Ecological role of estuarine brachyuran crabs in mangrove and salt marsh estuaries, Eastern Cape, South Africa
- Authors: Vorsatz, Jeanne Pauline
- Date: 2009
- Subjects: Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10698 , http://hdl.handle.net/10948/1108 , Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Description: Crabs are conspicuous inhabitants of temperate salt marshes and tropical mangroves and interact with their environment through several processes. However, detailed information on crab community processes is absent for most South African estuaries and nearshore coastal regions. This study evaluated the primary producers supporting crab species in the salt marsh dominated Swartkops estuary and the mangrove Mngazana estuary. Various methods estimating crab abundances were also assessed in different microhabitats and the larval distribution of crabs in the coastal zone was also investigated. Various methods for estimating crab abundance have been employed in the past, each with its inherent biases. The microhabitat of a mangrove forest in Australia was structurally altered by the manipulation of the litter, pneumatophores and the associated algae. These alterations did not affect the behavioural activity or the numbers of crabs recorded in any of the experimental treatments by either visual counts or pitfall traps. However, the number of crabs caught in the pitfall traps differed between the sites. Species-specific behaviour which was not investigated in this study may bias crab abundance estimates when using pitfall traps and therefore requires further investigation. Benthic consumers inhabiting shallow coastal environments may ultimately have the origin of their nutrition in a number of possible sources. Isotopic and gut content analysis of Thalamita crenata and juvenile Scylla serrata in the Mngazana estuary in South Africa revealed that these two portunids are able to share a habitat by resource partitioning. Differences were noted for species-specific utilization of primary producers not only between seasons within a site, but also between sites. This highlighted the use of locally produced primary producers sustaining food webs in estuaries. Mangrove production in the Mngazana estuary is very important and contributes to most of the carbon in the underlying sediments in the mangrove forest. However, the relatively large number of species and biomass encountered in this estuary may also be attributed to the fact that the different species are able to exploit of a number of different resources. The variation in stable isotope analysis of the different crab species throughout the estuary indicated that these crabs able to occupy the same habitat by feeding on a number of different resources and may preferentially select for a specific primary producer. A stable isotope of crabs in the salt marsh Swartkops estuary indicated that the dominant primary producer sustaining crab communities may even take place on a relatively smallscale. Sesarma catenata found at the inner marsh site recorded more depleted carbon signatures than those encountered in the other sites approximately 100 m away, and reflected signatures similar to the locally-encountered inner marsh plants. The relatively enriched nitrogen signatures of the anthropogenically-impacted Swartkops estuary is an indication of extensive inputs due to urbanization and industrialization, in contrast to the relatively pristine Mngazana estuary which exhibited low nitrogen signatures. Emphasis has been placed on the abiotic component of the exchange of nutrients and energy, although living organisms may also be transported, both actively and passively, between ecosystems. Little variation in either species composition or abundance was found between seasons for the larval distribution of brachyuran crabs on the east coast of South Africa. Due to the lack of published larval descriptions, larvae could not be identified to species level and it was therefore not possible to identify whether the larvae were hatched or spawned in an estuary or in a marine environment, or whether the larvae originated in the northern tropical regions. Frequent wind-reversals which are common in this region may retain larvae close inshore and supply the southern temperate locations with larvae from the northern locations. In conclusion, this study has shown that in highly productive systems with a number of potential primary producers, the crabs that inhabit the estuary show a marked diversity in resource utilization which could potentially allow a number of closely related species to occupy different trophic levels. This study also highlights the importance of locally produced sources in an estuary, which may occur on very small scales and this needs to be factored in with the design of any future stable isotope studies of this nature.
- Full Text:
- Date Issued: 2009
- Authors: Vorsatz, Jeanne Pauline
- Date: 2009
- Subjects: Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10698 , http://hdl.handle.net/10948/1108 , Crabs -- South Africa -- Mangrove Estuary , Crabs -- South Africa -- Salt Marsh Estuary , Salt marsh ecology , Mangrove ecology
- Description: Crabs are conspicuous inhabitants of temperate salt marshes and tropical mangroves and interact with their environment through several processes. However, detailed information on crab community processes is absent for most South African estuaries and nearshore coastal regions. This study evaluated the primary producers supporting crab species in the salt marsh dominated Swartkops estuary and the mangrove Mngazana estuary. Various methods estimating crab abundances were also assessed in different microhabitats and the larval distribution of crabs in the coastal zone was also investigated. Various methods for estimating crab abundance have been employed in the past, each with its inherent biases. The microhabitat of a mangrove forest in Australia was structurally altered by the manipulation of the litter, pneumatophores and the associated algae. These alterations did not affect the behavioural activity or the numbers of crabs recorded in any of the experimental treatments by either visual counts or pitfall traps. However, the number of crabs caught in the pitfall traps differed between the sites. Species-specific behaviour which was not investigated in this study may bias crab abundance estimates when using pitfall traps and therefore requires further investigation. Benthic consumers inhabiting shallow coastal environments may ultimately have the origin of their nutrition in a number of possible sources. Isotopic and gut content analysis of Thalamita crenata and juvenile Scylla serrata in the Mngazana estuary in South Africa revealed that these two portunids are able to share a habitat by resource partitioning. Differences were noted for species-specific utilization of primary producers not only between seasons within a site, but also between sites. This highlighted the use of locally produced primary producers sustaining food webs in estuaries. Mangrove production in the Mngazana estuary is very important and contributes to most of the carbon in the underlying sediments in the mangrove forest. However, the relatively large number of species and biomass encountered in this estuary may also be attributed to the fact that the different species are able to exploit of a number of different resources. The variation in stable isotope analysis of the different crab species throughout the estuary indicated that these crabs able to occupy the same habitat by feeding on a number of different resources and may preferentially select for a specific primary producer. A stable isotope of crabs in the salt marsh Swartkops estuary indicated that the dominant primary producer sustaining crab communities may even take place on a relatively smallscale. Sesarma catenata found at the inner marsh site recorded more depleted carbon signatures than those encountered in the other sites approximately 100 m away, and reflected signatures similar to the locally-encountered inner marsh plants. The relatively enriched nitrogen signatures of the anthropogenically-impacted Swartkops estuary is an indication of extensive inputs due to urbanization and industrialization, in contrast to the relatively pristine Mngazana estuary which exhibited low nitrogen signatures. Emphasis has been placed on the abiotic component of the exchange of nutrients and energy, although living organisms may also be transported, both actively and passively, between ecosystems. Little variation in either species composition or abundance was found between seasons for the larval distribution of brachyuran crabs on the east coast of South Africa. Due to the lack of published larval descriptions, larvae could not be identified to species level and it was therefore not possible to identify whether the larvae were hatched or spawned in an estuary or in a marine environment, or whether the larvae originated in the northern tropical regions. Frequent wind-reversals which are common in this region may retain larvae close inshore and supply the southern temperate locations with larvae from the northern locations. In conclusion, this study has shown that in highly productive systems with a number of potential primary producers, the crabs that inhabit the estuary show a marked diversity in resource utilization which could potentially allow a number of closely related species to occupy different trophic levels. This study also highlights the importance of locally produced sources in an estuary, which may occur on very small scales and this needs to be factored in with the design of any future stable isotope studies of this nature.
- Full Text:
- Date Issued: 2009
Investigation of device and performance parameters of photovoltaic devices
- Macabebe, Erees Queen Barrido
- Authors: Macabebe, Erees Queen Barrido
- Date: 2009
- Subjects: Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10538 , http://hdl.handle.net/10948/1003 , http://hdl.handle.net/10948/d1012890 , Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Description: In order to investigate the influence of parasitic resistances, saturation current and diode ideality factor on the performance of photovoltaic devices, parameter extraction routines employing the standard iteration (SI) method and the particle swarm optimization (PSO) method were developed to extract the series resistance, shunt resistance, saturation current and ideality factor from the I-V characteristics of solar cells and PV modules. The well-known one- and two-diode models were used to describe the behavior of the I-V curve and the parameters of the models were determined by approximation and iteration techniques. The SI and the PSO extraction programmes were used to assess the suitability of the one- and the two-diode solar cell models in describing the I-V characteristics of mono- and multicrystalline silicon solar cells, CISS- and CIGSS-based solar cells. This exercise revealed that the two-diode model provides more information regarding the different processes involved in solar cell operation. Between the two methods developed, the PSO method is faster, yielded fitted curves with lower standard deviation of residuals and, therefore, was the preferred extraction method. The PSO method was then used to extract the device parameters of CISS-based solar cells with the CISS layer selenized under different selenization process conditions and CIGSS-based solar cells with varying i-ZnO layer thickness. For the CISS-based solar cells, the detrimental effect of parasitic resistances on device performance increased when the temperature and duration of the selenization process was increased. For the CIGSS-based devices, photogeneration improved with increasing i-ZnO layer thickness. At high forward bias, bulk recombination and/or tunneling-assisted recombination were the dominant processes affecting the I-V characteristics of the devices. v Lastly, device and performance parameters of mono-, multicrystalline silicon and CIS modules derived from I-V characteristics obtained under dark and illuminated conditions were analyzed considering the effects of temperature on the performance of the devices. Results showed that the effects of parasitic resistances are greater under illumination and, under outdoor conditions, the values further declined due to increasing temperature. The saturation current and ideality factor also increased under outdoor conditions which suggest increased recombination and, coupled with the adverse effects of parasitic resistances, these factors result in lower FF and lower maximum power point. Analysis performed on crystalline silicon and thin film devices utilized in this study revealed that parameter extraction from I-V characteristics of photovoltaic devices and, in particular, the implementation of PSO in solar cell device parameter extraction developed in this work is a useful characterization technique.
- Full Text:
- Date Issued: 2009
- Authors: Macabebe, Erees Queen Barrido
- Date: 2009
- Subjects: Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10538 , http://hdl.handle.net/10948/1003 , http://hdl.handle.net/10948/d1012890 , Photovoltaic cells , Solar cells , Photovoltaic power systems , Photovoltaic power generation
- Description: In order to investigate the influence of parasitic resistances, saturation current and diode ideality factor on the performance of photovoltaic devices, parameter extraction routines employing the standard iteration (SI) method and the particle swarm optimization (PSO) method were developed to extract the series resistance, shunt resistance, saturation current and ideality factor from the I-V characteristics of solar cells and PV modules. The well-known one- and two-diode models were used to describe the behavior of the I-V curve and the parameters of the models were determined by approximation and iteration techniques. The SI and the PSO extraction programmes were used to assess the suitability of the one- and the two-diode solar cell models in describing the I-V characteristics of mono- and multicrystalline silicon solar cells, CISS- and CIGSS-based solar cells. This exercise revealed that the two-diode model provides more information regarding the different processes involved in solar cell operation. Between the two methods developed, the PSO method is faster, yielded fitted curves with lower standard deviation of residuals and, therefore, was the preferred extraction method. The PSO method was then used to extract the device parameters of CISS-based solar cells with the CISS layer selenized under different selenization process conditions and CIGSS-based solar cells with varying i-ZnO layer thickness. For the CISS-based solar cells, the detrimental effect of parasitic resistances on device performance increased when the temperature and duration of the selenization process was increased. For the CIGSS-based devices, photogeneration improved with increasing i-ZnO layer thickness. At high forward bias, bulk recombination and/or tunneling-assisted recombination were the dominant processes affecting the I-V characteristics of the devices. v Lastly, device and performance parameters of mono-, multicrystalline silicon and CIS modules derived from I-V characteristics obtained under dark and illuminated conditions were analyzed considering the effects of temperature on the performance of the devices. Results showed that the effects of parasitic resistances are greater under illumination and, under outdoor conditions, the values further declined due to increasing temperature. The saturation current and ideality factor also increased under outdoor conditions which suggest increased recombination and, coupled with the adverse effects of parasitic resistances, these factors result in lower FF and lower maximum power point. Analysis performed on crystalline silicon and thin film devices utilized in this study revealed that parameter extraction from I-V characteristics of photovoltaic devices and, in particular, the implementation of PSO in solar cell device parameter extraction developed in this work is a useful characterization technique.
- Full Text:
- Date Issued: 2009
Mathematical requirements for first-year BCOM students at NMMU
- Authors: Walton, Marguerite
- Date: 2009
- Subjects: Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10502 , http://hdl.handle.net/10948/886 , Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Description: These studies have focused on identifying the mathematical requirements of first-year BCom students at Nelson Mandela Metropolitan University. The research methodology used in this quantitative study was to make use of interviewing, questionnaire investigation, and document analysis in the form of textbook, test and examination analysis. These methods provided data that fitted into a grounded theory approach. The study concluded by identifying the list of mathematical topics required for the first year of the core subjects in the BCom degree programme. In addition, the study found that learners who study Mathematics in the National Senior Certificate should be able to cope with the mathematical content included in their BCom degree programme, while learners studying Mathematical Literacy would probably need support in some of the areas of mathematics, especially algebra, in order to cope with the mathematical content included in their BCom degree programme. It makes a valuable contribution towards elucidating the mathematical requirements needed to improve the chances of successful BCom degree programme studies at South African universities. It also draws the contours for starting to design an efficient support course for future “at-risk” students who enter higher education studies.
- Full Text:
- Date Issued: 2009
- Authors: Walton, Marguerite
- Date: 2009
- Subjects: Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10502 , http://hdl.handle.net/10948/886 , Business mathematics -- South Africa , Mathematics -- Study and teaching (Higher) -- South Africa
- Description: These studies have focused on identifying the mathematical requirements of first-year BCom students at Nelson Mandela Metropolitan University. The research methodology used in this quantitative study was to make use of interviewing, questionnaire investigation, and document analysis in the form of textbook, test and examination analysis. These methods provided data that fitted into a grounded theory approach. The study concluded by identifying the list of mathematical topics required for the first year of the core subjects in the BCom degree programme. In addition, the study found that learners who study Mathematics in the National Senior Certificate should be able to cope with the mathematical content included in their BCom degree programme, while learners studying Mathematical Literacy would probably need support in some of the areas of mathematics, especially algebra, in order to cope with the mathematical content included in their BCom degree programme. It makes a valuable contribution towards elucidating the mathematical requirements needed to improve the chances of successful BCom degree programme studies at South African universities. It also draws the contours for starting to design an efficient support course for future “at-risk” students who enter higher education studies.
- Full Text:
- Date Issued: 2009
New platinum coordination compounds : their synthesis, characterization and anticancer application
- Authors: Oosthuizen, Lukas Marthinus
- Date: 2009
- Subjects: Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10430 , http://hdl.handle.net/10948/d1018795
- Description: The aim of this thesis was to investigate the properties of novel platinum compounds with possible potential as anticancer agents, and to determine how their behaviour could lead to a better understanding of the chemistry involved. The final criteria were improvement of their anticancer behaviour. Since many questions are still unanswered as to the role of sulfur in anticancer action, studies were undertaken to synthesize novel platinum(II) complexes having non-leaving groups consisting of a combination of an aromatic nitrogen and thioetherial sulfur capable of forming a five membered ring upon coordination. The structural unit was 1-methyl-2-methylthioalkyl/aryl. Numerous complexes formed by these ligands each having chloro, bromo, iodo and oxalato leaving groups were then fully characterized. The results obtained by the various synthetic methods were compared and explained in terms of the chemistry involved. The role of the sulfur donor was indicated in both the halo- and oxalato-complexes and proved to be strongly influenced by the nature of the leaving groups. Their differences are reflected in their anticancer behaviour. The study was extended to mononitroplatinum(IV) complexes, in view of the kinetically stable platinum(IV) compounds and advantages related to this. A specific mononitroplatinum(IV) complex which proved to have good anticancer and STAT 3 properties could according to the literature not be synthesized successfully in a good yield and a high degree of purity. The results of extensive studies showed that the main problem centred around the simultaneous reactions in equilibrium during the synthesis. A number of these species formed as a result of side reactions could be identified and their close separation factors indicated chromatographically. The mechanism of these reactions and the unstable intermediate species involved could be rationalized and compared to analogues in the literature. All the complexes studied were characterized by spectral and thermal methods both in solution as well as the solid state. Their anticancer behaviour towards three anticancer cell lines (Hela, MCF 7, Ht 29) were determined and acted as a guide towards possible structural modifications for their improved capability. Three crystal structures of platinum(II) complexes were determined. The extent of the ionization of the platinum(II) complexes as well the redox potentials (Pt(II) / Pt(IV)) of the platinum(IV) complexes were particularly important factors pertaining to their anticancer action.
- Full Text:
- Date Issued: 2009
- Authors: Oosthuizen, Lukas Marthinus
- Date: 2009
- Subjects: Platinum compounds , Antineoplastic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10430 , http://hdl.handle.net/10948/d1018795
- Description: The aim of this thesis was to investigate the properties of novel platinum compounds with possible potential as anticancer agents, and to determine how their behaviour could lead to a better understanding of the chemistry involved. The final criteria were improvement of their anticancer behaviour. Since many questions are still unanswered as to the role of sulfur in anticancer action, studies were undertaken to synthesize novel platinum(II) complexes having non-leaving groups consisting of a combination of an aromatic nitrogen and thioetherial sulfur capable of forming a five membered ring upon coordination. The structural unit was 1-methyl-2-methylthioalkyl/aryl. Numerous complexes formed by these ligands each having chloro, bromo, iodo and oxalato leaving groups were then fully characterized. The results obtained by the various synthetic methods were compared and explained in terms of the chemistry involved. The role of the sulfur donor was indicated in both the halo- and oxalato-complexes and proved to be strongly influenced by the nature of the leaving groups. Their differences are reflected in their anticancer behaviour. The study was extended to mononitroplatinum(IV) complexes, in view of the kinetically stable platinum(IV) compounds and advantages related to this. A specific mononitroplatinum(IV) complex which proved to have good anticancer and STAT 3 properties could according to the literature not be synthesized successfully in a good yield and a high degree of purity. The results of extensive studies showed that the main problem centred around the simultaneous reactions in equilibrium during the synthesis. A number of these species formed as a result of side reactions could be identified and their close separation factors indicated chromatographically. The mechanism of these reactions and the unstable intermediate species involved could be rationalized and compared to analogues in the literature. All the complexes studied were characterized by spectral and thermal methods both in solution as well as the solid state. Their anticancer behaviour towards three anticancer cell lines (Hela, MCF 7, Ht 29) were determined and acted as a guide towards possible structural modifications for their improved capability. Three crystal structures of platinum(II) complexes were determined. The extent of the ionization of the platinum(II) complexes as well the redox potentials (Pt(II) / Pt(IV)) of the platinum(IV) complexes were particularly important factors pertaining to their anticancer action.
- Full Text:
- Date Issued: 2009
Patterns and determinants of species richness in mesic temparate grasslands of South Africa
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
- Authors: Hoare, David Barry
- Date: 2009
- Subjects: Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10613 , http://hdl.handle.net/10948/1275 , Grassland ecology -- South Africa -- Eastern Cape , Plant diversity -- South Africa -- Eastern Cape , Vegetation and climate
- Description: The aim of this study is to gain a predictive understanding of the patterns and determinants of plant biodiversity in temperate, mesic grasslands of South Africa with a primary focus on the geographical area of the Eastern Cape. From a review of the literature on hypotheses explaining diversity (Chapter 2) it was possible to formulate a number of hypotheses that could be tested to explain species richness patterns in Eastern Cape grasslands. This thesis is organised so that each main chapter deals with a specific body of theory concerning the explanation of diversity patterns. A detailed description of the study area is provided (Chapter 3), including environmental variation and a description of major vegetation patterns. A summary is provided of grassland plant community patterns, as determined by phytosociological studies in the study area. A multivariate analysis of environmental variables was undertaken to determine which variables contributed the most towards explaining environmental variation in the study area and to determine whether any variables co-vary, a possible problem for any multivariate analysis in later chapters. Altitude produced one of the strongest gradients in the study area. There were a number of variables that were correlated with altitude, most notably temperature. Rainfall co-varied partially with altitude, but there was also a strong rainfall gradient perpendicular to the altitude gradient. A description of species richness, diversity and evenness patterns at the plot scale within different grassland plant communities of the Eastern Cape is provided in Chapter 4. To determine whether the environment acts differently on different growth forms, the contribution to species richness by different major growth forms is analysed. Furthermore, since the majority of literature attempts to explain diversity in terms of environmental factors, it was necessary to analyse the relationship between species richness and various environmental variables. The results indicate that there is high variation in species richness both within and among grassland communities. Forbs make the most significant contribution to overall species richness per 100 m2, followed by grasses. Variance in richness of all species together is not significantly related to environmental variables in mesic grasslands, but is significantly related to environmental variables in semi-arid grasslands. The result of greatest interest from this chapter is the fact that richness amongst different life-forms in the same place is explained by different environmental factors, indicating that the environmental factors that affect coexistence of species have a different effect on different life-forms. A classification of all the species of the dataset into plant functional types using a multivariate approach based on functional traits was conducted (Chapter 5). The grass species were classified into 16 functional types and the forbs into 14 functional types. The functional type classification provided the opportunity for undertaking analyses to develop an understanding of 8 the contribution by niche differentiation towards promoting species richness (Chapter 6). The results provide evidence of niche differentiation in the grasslands of the study area and also that niche differentiation promotes species richness in the grasslands of the study area. It was found that higher rainfall grasslands are less structured by niche differentiation than semi-arid grasslands. A regional / historical analysis is undertaken (Chapter 7) to investigate the relationship between the regional species pool and local richness, and the relationship between local richness and phytochorological diversity. Regional richness appears to have little effect in promoting local richness in grassland plant communities of the study area except at sites where there is high local richness. This provides an indication that regional richness only promotes local richness in the absence of local limiting factors. Phytochorological diversity promotes local richness, but mostly through diversity amongst species with narrow distribution ranges. Some theories ascertain that seasonal uncertainty may provide opportunities to species that would otherwise be outcompeted and thereby promote local richness. The degree to which seasonal uncertainty and seasonality promote local richness in the Eastern Cape grasslands was therefore investigated (Chapter 8). A weak relationship exists between these variables and local species richness in grassland communities of the study area, indicating that they do not promote niche differentiation to a significant degree in the study area. It is clear that in the grasslands of the Eastern Cape, environmental limiting factors are more important in semi-arid grasslands and species interactions are more important in mesic grasslands for structuring plant communities (Chapter 9, Discussion). Regional processes do not appear to be important in structuring local communities, but the analysis undertaken in this study shows that they may be significant when factors operating at the other two levels are overcome (species interactions and environmental limiting factors.
- Full Text:
- Date Issued: 2009
Polarization mode dispersion emulation and the impact of high first-order PMD segments in optical telecommunication systems
- Authors: Musara, Vitalis
- Date: 2009
- Subjects: Optical communications , Fiber optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10519 , http://hdl.handle.net/10948/1138 , Optical communications , Fiber optics , Polarization (Light)
- Description: In this study, focus is centred on the measurement and emulation of first-order (FO-) and second-order (SO-) polarization mode dispersion (PMD). PMD has deleterious effects on the performance of high speed optical transmission network systems from 10 Gb/s and above. The first step was characterising deployed fibres for PMD and monitoring the state of polarization (SOP) light experiences as it propagates through the fibre. The PMD and SOP changes in deployed fibres were stochastic due to varying intrinsic and extrinsic perturbation changes. To fully understand the PMD phenomenon in terms of measurement accuracy, its complex behaviour, its implications, mitigation and compensation, PMD emulation is crucial. This thesis presents emulator designs which fall into different emulator categories. The key to these designs were the PMD equations and background on the PMD phenomenon. The cross product from the concatenation equation was applied in order to determine the coupling angle β (between 0o and 180o) that results in the SO-PMD of the emulator designs to be either adjustable or fixed. The digital delay line (DDL) or single polarization maintaining fibre (PMF) section was used to give a certain amount of FO-PMD but negligible SO-PMD. PMF sections (birefringent sections) were concatenated together to ensure FO- and SO-PMD coexist, emulating deployed fibres. FO- and SO-PMD can be controlled by altering mode coupling (coupling angles) and birefringence distribution. Emulators with PMD statistics approaching the theoretical distributions had high random coupling and several numbers of randomly distributed PMF sections. In addition, the lengths of their PMF sections lie within 20% standard deviation of the mean emulator length. Those emulators with PMD statistics that did not approach the theoretical distributions had limited numbers of randomly distributed PMF sections and mode coupling. Results also show that even when an emulator has high random mode coupling and several numbers of randomly distributed PMFs, its PMD statistics deviates away from expected theoretical distributions in the presence of polarization dependent loss (PDL). The emulators showed that the background autocorrelation function (BACF) approaches zero with increasing number of randomly mode coupled fibre sections. A zero BACF signifies that an emulator has large numbers of randomly distributed PMF sections and its presence means the opposite. The availability of SO-PMD in the emulators made the autocorrelation function (ACF) x asymmetric. In the absence of SO-PMD the ACF for a PMD emulator is symmetric. SO-PMD has no effect on the BACF. Polarization-optical time domain reflectometry (P-OTDR) measurements have shown that certain fibre sections along fibre link lengths have higher FO-PMD (HiFO-PMD) than other sections. This study investigates the impact of a HiFO-PMD section on the overall FO- and SO-PMD, the output state of polarization (SOP) and system performance on deployed fibres (through emulation). Results show that when the wavelength-independent FO-PMD vector of the HiFO-PMD section is greater than the FO-PMD contributions from the rest of the fibre link, the mean FO-PMD of the entire link is biased towards that of the HiFO-PMD section and the SO-PMD increases (β ≠ 0o or 180o) or remains fixed (β = 0o or 180o) depending on the coupling angle β between the HiFO-PMD section and the rest of the fibre link. In addition, the FO-PMD statistics deviates away from the theoretical Maxwellian distribution. However, experimental results show that the HiFO-PMD section has negligible influence on the SOPMD statistical distribution. An increase in the amount of FO-PMD on a HiFO-PMD section reduces the output SOP spread to a given minimum, in this study the minimum was reached when the HiFO-PMD ≥ 35 ps. However, the outcome of the output SOP spread depends on the location of the HiFO-PMD section along the fibre link length. It was found that when the HiFO-PMD section introduces SO-PMD, the bit error rate (BER) is much higher compared to when it does not introduce SO-PMD.
- Full Text:
- Date Issued: 2009
- Authors: Musara, Vitalis
- Date: 2009
- Subjects: Optical communications , Fiber optics , Polarization (Light)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10519 , http://hdl.handle.net/10948/1138 , Optical communications , Fiber optics , Polarization (Light)
- Description: In this study, focus is centred on the measurement and emulation of first-order (FO-) and second-order (SO-) polarization mode dispersion (PMD). PMD has deleterious effects on the performance of high speed optical transmission network systems from 10 Gb/s and above. The first step was characterising deployed fibres for PMD and monitoring the state of polarization (SOP) light experiences as it propagates through the fibre. The PMD and SOP changes in deployed fibres were stochastic due to varying intrinsic and extrinsic perturbation changes. To fully understand the PMD phenomenon in terms of measurement accuracy, its complex behaviour, its implications, mitigation and compensation, PMD emulation is crucial. This thesis presents emulator designs which fall into different emulator categories. The key to these designs were the PMD equations and background on the PMD phenomenon. The cross product from the concatenation equation was applied in order to determine the coupling angle β (between 0o and 180o) that results in the SO-PMD of the emulator designs to be either adjustable or fixed. The digital delay line (DDL) or single polarization maintaining fibre (PMF) section was used to give a certain amount of FO-PMD but negligible SO-PMD. PMF sections (birefringent sections) were concatenated together to ensure FO- and SO-PMD coexist, emulating deployed fibres. FO- and SO-PMD can be controlled by altering mode coupling (coupling angles) and birefringence distribution. Emulators with PMD statistics approaching the theoretical distributions had high random coupling and several numbers of randomly distributed PMF sections. In addition, the lengths of their PMF sections lie within 20% standard deviation of the mean emulator length. Those emulators with PMD statistics that did not approach the theoretical distributions had limited numbers of randomly distributed PMF sections and mode coupling. Results also show that even when an emulator has high random mode coupling and several numbers of randomly distributed PMFs, its PMD statistics deviates away from expected theoretical distributions in the presence of polarization dependent loss (PDL). The emulators showed that the background autocorrelation function (BACF) approaches zero with increasing number of randomly mode coupled fibre sections. A zero BACF signifies that an emulator has large numbers of randomly distributed PMF sections and its presence means the opposite. The availability of SO-PMD in the emulators made the autocorrelation function (ACF) x asymmetric. In the absence of SO-PMD the ACF for a PMD emulator is symmetric. SO-PMD has no effect on the BACF. Polarization-optical time domain reflectometry (P-OTDR) measurements have shown that certain fibre sections along fibre link lengths have higher FO-PMD (HiFO-PMD) than other sections. This study investigates the impact of a HiFO-PMD section on the overall FO- and SO-PMD, the output state of polarization (SOP) and system performance on deployed fibres (through emulation). Results show that when the wavelength-independent FO-PMD vector of the HiFO-PMD section is greater than the FO-PMD contributions from the rest of the fibre link, the mean FO-PMD of the entire link is biased towards that of the HiFO-PMD section and the SO-PMD increases (β ≠ 0o or 180o) or remains fixed (β = 0o or 180o) depending on the coupling angle β between the HiFO-PMD section and the rest of the fibre link. In addition, the FO-PMD statistics deviates away from the theoretical Maxwellian distribution. However, experimental results show that the HiFO-PMD section has negligible influence on the SOPMD statistical distribution. An increase in the amount of FO-PMD on a HiFO-PMD section reduces the output SOP spread to a given minimum, in this study the minimum was reached when the HiFO-PMD ≥ 35 ps. However, the outcome of the output SOP spread depends on the location of the HiFO-PMD section along the fibre link length. It was found that when the HiFO-PMD section introduces SO-PMD, the bit error rate (BER) is much higher compared to when it does not introduce SO-PMD.
- Full Text:
- Date Issued: 2009
Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
- Authors: Booysen, Irvin Noel
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10386 , http://hdl.handle.net/10948/1270 , Rhenium , Ligands
- Description: The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. A new nitrosylrhenium(II) complex salt, [Re(NO)BrL2(PPh3)2](ReO4) (H2L2 = 2-amino-5- (triphenylphosphino)phenol), is the first example of a complex containing the triphenylphosphonium-amidophenolate ligand L2, formed by the nucleophilic attack of a PPh3 on a coordinated amidophenolate ring. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps = N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The six-coordinated complex cis-[Re(mps)Cl2(PPh3)2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H3mps in benzene. The X-ray crystal structure show that the mps ligand coordinates as a tridentate chelate via the doubly deprotonated 2-amino nitrogen, the neutral imino nitrogen and the phenolate oxygen. The imide and phenolate oxygen coordinate trans to each other in a distorted octahedral geometry, around the rhenium(V) centre, with the two chlorides in cis positions. A new oxofree rhenium(V) complex salt, [Re(bbd)2](ReO4) ( H2bbd = N-(2- Abstract I.N. Booysen Nelson Mandela Metropolitan University viii aminobenzylidene)benzene-1,2-diamine), has been synthesized and the chelates bbd are coordinated as dianionic tridentate N,N,N-donor diamidoimines. The rhenium(V) ion is centered in a distorted trigonal prism. The rhenium(I) compound fac-[Re(CO)3(daa)].Hpab.H2O (Hpab = N1,N2-(1,2- phenylene)bis(2-aminobenzamide); Hdaa = 2-amino-N-(2-aminophenyl)benzamide) was synthesized from the reaction of [Re(CO)5Br] with a two equivalents of Hpab in toluene. The monoanionic tridentate ligand daa was formed by the rhenium-mediated cleavage of an amido N-C bond of the potentially tetradentate ligand Hpab. Daa is coordinated as a diaminoamide via three nitrogen-donor atoms. The reaction of a twofold molar excess of H2amben (H2amben = N1,N2-bis(2-aminobenzylidene)ethane-1,2-diamine) with trans- [ReOBr3(PPh3)2] gave the oxorhenium(V) cationic complex [ReO(amben)]X (X = Br-, PF6 -). The Re(V) oxo-bridged compound, {μ-O}[ReO(omben)]2.H2O (H2omben = N1,N2- bis(2-hydroxybenzylidene)ethane-1,2-diamine) was isolated from the reaction of a 2:1 molar ratio of H2omben and trans-[ReO2(py)4]Cl in methanol. The seven-coordinate rhenium(III) complex cation [ReIII(dhp)(PPh3)2]+ was isolated as the [ReO4]- salt from the reaction of cis-[ReVO2I(PPh3)2] with 2,6-bis(2- hydroxyphenyliminomethyl)pyridine (H2dhp) in ethanol. In the complex fac- [Re(CO)3(H2dhp)Br], prepared from [Re(CO)5Br] and H2dhp in toluene, the H2dhp ligand acts as a neutral bidentate N,N-donor chelate. An equimolar ratio reaction of 2-aminobenzaldehyde and 2-(2-aminophenyl)-1- benzimidazole in methanol led to 2-(5,6-dihydrobenzimidazolo[1,2-c]-quinazolin-6- yl)aniline. In an attempt to explore the template formation of this class of ligand with rhenium, the reaction of salicylaldehyde and 2-(2-aminophenyl)-1-benzimidazole in ethanol which was followed by the addition of trans-[ReOBr3(PPh3)2] led to the formation of the salt, 6-(2-hydroxyphenyl)-5,6-dihydrobenzimidazolo[1,2-c]quinazolin- 12-ium bromide. The compound 6-(2-methylthiophenyl)-5,6-dihydrobenzimidazolo[1,2- c]quinazolin-12-ium was synthesized via the reaction of 2-aminobenzaldehyde and 2- methylthiobenzaldehyde in methanol.
- Full Text:
- Date Issued: 2009
The coordination chemistry of Rhenium(V) with multidentate no-donor ligands
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
- Authors: Abrahams, Abubak'r
- Date: 2009
- Subjects: Rhenium , Ligands
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10370 , http://hdl.handle.net/10948/912 , Rhenium , Ligands
- Description: The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate uninegative chelate, with deprotonation of the amine nitrogen. The water molecule is coordinated trans to the oxo group, with the Re=O and Re-OH2 bond distances equal to 1.663(9) and 2.21(1) Å respectively. Complexes of the general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X = Cl, I) were prepared by the reactions of trans-[ReOCl3(PPh3)2] and trans- [ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. Experimental evidence shows that the coordinated DPE ligand has undergone addition of water at the ethylenic carbons, and that the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative tridentate NON-donor ligand. The X-ray crystal structures of both complexes show a distorted octahedral geometry around the rhenium(V) centre. The treatment of trans-[ReOCl3(PPh3)2] with H2dbd in a 2:1 molar ratio in acetonitrile led to the isolation of the ligand-bridged dimer (μ-dbd)[ReOCl2(PPh3)]2. The X-ray crystal structure of the complex reveals a dinuclear structure in which two rhenium(V) ions are bridged by the dbd ligand. Each rhenium ion is in a x A. Abrahams Nelson Mandela Metropolitan University distorted octahedral geometry. The basal plane is defined by a phosphorus atom of the PPh3 group, two chlorides cis to each other, and a pyridyl nitrogen atom of dbd. The oxo group and alcoholate oxygen of dbd lie in trans axial positions. The complexes cis-[ReOX2(msa)(PPh3)] (X = Cl, Br, I) were prepared from trans- [ReOCl3(PPh3)2], trans-[ReOBr3(PPh3)2] or trans-[ReOI2(OEt)(PPh3)2] with 2-(1- iminoethyl)phenol (Hmsa) in acetonitrile. An X-ray crystallographic study shows that the bonding distances and angles in the comlexes are nearly identical, and that the two halides in each complex are coordinated cis to each other in the equatorial plane cis to the oxo group. The oxo-bridged dinuclear rhenium(V) complex [(μ-O){ReOCl(amp)}2] was prepared by the reaction of trans-[ReOCl3(PPh3)2] and 6-amino-3-methyl-1-phenyl- 4-azahept-2-ene-1-one (Hamp) in acetone. The characterization of the complex by elemental analysis, infrared and 1H NMR spectroscopy and X-ray crystallography shows that amp is coordinated as a monoanionic NNO-donor chelate as an amino-amido ketone. However, the reaction of the similar ligand 7- amino-4,7-dimethyl-5-aza-3-octen-2-one (Hada) with [Re(CO)5Br] produced the product fac-[Re(CO)3Br(Hada)], with Hada coordinated as a neutral NN-donor amino-imino-ketone.
- Full Text:
- Date Issued: 2009
The development and evaluation of gaze selection techniques
- Authors: Van Tonder, Martin Stephen
- Date: 2009
- Subjects: Human-computer interaction , User interfaces (Computer systems) , Gaze
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10469 , http://hdl.handle.net/10948/882 , Human-computer interaction , User interfaces (Computer systems) , Gaze
- Description: Eye gaze interaction enables users to interact with computers using their eyes. A wide variety of eye gaze interaction techniques have been developed to support this type of interaction. Gaze selection techniques, a class of eye gaze interaction techniques which support target selection, are the subject of this research. Researchers developing these techniques face a number of challenges. The most significant challenge is the limited accuracy of eye tracking equipment (due to the properties of the human eye). The design of gaze selection techniques is dominated by this constraint. Despite decades of research, existing techniques are still significantly less accurate than the mouse. A recently developed technique, EyePoint, represents the state of the art in gaze selection techniques. EyePoint combines gaze input with keyboard input. Evaluation results for this technique are encouraging, but accuracy is still a concern. Early trigger errors, resulting from users triggering a selection before looking at the intended target, were found to be the most commonly occurring errors for this technique. The primary goal of this research was to improve the usability of gaze selection techniques. In order to achieve this goal, novel gaze selection techniques were developed. New techniques were developed by combining elements of existing techniques in novel ways. Seven novel gaze selection techniques were developed. Three of these techniques were selected for evaluation. A software framework was developed for implementing and evaluating gaze selection techniques. This framework was used to implement the gaze selection techniques developed during this research. Implementing and evaluating all of the techniques using a common framework ensured consistency when comparing the techniques. The novel techniques which were developed were evaluated against EyePoint and the mouse using the framework. The three novel techniques evaluated were named TargetPoint, StaggerPoint and ScanPoint. TargetPoint combines motor space expansion with a visual feedback highlight whereas the StaggerPoint and TargetPoint designs explore novel approaches to target selection disambiguation. A usability evaluation of the three novel techniques alongside EyePoint and the mouse revealed some interesting trends. TargetPoint was found to be more usable and accurate than EyePoint. This novel technique also proved more popular with test participants. One aspect of TargetPoint which proved particularly popular was the visual feedback highlight, a feature which was found to be a more effective method of combating early trigger errors than existing approaches. StaggerPoint was more efficient than EyePoint, but was less effective and satisfying. ScanPoint was the least popular technique. The benefits of providing a visual feedback highlight and test participants' positive views thereof contradict views expressed in existing research regarding the usability of visual feedback. These results have implications for the design of future gaze selection techniques. A set of design principles was developed for designing new gaze selection techniques. The designers of gaze selection techniques can benefit from these design principles by applying them to their techniques
- Full Text:
- Date Issued: 2009
- Authors: Van Tonder, Martin Stephen
- Date: 2009
- Subjects: Human-computer interaction , User interfaces (Computer systems) , Gaze
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10469 , http://hdl.handle.net/10948/882 , Human-computer interaction , User interfaces (Computer systems) , Gaze
- Description: Eye gaze interaction enables users to interact with computers using their eyes. A wide variety of eye gaze interaction techniques have been developed to support this type of interaction. Gaze selection techniques, a class of eye gaze interaction techniques which support target selection, are the subject of this research. Researchers developing these techniques face a number of challenges. The most significant challenge is the limited accuracy of eye tracking equipment (due to the properties of the human eye). The design of gaze selection techniques is dominated by this constraint. Despite decades of research, existing techniques are still significantly less accurate than the mouse. A recently developed technique, EyePoint, represents the state of the art in gaze selection techniques. EyePoint combines gaze input with keyboard input. Evaluation results for this technique are encouraging, but accuracy is still a concern. Early trigger errors, resulting from users triggering a selection before looking at the intended target, were found to be the most commonly occurring errors for this technique. The primary goal of this research was to improve the usability of gaze selection techniques. In order to achieve this goal, novel gaze selection techniques were developed. New techniques were developed by combining elements of existing techniques in novel ways. Seven novel gaze selection techniques were developed. Three of these techniques were selected for evaluation. A software framework was developed for implementing and evaluating gaze selection techniques. This framework was used to implement the gaze selection techniques developed during this research. Implementing and evaluating all of the techniques using a common framework ensured consistency when comparing the techniques. The novel techniques which were developed were evaluated against EyePoint and the mouse using the framework. The three novel techniques evaluated were named TargetPoint, StaggerPoint and ScanPoint. TargetPoint combines motor space expansion with a visual feedback highlight whereas the StaggerPoint and TargetPoint designs explore novel approaches to target selection disambiguation. A usability evaluation of the three novel techniques alongside EyePoint and the mouse revealed some interesting trends. TargetPoint was found to be more usable and accurate than EyePoint. This novel technique also proved more popular with test participants. One aspect of TargetPoint which proved particularly popular was the visual feedback highlight, a feature which was found to be a more effective method of combating early trigger errors than existing approaches. StaggerPoint was more efficient than EyePoint, but was less effective and satisfying. ScanPoint was the least popular technique. The benefits of providing a visual feedback highlight and test participants' positive views thereof contradict views expressed in existing research regarding the usability of visual feedback. These results have implications for the design of future gaze selection techniques. A set of design principles was developed for designing new gaze selection techniques. The designers of gaze selection techniques can benefit from these design principles by applying them to their techniques
- Full Text:
- Date Issued: 2009
The ecophysiology of Gelidium Pristoides (Turner) Kuetzing : towards commercial cultivation
- Authors: Steyn, Paul-Pierre
- Date: 2009
- Subjects: Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10617 , http://hdl.handle.net/10948/1117 , Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Description: The ecophysiology of the red alga Gelidium pristoides (Turner) Kuetzing was investigated in an effort to establish a technique for commercial cultivation. The seaweed is of commercial importance in South Africa where it is harvested from the intertidal zone rocky shores along the coast. It is dried and exported abroad for the extraction of agar. Yields and quality could be improved by cultivation in commercial systems. However, attempts at growing the seaweed in experimental systems have all ended in failure. This study aimed to describe the conditions in which the seaweed grows naturally; and investigate its physiological response to selected physical conditions in the laboratory in order to determine suitable conditions for mariculture. Ecological studies showed that G. pristoides grew above the spring low tide water level. The upper limit of the seaweed’s vertical distribution range, as well as its abundance, was largely dependent on wave exposure. The zone normally inhabited by G. pristoides was dominated by coralline turf in sheltered areas, while the abundance of G. pristoides increased towards more exposed rocky shore sites. The seaweed occurred among species such as Pattelid limpets and barnacles, but was usually the dominant macroalga in this zone, with coralline turf and encrusting algae being the only others. Physical conditions in the part of the intertidal zone inhabited by G. pristoides were highly variable. During low tide temperatures could vary by as much as 10°C within the three hours between tidal inundation of the seaweed population, while salinity varied by up to 9 ppt, and light intensity by as much as 800 μmol m-2 s-1. During these exposure periods the seaweed suffered up to 20% moisture loss. Laboratory experiments on the seaweed’s response to these conditions indicated that it was well adapted to such fluctuations. It had a broad salinity (20 and 40 ppt), and temperature tolerance range (18 to 24°C), with an o ptimum of temperature of 21°C for photosynthesis, while there was no difference in the photosynthetic rate of the alga within the 20 to 40 ppt salinity range. The alga had a low saturating irradiance (ca. 45 – 80 μmol m-2 s-1) equipping it well for photosynthesis in turbulent environments, with high light attenuation, but poorly to unattenuated light conditions. Exposure resulted in an initial increase in photosynthetic rate followed by a gradual decrease thereafter. pH drift experiments showed that low seawater pH, and associated increased carbon dioxide availability, resulted in an increase in photosynthetic rate. This response suggests that the seaweed has a high affinity for carbon dioxide, while the reduction in photosynthetic rate in response to bicarbonate use inhibition indicates that it also has the capacity for bicarbonate use. The high affinity of Gelidium pristoides for carbon dioxide as an inorganic carbon source appears to be the primary reason for the low abundance of the alga on sheltered rocky shore areas, and also explains the failure of the alga to grow in tank or open-water mariculture systems. Exposed rocky shores have experience heavy wave action, and the resultant aeration and mixing of nearshore waters increases the availability of carbon dioxide, which is considered a limiting resource. The absence of such mixing and aeration at sheltered site makes this less suitable habitat for G. pristoides. Periodic exposure also makes high levels of atmospheric carbon dioxide available from which the seaweed benefits. The traditional mariculture systems in which attempts have been made to cultivate the seaweed failed to satisfy either of the above conditions.
- Full Text:
- Date Issued: 2009
- Authors: Steyn, Paul-Pierre
- Date: 2009
- Subjects: Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10617 , http://hdl.handle.net/10948/1117 , Marine algae -- South Africa , Marine algae -- Ecophysiology , Red algae -- South Africa , Gelidium -- South Africa
- Description: The ecophysiology of the red alga Gelidium pristoides (Turner) Kuetzing was investigated in an effort to establish a technique for commercial cultivation. The seaweed is of commercial importance in South Africa where it is harvested from the intertidal zone rocky shores along the coast. It is dried and exported abroad for the extraction of agar. Yields and quality could be improved by cultivation in commercial systems. However, attempts at growing the seaweed in experimental systems have all ended in failure. This study aimed to describe the conditions in which the seaweed grows naturally; and investigate its physiological response to selected physical conditions in the laboratory in order to determine suitable conditions for mariculture. Ecological studies showed that G. pristoides grew above the spring low tide water level. The upper limit of the seaweed’s vertical distribution range, as well as its abundance, was largely dependent on wave exposure. The zone normally inhabited by G. pristoides was dominated by coralline turf in sheltered areas, while the abundance of G. pristoides increased towards more exposed rocky shore sites. The seaweed occurred among species such as Pattelid limpets and barnacles, but was usually the dominant macroalga in this zone, with coralline turf and encrusting algae being the only others. Physical conditions in the part of the intertidal zone inhabited by G. pristoides were highly variable. During low tide temperatures could vary by as much as 10°C within the three hours between tidal inundation of the seaweed population, while salinity varied by up to 9 ppt, and light intensity by as much as 800 μmol m-2 s-1. During these exposure periods the seaweed suffered up to 20% moisture loss. Laboratory experiments on the seaweed’s response to these conditions indicated that it was well adapted to such fluctuations. It had a broad salinity (20 and 40 ppt), and temperature tolerance range (18 to 24°C), with an o ptimum of temperature of 21°C for photosynthesis, while there was no difference in the photosynthetic rate of the alga within the 20 to 40 ppt salinity range. The alga had a low saturating irradiance (ca. 45 – 80 μmol m-2 s-1) equipping it well for photosynthesis in turbulent environments, with high light attenuation, but poorly to unattenuated light conditions. Exposure resulted in an initial increase in photosynthetic rate followed by a gradual decrease thereafter. pH drift experiments showed that low seawater pH, and associated increased carbon dioxide availability, resulted in an increase in photosynthetic rate. This response suggests that the seaweed has a high affinity for carbon dioxide, while the reduction in photosynthetic rate in response to bicarbonate use inhibition indicates that it also has the capacity for bicarbonate use. The high affinity of Gelidium pristoides for carbon dioxide as an inorganic carbon source appears to be the primary reason for the low abundance of the alga on sheltered rocky shore areas, and also explains the failure of the alga to grow in tank or open-water mariculture systems. Exposed rocky shores have experience heavy wave action, and the resultant aeration and mixing of nearshore waters increases the availability of carbon dioxide, which is considered a limiting resource. The absence of such mixing and aeration at sheltered site makes this less suitable habitat for G. pristoides. Periodic exposure also makes high levels of atmospheric carbon dioxide available from which the seaweed benefits. The traditional mariculture systems in which attempts have been made to cultivate the seaweed failed to satisfy either of the above conditions.
- Full Text:
- Date Issued: 2009
The invasion of pteronia incana (blue bush) along a range of gradients in the Eastern Cape Province : it's spectral chacteristics and implications for soil moisture
- Authors: Odindi, John Odhiambo
- Date: 2009
- Subjects: Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10650 , http://hdl.handle.net/10948/1052 , Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Description: Extensive areas of the Eastern Cape Province have been invaded by Pteronia incana (Blue bush), a non-palatable patchy invader shrub that is associated with soil degradation. This study sought to establish the relationship between the invasion and a range of eco-physical and land use gradients. The impact of the invader on soil moisture flux was investigated by comparing soil moisture variations under grass, bare and P. incana invaded surfaces. Field based and laboratory spectroscopy was used to validate P. incana spectral characteristics identified from multi-temporal High Resolution Imagery (HRI). A belt transect was surveyed to gain an understanding of the occurrence of the invasion across land use, isohyetic, geologic, vegetation, pedologic and altitudinal gradients. Soil moisture sensors were calibrated and installed under the respective surfaces in order to determine soil moisture trends over a period of six months. To classify the surfaces using HRI, the pixel and sub-pixel based Perpendicular Vegetation Index (PVI) and Spectral Mixture Analysis (SMA) respectively were used. There was no clear trend established between the underlying geology and P. incana invasion. Land disturbance in general was strongly associated with the invasion, as the endemic zone for the invasion mainly comprised abandoned cultivated and overgrazed land. Isohyetic gradients emerged as the major limiting factor of the invasion; a distinct zone below 619mm of mean annual rainfall was identified as the apparent boundary for the invasion. Low organic matter content identified under invaded areas was attributed to the patchy nature of the invader, leading to loss of the top soil in the bare inter-patch areas. The area covered by grass had consistently higher moisture values than P. incana and bare surfaces. The difference in post-rainfall moisture retention between grass and P. incana surfaces was significant up to about six days, after which a near parallel trend was noticed towards the ensuing rainfall episode. Whereas a higher amount of moisture was recorded on grass, the surface experienced moisture loss faster than the invaded and bare surfaces after each rainfall episode. ii There was consistency in multi-temporal Digital Number (DN) values for the surfaces investigated. The typically low P. incana reflectance in the Near Infrared band, identified from the multi-temporal HRI was validated by field and laboratory spectroscopy. The PVI showed clear spectral separability between all the land surfaces in the respective multi-temporal HRI. The consistence of the PVI with the unmixed surface image fractions from the SMA illustrates that using HRI, the effectiveness of the PVI is not impeded by the mixed pixel problem. Results of the laboratory spectroscopy that validated HRI analyses showed that P. incana’s typically low reflectance is a function of its leaf canopy, as higher proportions of leaves gave a higher reflectance. Future research directions could focus on comparisons between P. incana and typical green vegetation internal leaf structures as potential causes of spectral differences. Collection of spectra for P incana and other invader vegetation types, some of which have similar characteristics, with a view to assembling a spectral library for delineating invaded environments using imagery, is another research direction.
- Full Text:
- Date Issued: 2009
- Authors: Odindi, John Odhiambo
- Date: 2009
- Subjects: Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10650 , http://hdl.handle.net/10948/1052 , Invasive plants -- South Africa -- Eastern Cape , Alien plants -- South Africa -- Eastern Cape , Soil moisture -- South Africa -- Eastern Cape
- Description: Extensive areas of the Eastern Cape Province have been invaded by Pteronia incana (Blue bush), a non-palatable patchy invader shrub that is associated with soil degradation. This study sought to establish the relationship between the invasion and a range of eco-physical and land use gradients. The impact of the invader on soil moisture flux was investigated by comparing soil moisture variations under grass, bare and P. incana invaded surfaces. Field based and laboratory spectroscopy was used to validate P. incana spectral characteristics identified from multi-temporal High Resolution Imagery (HRI). A belt transect was surveyed to gain an understanding of the occurrence of the invasion across land use, isohyetic, geologic, vegetation, pedologic and altitudinal gradients. Soil moisture sensors were calibrated and installed under the respective surfaces in order to determine soil moisture trends over a period of six months. To classify the surfaces using HRI, the pixel and sub-pixel based Perpendicular Vegetation Index (PVI) and Spectral Mixture Analysis (SMA) respectively were used. There was no clear trend established between the underlying geology and P. incana invasion. Land disturbance in general was strongly associated with the invasion, as the endemic zone for the invasion mainly comprised abandoned cultivated and overgrazed land. Isohyetic gradients emerged as the major limiting factor of the invasion; a distinct zone below 619mm of mean annual rainfall was identified as the apparent boundary for the invasion. Low organic matter content identified under invaded areas was attributed to the patchy nature of the invader, leading to loss of the top soil in the bare inter-patch areas. The area covered by grass had consistently higher moisture values than P. incana and bare surfaces. The difference in post-rainfall moisture retention between grass and P. incana surfaces was significant up to about six days, after which a near parallel trend was noticed towards the ensuing rainfall episode. Whereas a higher amount of moisture was recorded on grass, the surface experienced moisture loss faster than the invaded and bare surfaces after each rainfall episode. ii There was consistency in multi-temporal Digital Number (DN) values for the surfaces investigated. The typically low P. incana reflectance in the Near Infrared band, identified from the multi-temporal HRI was validated by field and laboratory spectroscopy. The PVI showed clear spectral separability between all the land surfaces in the respective multi-temporal HRI. The consistence of the PVI with the unmixed surface image fractions from the SMA illustrates that using HRI, the effectiveness of the PVI is not impeded by the mixed pixel problem. Results of the laboratory spectroscopy that validated HRI analyses showed that P. incana’s typically low reflectance is a function of its leaf canopy, as higher proportions of leaves gave a higher reflectance. Future research directions could focus on comparisons between P. incana and typical green vegetation internal leaf structures as potential causes of spectral differences. Collection of spectra for P incana and other invader vegetation types, some of which have similar characteristics, with a view to assembling a spectral library for delineating invaded environments using imagery, is another research direction.
- Full Text:
- Date Issued: 2009
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
- 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
- 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
- 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
- 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
- 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
The separation of platinum and gold from an industrial feed solution
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
The solvent-free approach versus the use of ionic liquids in the synthesis of ferrocenes
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
- Authors: Elago, Elago R T
- Date: 2008
- Subjects: Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10396 , http://hdl.handle.net/10948/853 , Ferrocene , Inorganic compounds -- Synthesis , Ionic solutions , Solvents
- Description: The philosophy of green chemistry has seen much development in the past decade. The use of environmentally benign solvents is amongst the areas of green chemistry that have received the most attention. In this context, imidazolium ionic liquids have been widely reported to offer high product yields, fast reaction rates, excellent selectivity and generally mild working conditions, when used as reaction media. In addition, concerns about costs of solvents and the long-term environmental impact that can potentially result when solvents are discarded after their use have led to focused investigations into solvent-free procedures, as reported in recent literature. We have set out to explore the extent to which these advantages could be realized within our research. Non-volatile, non-flammable imidazolium ionic liquids [bmim][I], [bmim][BF4] and [bmim][PF6] were used as green solvents in ferrocene chemistry. Ferrocenoate esters were synthesised efficiently by the respective DCC/DMAP-promoted reactions of ferrocenecarboxylic acid and substituted benzoic acids or, alternatively, the DMAP-promoted reactions of ferrocenoyl fluoride with a range of substituted phenols in [bmim][BF4] and [bmim][PF6]. High yields and short reaction times were achieved. In addition, the ionic liquid was reused several times without a reduction in product yields. Under solvent-free conditions, DCC/DMAP-promoted reactions provided high yields within 3 min of reaction. The possible rearrangement of one of the intermediates in these reactions was modelled theoretically using density function theory (DFT) at the B3LYP/6-31G* level of approximation. Catalyst-free esterification was achieved by the application of microwave radiation to the reaction of ferrocenoyl fluoride and a range of substituted phenols. All the reactions were complete after 1 min of irradiation and products were isolated in high yield. DPAT, HfCl4, Sc(OTf)3 and Al(OTf)3 were screened as catalysts for esterification in [bmim][BF4] and under solvent-free conditions at various temperatures. All attempts at esterification of ferrocenecarboxylic acid with alcohols and phenols were unsuccessful. The Suzuki cross-coupling reaction was carried out in [bmim][BF4]. The isolated yields are, however, poor and suffer from poor reproducibility with different batches of [bmim][BF4] used.
- Full Text:
- Date Issued: 2008
Towards the bioremediation of the hypertrophic Swartkops Solar Salt-works
- Authors: Difford, Mark
- Date: 2008
- Subjects: Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10606 , http://hdl.handle.net/10948/1506 , Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Description: This thesis presents the results of three studies aimed at improving brine-quality at the Swartkops solar salt-works (Swartkops Sea Salt [Pty] Ltd) on the outskirts of Port Elizabeth, South Africa. This is a highly eutrophic salt-works, the management of which has become increasingly difficult in recent years. The fundamental problem is how best to operate the system at maximum capacity while limiting nutrient inputs from the nutrient-rich microtidal Swartkops Estuary. In the first study, brine-quality at several sites along the axis of the Swartkops Estuary, and the extent to which it is affected by a variety of factors, is compared. Sites were sampled on micro- and macrotidal time scales, and were selected by the management of the salt-works as possible locations for a new pump-house (for extracting brine from the estuary) for their salt-work operations at Swartkops and Missionvale. The study showed that there are incremental benefits to be had from moving the site of extraction downstream from its present position to a site closer to the mouth of the estuary, where the concentration of nutrients usually is lower and where salinity usually is higher. There is little to be gained from moving the site of extraction laterally, to the mouth of the Inlet from which brine currently is extracted, so that brine is extracted directly from the estuary itself. A set of models relating the concentrations of NH+ 4 , NO{u100000}3 , and PO34{u100000} to salinity is proposed. These take into account the influences of site and season and may be used to estimate the concentration of these nutrients from a measurement of salinity. The model for PO34{u100000} shows that it would be more damaging to the salt-works’ operations to pump “low”-salinity brine during the early months of summer than during autumn. Evidence is also presented to show that Wylde Bridge has no influence on nutrient concentrations in the estuary, with tidal flushing generally passing beyond the Wylde-Bridge break-point. The exceptionally heavy flooding of the estuary that occurred in September 2002 may, however, have biased this conclusion, because of its scouring effect. The second study concentrated on monitoring the effect of (1) decreasing pond depth and (2) increasing pond salinity—two readily available management tools—on brine quality at the salt-works. Pond depth throughout the salt-works was decreased by 40 cm, and the salinity of Pond 5, a pond in the middle of the system, was increased to 175 S. Both measures were kept in place for the duration of the study (Nov. 2002–Aug. 2004). The pond-depth experiment did not have the expected result, there being no evidence of the increase in microalgal growth in the water column that was predicted based on previous research. There was, however, a significant increase in benthic chlorophyll-a, and there was a general improvement in the condition of the sedimentary system of the salt-works. There was also a substantial decrease in particulate organic matter in the water column, with clear evidence that the remaining fraction was closely associated with living forms of particulate matter rather than with detritus. The pond-salinity experiment proves that there is a flourishing, and resilient, population of brine shrimp (Artemia salina L.) at the salt-works. Restocking the salina, or stocking it with a different strain of brine shrimp, is therefore not necessary. The results of this study show that the brine shrimp population at the salt-works needs salinities of greater than about 65–70 S to survive. As a living force they almost certainly need a protective salinity that is greater than about 120–140 S, perhaps even as great as 160 S. Brine shrimp thrived in the high salinity milieu of the experimental pond for the duration of the study, but dwindled from three other ponds of the system once their salinities fell to below 90 S, eventually to disappear from them, apparently completely, once salinity fell to below 65 S. The third and final study concentrated on establishing whether the products released by decomposing barley straw could be used in a solar salt-works to control macroalgal blooms without detrimentally affecting the benthic-mat. Previous research has shown that these products are effective inhibitors of macroalgal growth and that they remain effective under saline conditions. The results presented here show that the same products, or products released under similar conditions of decomposition, adversely effect both the structure and the function of the mat. Consequently, their use in a solar salt-works cannot be recommended.
- Full Text:
- Date Issued: 2008
- Authors: Difford, Mark
- Date: 2008
- Subjects: Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10606 , http://hdl.handle.net/10948/1506 , Salt industry and trade -- South Africa -- Port Elizabeth , Bioremediation
- Description: This thesis presents the results of three studies aimed at improving brine-quality at the Swartkops solar salt-works (Swartkops Sea Salt [Pty] Ltd) on the outskirts of Port Elizabeth, South Africa. This is a highly eutrophic salt-works, the management of which has become increasingly difficult in recent years. The fundamental problem is how best to operate the system at maximum capacity while limiting nutrient inputs from the nutrient-rich microtidal Swartkops Estuary. In the first study, brine-quality at several sites along the axis of the Swartkops Estuary, and the extent to which it is affected by a variety of factors, is compared. Sites were sampled on micro- and macrotidal time scales, and were selected by the management of the salt-works as possible locations for a new pump-house (for extracting brine from the estuary) for their salt-work operations at Swartkops and Missionvale. The study showed that there are incremental benefits to be had from moving the site of extraction downstream from its present position to a site closer to the mouth of the estuary, where the concentration of nutrients usually is lower and where salinity usually is higher. There is little to be gained from moving the site of extraction laterally, to the mouth of the Inlet from which brine currently is extracted, so that brine is extracted directly from the estuary itself. A set of models relating the concentrations of NH+ 4 , NO{u100000}3 , and PO34{u100000} to salinity is proposed. These take into account the influences of site and season and may be used to estimate the concentration of these nutrients from a measurement of salinity. The model for PO34{u100000} shows that it would be more damaging to the salt-works’ operations to pump “low”-salinity brine during the early months of summer than during autumn. Evidence is also presented to show that Wylde Bridge has no influence on nutrient concentrations in the estuary, with tidal flushing generally passing beyond the Wylde-Bridge break-point. The exceptionally heavy flooding of the estuary that occurred in September 2002 may, however, have biased this conclusion, because of its scouring effect. The second study concentrated on monitoring the effect of (1) decreasing pond depth and (2) increasing pond salinity—two readily available management tools—on brine quality at the salt-works. Pond depth throughout the salt-works was decreased by 40 cm, and the salinity of Pond 5, a pond in the middle of the system, was increased to 175 S. Both measures were kept in place for the duration of the study (Nov. 2002–Aug. 2004). The pond-depth experiment did not have the expected result, there being no evidence of the increase in microalgal growth in the water column that was predicted based on previous research. There was, however, a significant increase in benthic chlorophyll-a, and there was a general improvement in the condition of the sedimentary system of the salt-works. There was also a substantial decrease in particulate organic matter in the water column, with clear evidence that the remaining fraction was closely associated with living forms of particulate matter rather than with detritus. The pond-salinity experiment proves that there is a flourishing, and resilient, population of brine shrimp (Artemia salina L.) at the salt-works. Restocking the salina, or stocking it with a different strain of brine shrimp, is therefore not necessary. The results of this study show that the brine shrimp population at the salt-works needs salinities of greater than about 65–70 S to survive. As a living force they almost certainly need a protective salinity that is greater than about 120–140 S, perhaps even as great as 160 S. Brine shrimp thrived in the high salinity milieu of the experimental pond for the duration of the study, but dwindled from three other ponds of the system once their salinities fell to below 90 S, eventually to disappear from them, apparently completely, once salinity fell to below 65 S. The third and final study concentrated on establishing whether the products released by decomposing barley straw could be used in a solar salt-works to control macroalgal blooms without detrimentally affecting the benthic-mat. Previous research has shown that these products are effective inhibitors of macroalgal growth and that they remain effective under saline conditions. The results presented here show that the same products, or products released under similar conditions of decomposition, adversely effect both the structure and the function of the mat. Consequently, their use in a solar salt-works cannot be recommended.
- Full Text:
- Date Issued: 2008
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
- 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