible, all compounds were studied by spectrometric, chromatographic and thermal methods. They were also tested against 3 cancer cell lines namely cervical (Hela), Colon (HT29) and Breast (MCF7) cancer cells.
- Full Text:
- Date Issued: 2008
Novel camphor derivatives as potential asymmetric alkylation auxiliaries
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
On the optical characterization of photovoltaic devices
- Authors: Gxasheka, Andile Richman
- Date: 2008
- Subjects: Photovoltaic power systems -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10529 , http://hdl.handle.net/10948/692 , Photovoltaic power systems -- South Africa
- Description: Semiconductor materials used for making photovoltaic (PV) cells have defects and impurities due to constraints of keeping production costs low. Electrically active defects that are distributed over the bulk material lead to reduced overall performance of a photovoltaic (PV) cell. In this study an adaptable Light Beam Induced Current (LBIC) system was designed in order to characterize the local performance of PV cells. The system uses a laser source and objective lens mounted vertically above the sample on the X-Y stage. Two current pre-amplifiers are used for converting the photo-generated current from the PV cell and the signal from the reflection detector cell into a voltage that can be measured by the data acquisition board. Two configurations for measuring the photo-current maps of either bare cells or encapsulated PV mini-modules can be used. To add flexibility it was envisaged that the system would be built in such a way that it allows easy integration of carrier lifetime mapping capabilities while keeping costs to a minimum. The carrier lifetime measurement technique integrated into the LBIC system is based on the optical Open-Circuit Voltage-Decay (OCVD) method. In a single-crystalline silicon PV cell that was tested, photo-current and opencircuit voltage LBIC scans revealed shunting behaviour due to scratch marks on the front surface. The marks are believed to have been caused by poor handling during manufacturing process. Reduced photo-current due to edge shunting was observed towards the edges of the PV cell. In another sample of single crystalline silicon cell an edge shunt resulted in a 30 percent drop in photo-current measured. LBIC measurements performed on multi-crystalline cells revealed nonuniformities such as enhanced photo-current on one side of grain boundaries. These asymmetric enhancements of local photo-current are attributed to the incline of the grain boundary into the bulk of the material. LBIC results obtained from mini modules showed a high degree of mismatching from cell to cell. It is well known that mismatching can degrade the performance of a PV module with series connected cells. The LBIC measurements presented also illustrated the negative effects of delamination on the photo-current of PV modules. The LBIC measurements performed on mini PV modules highlight some of the benefits of using an LBIC technique as a tool for investigating PV cell’s local photo-current response. The effective lifetime maps obtained highlight the importance of optical OCVD method as a tool that can be used in conjunction with conventional LBIC technique. Effective minority carrier lifetimes around 40 ms were measured on a single crystalline silicon cell of 2.5 x 2.5 cm2. Local features such as cracks and lifetime degrading defects were revealed by LBIC maps and were also confirmed on effective lifetime maps. The results presented demonstrate the importance of using effective carrier lifetime maps to complement photocurrent maps of PV cells and identification of areas where defects are located.
- Full Text:
- Date Issued: 2008
Phytoplankton chlorophyll a concentration and community structure in two temporarily open/closed estuaries in the Eastern Cape, South Africa
- Authors: Gama, Phumelele Thuthuka
- Date: 2008
- Subjects: Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10621 , http://hdl.handle.net/10948/707 , Estuarine ecology -- South Africa , Chlorophyll -- South Africa , Estuaries -- South Africa , Phytoplankton populations -- South Africa
- Description: River flow is important in controlling phytoplankton distribution in estuaries. Data on the effect of river inflow on phytoplankton distribution patterns in temporarily open/closed estuaries is lacking. This study investigated the influence of river inflow on size-fractionated phytoplankton biomass (Chl a), community composition and environmental parameters measured monthly over three years in two temporarily open/closed estuaries in the Eastern Cape, South Africa. A once-off primary production study over an annual cycle was completed in the Van Stadens and Maitland estuaries. The study monitored physical, chemical and biological characteristics in both estuaries to examine the effects of changes in environmental factors and river inflow. Daily sampling of physico-chemical and biological variables from river to sea was carried out in the Van Stadens to investigate short-time scale effects of changes in environmental factors and river inflow on the phytoplankton biomass. Five and three stations in the main channel of the Van Stadens and Maitland estuaries respectively were sampled at 0.5 m below the water surface and 0.5 m above the sediment surface for biological and chemical variables and at the surface, 0.25 m and every 0.5 m thereafter for physical parameters. Five stations adjacent to the main channel along the estuary were monitored for groundwater macronutrient concentrations and five additional sites located within the upper catchment of the Van Stadens River were sampled on a quarterly basis over two years. Both estuaries were characterised by distinct hydrological conditions, an overwash, an open, a closed and a semi-closed mouth phase. Flooding in the Maitland and Van Stadens estuaries in 2001 and 2002 caused sediment scour, altered channel morphology and brought about breaching of the mouth. Flood driven mouth-breaching events occurred three and four times in each of the estuaries during the study. The mouth stayed open 20 – 25 percent and was closed 60 – 65 percent of the time. In the Van Stadens the closed overwash mouth condition occurred approximately 10 – 20 percent of the time while in the Maitland it occurred less with the semi-closed mouth condition occurring 10 – 20 percent of the time. Incidents related to mouth opening not associated with strong river floods occurred approximately 10 – 15 percent of the time, although in the Maitland a semi-closed mouth state persisted more frequently than in the Van Stadens Estuary. During flooding events salinity dropped to low levels (< 5 psu) but soon recovered to brackish conditions when river flow was reduced and marine water penetrated deep upstream. Reduction in river flow combined with marine sediment deposition resulted in the closure of the mouth. During closed mouth conditions strong onshore storm surges and spring high tides introduced marine water through overwash that kept salinity high. In both estuaries salinity showed a negative correlation with rainfall (R2 = 0.12), indicative of the strong influence of marine overwash that kept salinity high thus masking the influence of freshwater. High rainfall in the Van Stadens Estuary caused high levels of turbidity that reduced light penetration at depth. Light attenuation was positively correlated with the high rainfall (R 2 = 0.26) suggesting that increased turbidity was linked to rainfall induced discharge. In contrast, in the Maitland Estuary light attenuation did not show any correlation with increased rainfall possibly because of the reduced water depth and increased euphotic zone following the floods in 2002. High river inflow introduced macronutrients in both estuaries such that dissolved inorganic phosphates (DIP) and dissolved inorganic nitrogen (DIN) concentrations in the Van Stadens Estuary were strongly correlated with rainfall (R2 = 0.78 and 0.57 respectively). In the Maitland Estuary DIP and DIN concentrations remained significantly higher (p < 0.05) compared to that in the Van Stadens suggesting that the Maitland catchment contributed greater nutrient input into the estuary and may be associated with farming activities. Phytoplankton chlorophyll a (Chl a) ranged from 0.8 – 13.9 μg L-1 in the Van Stadens and in the Maitland Estuary from 5.3 – 138 μg L-1 during the 3-year study. During the open mouth condition Chl a biomass and primary production ranged from 5.4 – 52.9 μg Chl a L-1 and 1.2 – 11.7 mg C m-2 d-1 in the Maitland and in the Van Stadens from 1.6 – 9.8 μg Chl a L-1 and 1.2 - 14 mg C m-2 d-1 respectively. Maximum annual primary production in the Maitland and Van Stadens estuaries was 8.8 and 5.1 g C m-2 y-1 respectively. When the mouth was open in the Van Stadens Estuary the microphytoplankton (> 20 μm) accounted for > 65 percent of the Chl a, whereas during closed mouth conditions they accounted for about 55 percent of the Chl a biomass. Chlorophytes became the dominant taxon in the dry summer months but were replaced by cryptophytes and dinoflagellates during the wet season. When nutrient concentrations were low during low flow conditions in the Van Stadens Estuary mixotrophic microphytoplankton became an important fraction of the water column together with phototrophic dinoflagellates and cryptophytes. In the Maitland large sized chlorophytes were the dominant taxa in late spring and summer seasons and made up more than 80 percent of the cell numbers. In the Maitland before the floods in 2002 cyanophytes were the dominant group in late spring contributing more than 75 percent in cell abundance. Data from the short-term study in the Van Stadens Estuary showed similarities and differences in the Chl a response to increased river inflow. High river inflow initially reduced Chl a biomass followed by a recovery period of a couple of days compared to a 8 – 10 week recovery period in studies monitored over seasonal and annual temporal scales. The responses may be dissimilar but help to illustrate that there are similar response patterns to environmental forcing necessary to support phytoplankton biomass at different temporal scales. This study has demonstrated that flooding events caused by strong river flow cause breaching of the mouth, a reduction in salinity and marked nutrient input. Although the causes of flooding can be similar in both estuaries the resultant effects are varied and can alter the ability of the estuary to retain water. This study was able to demonstrate that the supply of macronutrients from the catchment was strongly correlated with rainfall (R2 = 0.67) and that phytoplankton growth mainly depended on an allochthonous source of macronutrients although internal supplies could be critical at times in controlling microalgal biomass.
- Full Text:
- Date Issued: 2008